Compact and efficient 2μm Tm:YAP lasers with mechanical or passive Q-switching

NASA Astrophysics Data System (ADS)

Cole, Brian; Goldberg, Lew

2017-02-01

We describe compact and efficient Q-switched diode-pumped, Tm:YAP lasers operating at 1.94μm. Laser CW and Q-switched performance is compared, using both compact mechanical as well as passive Q-switching. For passive Q-switching using a Cr:ZnS saturable absorber (unsaturated transmission of 95%), the laser produced 0.5mJ pulses with an average power of 4.4W and 6.5kW peak power, and had an optical efficiency of 30%. A resonant mirror mechanical Q-switch resulted in a 4 kHz PRF pulse train, with an optical slope efficiency of 52% and an optical-to-optical conversion efficiency of 41%. The laser generated 1.5 mJ, 45 ns FWHM, 33kW peak power pulses, and 6.2W of average output. A second mechanically Q-switched laser operating at 10 kHz PRF produced 1mJ, 35kW peak power pulses, generating 11W average power with an optical efficiency of 46%, and a beam quality of 1.4x diffraction limit.

Compact radio sources in luminous infrared galaxies

NASA Astrophysics Data System (ADS)

Parra, Rodrigo

2007-08-01

Radio interferometry is an observational technique of high sensitivity and incomparably high spatial resolution. Moreover, because radio waves can freely propagate through interstellar dust and gas, it allows the study of regions of the universe completely obscured at other wavelengths. This thesis reports the observational and theoretical results of my research during the past four years which are mostly based on interferometric radio data. The COLA sample is an infrared selected sample of active star forming galaxies. We conducted 6 cm VLA and VLBI snapshot observations of the northern half of this sample. The radio emission seen at VLA scales is consistent with being powered by star formation activity because it follows the far infrared to radio correlation. We detect 22% of the sample sources in our VLBI snapshots. Based on luminosity arguments, we argue that these sub-parsec VLBI sources are powered by AGN activity. Furthermore, we find that VLBI detections are preferentially found in sources whose VLA scale structures have the highest peak brightnesses suggesting a strong correlation between compact starburst and AGN activity. This observational result is consistent with the theoretical picture of an Eddington-limited nuclear starburst acting as the last valve in the pipeline transporting the gas from kiloparsec scales onto the accretion disc of a buried AGN. Arp 220 is the archetypical ultra luminous infrared galaxy. For many years this source has been known to harbour a compact (~100 pc) cluster of unresolved 18 cm bright sources believed to be bright core collapse supernovae. Using multiwavelength VLBI observations, we obtained for the first time radio spectra for 18 of these sources. We find that over a half of them have spectra consistent with young supernovae. The rest can be better explained as older supernova remnants interacting with the high density starburst ISM. This finding allowed us to constrain the number of possible scenarios for the Arp 220 starburst. A subset of luminous infrared galaxies contain non-thermal spectral line emission from the OH radical. These OH megamasers often show diffuse extended (~100 pc) low gain emission surrounding compact ([Special characters omitted. 1 pc) high gain maser spots. These observational features have been explained in terms of unsaturated and saturated masers. Using numerical simulations we have shown how both the diffuse and compact components of the OH megamaser observed towards the luminous infrared galaxy IIIZw35 can be explained by a single phase of unsaturated maser clouds in which the compact bright masers are caused by the random line-of-sight overlap of several such clouds and the diffuse component by the beam spatial average of many low gain clouds too weak to be seen independently. The theoretical tools developed to analyse this particular case have been extended to the general problem of propagation of radiation in clumpy media.

Mechano-Chemical Interactions at Cement-Geomaterial Interfaces in Repository and Borehole Scenarios

NASA Astrophysics Data System (ADS)

Mohagheghi, J. R.; Dewers, T. A.; Matteo, E. N.; Heath, J. E.; Jove Colon, C. F.; Fuller, T.

2017-12-01

A number of factors negatively affect wellbore integrity including interactions at boundaries between cement and surrounding geomaterial. These include mechanical and chemical mechanisms that can lead to wellbore failure. To examine these interactions, potential coupling, and pathways to failure, we discuss progress on an experimental and modeling study involving cement-clay and cement-salt interfaces. A sample shotcrete-bentonite interface from the FEBEX heater test at the Grimsel Test Site in Switzerland is examined using multi-beam scanning electron microscopy (mSEM) at 4 nm resolution over an area 10's of square millimeters. We examine changes in alteration as manifested by pore structural changes as a function of distance from the interface. A parallel effort examines time-dependent changes in interface structure in cement cores in a triaxial coreholder. Cores are exposed to conditions of 70oC, 14 MPa pressure, and small differential loads, with degradation being monitored by effluent pH, pulse-echo ultrasonics, and piston displacement (measuring sample shortening). We will measure the mechanical consequences of interface alteration using nano-indentation. Experimental results are being incorporated as a validation effort in a coupled reactive-transport mechanics model linking the Sandia ALBANY finite element code, the KAYENTA elasto-plastic constitutive model, with the reactive transport code PFLOTRAN. Plans call to apply the model to understanding the evolution of the FEBEX sample, as well as a cement-salt sample from the Waste Isolation Pilot Plant in Carlsbad, New Mexico. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. SAND 2017-8277 A

International Collaboration Activities on Engineered Barrier Systems

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

Jove-Colon, Carlos F.

The Used Fuel Disposition Campaign (UFDC) within the DOE Fuel Cycle Technologies (FCT) program has been engaging in international collaborations between repository R&D programs for high-level waste (HLW) disposal to leverage on gathered knowledge and laboratory/field data of near- and far-field processes from experiments at underground research laboratories (URL). Heater test experiments at URLs provide a unique opportunity to mimetically study the thermal effects of heat-generating nuclear waste in subsurface repository environments. Various configurations of these experiments have been carried out at various URLs according to the disposal design concepts of the hosting country repository program. The FEBEX (Full-scale Engineeredmore » Barrier Experiment in Crystalline Host Rock) project is a large-scale heater test experiment originated by the Spanish radioactive waste management agency (Empresa Nacional de Residuos Radiactivos S.A. – ENRESA) at the Grimsel Test Site (GTS) URL in Switzerland. The project was subsequently managed by CIEMAT. FEBEX-DP is a concerted effort of various international partners working on the evaluation of sensor data and characterization of samples obtained during the course of this field test and subsequent dismantling. The main purpose of these field-scale experiments is to evaluate feasibility for creation of an engineered barrier system (EBS) with a horizontal configuration according to the Spanish concept of deep geological disposal of high-level radioactive waste in crystalline rock. Another key aspect of this project is to improve the knowledge of coupled processes such as thermal-hydro-mechanical (THM) and thermal-hydro-chemical (THC) operating in the near-field environment. The focus of these is on model development and validation of predictions through model implementation in computational tools to simulate coupled THM and THC processes.« less

Water and tritium movement through the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Illinois, 1981-85

USGS Publications Warehouse

Mills, Patrick C.; Healy, Richard W.

1993-01-01

The movement of water and tritium through the unsaturated zone was studied at a low-level radioactive-waste disposal site near Sheffield, Bureau County, Illinois, from 1981 to 1985. Water and tritium movement occurred in an annual, seasonally timed cycle; recharge to the saturated zone generally occurred in the spring and early summer. Mean annual precipitation (1982-85) was 871 mm (millimeters); mean annual recharge to the disposal trenches (July 1982 through June 1984) was estimated to be 107 mm. Average annual tritium flux below the study trenches was estimated to be 3.4 mCi/yr (millicuries per year). Site geology, climate, and waste-disposal practices influenced the spatial and temporal variability of water and tritium movement. Of the components of the water budget, evapotranspiration contributed most to the temporal variability of water and tritium movement. Disposal trenches are constructed in complexly layered glacial and postglacial deposits that average 17 m (meters) in thickness and overlie a thick sequence of Pennsylvanian shale. The horizontal saturated hydraulic conductivity of the clayey-silt to sand-sized glacial and postglacial deposits ranges from 4.8x10 -1 to 3.4x10 4 mm/d (millimeters per day). A 120-m-long horizontal tunnel provided access for hydrologic measurements and collection of sediment and water samples from the unsaturated and saturated geologic deposits below four disposal trenches. Trench-cover and subtrench deposits were monitored with soil-moisture tensiometers, vacuum and gravity lysimeters, piezometers, and a nuclear soil-moisture gage. A cross-sectional, numerical ground-water-flow model was used to simulate water movement in the variably saturated geologic deposits in the tunnel area. Concurrent studies at the site provided water-budget data for estimating recharge to the disposal trenches. Vertical water movement directly above the trenches was impeded by a zone of compaction within the clayey-silt trench covers. Water entered the trenches primarily at the trench edges where the compacted zone was absent and the cover was relatively thin. Collapse holes in the trench covers that resulted from inadequate compaction of wastes within the trenches provided additional preferential pathways for surface-water drainage into the trenches; drainage into one collapse hole during a rainstorm was estimated to be 1,700 L (liters). Till deposits near trench bases induced lateral water and tritium movement. Limited temporal variation in water movement and small flow gradients (relative to the till deposits) were detected in the unsaturated subtrench sand deposit; maximum gradients during the spring recharge period averaged 1.62 mm/mm (millimeter per millimeter). Time-of-travel of water moving from the trench covers to below the trenches was estimated to be as rapid as 41 days (assuming individual water molecules move this distance in one recharge cycle). Tritium concentrations in water from the unsaturated zone ranged from 200 (background) to 10,000,000 pCi/L (picocuries per liter). Tritium concentrations generally were higher below trench bases (averaging 91,000 pCi/L) than below intertrench sediments (averaging 3,300 pCi/L), and in the subtrench Toulon Member of the Glasford Formation (sand) (averaging 110,000 pCi/L) than in the Hulick Till Member of the Glasford Formation (clayey silt) (averaging 59,000 pCi/L). Average subtrench tritium concentration increased from 28,000 to 100,000 pCi/L during the study period. Within the trench covers, there was a strong seasonal trend in tritium concentrations; the highest concentrations occurred in late summer when soil-moisture contents were at a minimum. Subtrench tritium movement occurred in association with the annual cycle of water movement, as well as independently of the cycle, in apparent response to continuous water movement through the subtrench sand deposits and to the deterioration of trench-waste containers. The increase in concen

Water and tritium movement through the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Illinois, 1981-85

USGS Publications Warehouse

Mills, Patrick C.; Healy, R.W.

1991-01-01

The movement of water and tritium through the unsaturated zone was studied at a low-level radioactive-waste disposal site near Sheffield, Bureau County, Illinois, from 1981 to 1985. Water and tritium movement occurred in an annual, seasonally timed cycle; recharge to the saturated zone generally occurred in the spring and early summer. Mean annual precipitation (1982-85) was 871 millimeters; mean annual recharge to the disposal trenches (July 1982 through June 1984) was estimated to be 107 millimeters. Average annual tritium flux below the study trenches was estimated to be 3.4 millicuries per year. Site geology, climate, and waste-disposal practices influenced the spatial and temporal variability of water and tritium movement. Of the components of the water budget, evapotranspiration contributed most to the temporal variability of water and tritium movement. Disposal trenches are constructed in complexly layered glacial and postglacial deposits that average 17 meters in thickness and overlie a thick sequence of Pennsylvanian shale. The horizontal saturated hydraulic conductivity of the clayey-silt to sand-sized glacial and postglacial deposits ranges from 4.8x10^-1 to 3.4x10^4 millimeters per day. A 120-meter-long horizontal tunnel provided access for hydrologic measurements and collection of sediment and water samples from the unsaturated and saturated geologic deposits below four disposal trenches. Trench-cover and subtrench deposits were monitored with soil-moisture tensiometers, vacuum and gravity lysimeters, piezometers, and a nuclear soil-moisture gage. A cross-sectional, numerical ground-water-flow model was used to simulate water movement in the variably saturated geologic deposits in the tunnel area. Concurrent studies at the site provided water-budget data for estimating recharge to the disposal trenches. Vertical water movement directly above the trenches was impeded by a zone of compaction within the clayey-silt trench covers. Water entered the trenches primarily at the trench edges where the compacted zone was absent and the cover was relatively thin. Collapse holes in the trench covers that resulted from inadequate compaction of wastes within the trenches provided additional preferential pathways for surface-water drainage into the trenches; drainage into one collapse hole during a rainstorm was estimated to be 1,700 liters. Till deposits near trench bases induced lateral water and tritium movement. Limited temporal variation in water movement and small flow gradients (relative to the till deposits) were detected in the unsaturated subtrench sand deposit; maximum gradients during the spring recharge period averaged 1.62 millimeters per millimeter. Time-of-travel of water moving from the trench covers to below the trenches was estimated to be as rapid as 41 days (assuming individual water molecules move this distance in one recharge cycle). Tritium concentrations in water from the unsaturated zone ranged from 200 (background) to 10,000,000 pCi/L (picocuries per liter). Tritium concentrations generally were higher below trench bases (averaging 91,000 pCi/L) than below intertrench sediments (averaging 3,300 pCi/L), and in the subtrench Toulon Member of the Glasford Formation (sand) (averaging 110,000 pCi/L) than in the Hulick Till Member of the Glasford Formation (clayey silt) (averaging 59,000 pCi/L). Average subtrench tritium concentration increased from 28,000 to 100,000 pCi/L during the study period. Within the trench covers, there was a strong seasonal trend in tritium concentrations; the highest concentrations occurred in late summer when soil-moisture contents were at a minimum. Subtrench tritium movement occurred in association with the annual cycle of water movement, as well as independently of the cycle, in apparent response to continuous water movement through the subtrench sand deposits and to the deterioration of trench-waste containers. The increase in concentrations of tritium with incre

Air and groundwater flow at the interface between fractured host rock and a bentonite buffer

NASA Astrophysics Data System (ADS)

Dessirier, B.; Jarsjo, J.; Frampton, A.

2014-12-01

Designs of deep geological repositories for spent nuclear fuel include several levels of confinement. The Swedish and Finnish concept KBS-3 targets for example sparsely fractured crystalline bedrock as host formation and would have the waste canisters embedded in an engineered buffer of compacted MX-80 bentonite. The host rock is a highly heterogeneous dual porosity material containing fractures and a rock matrix. Bentonite is a complex expansive porous material. Its water content and mechanical properties are interdependent. Beyond the specific physics of unsaturated flow and transport in each medium, the interface between them is critical. Detailed knowledge of the transitory two-phase flow regime, induced by the insertion of the unsaturated buffer in a saturated rock environment, is necessary to assess the performance of planned KBS-3 deposition holes. A set of numerical simulations based on the equations of two-phase flow for water and air in porous media were conducted to investigate the dynamics of air and groundwater flow near the rock/bentonite interface in the period following installation of the unsaturated bentonite buffer. We assume state of the two-phase flow parameter values for bentonite from laboratory water uptake tests and typical fracture and rock properties from the Äspö Hard rock laboratory (Sweden) gathered under several field characterization campaigns. The results point to desaturation of the rock domain as far as 10 cm away from the interface into matrix-dominated regions for up to 160 days. Similar observations were made during the Bentonite Rock Interaction Experiment (BRIE) at the Äspö HRL, with a desaturation sustained for even longer times. More than the mere time to mechanical and hydraulic equilibrium, the occurrence of sustained unsaturated conditions opens the possibility for biogeochemical processes that could be critical in the safety assessment of the planned repository.

Transient Point Infiltration In The Unsaturated Zone

NASA Astrophysics Data System (ADS)

Buecker-Gittel, M.; Mohrlok, U.

The risk assessment of leaking sewer pipes gets more and more important due to urban groundwater management and environmental as well as health safety. This requires the quantification and balancing of transport and transformation processes based on the water flow in the unsaturated zone. The water flow from a single sewer leakage could be described as a point infiltration with time varying hydraulic conditions externally and internally. External variations are caused by the discharge in the sewer pipe as well as the state of the leakage itself. Internal variations are the results of microbiological clogging effects associated with the transformation processes. Technical as well as small scale laboratory experiments were conducted in order to investigate the water transport from an transient point infiltration. From the technical scale experiment there was evidence that the water flow takes place under transient conditions when sewage infiltrates into an unsaturated soil. Whereas the small scale experiments investigated the hydraulics of the water transport and the associated so- lute and particle transport in unsaturated soils in detail. The small scale experiment was a two-dimensional representation of such a point infiltration source where the distributed water transport could be measured by several tensiometers in the soil as well as by a selective measurement of the discharge at the bottom of the experimental setup. Several series of experiments were conducted varying the boundary and initial con- ditions in order to derive the important parameters controlling the infiltration of pure water from the point source. The results showed that there is a significant difference between the infiltration rate in the point source and the discharge rate at the bottom, that could be explained by storage processes due to an outflow resistance at the bottom. This effect is overlayn by a decreasing water content decreases over time correlated with a decreasing infiltration rate. As expected the initial conditions mainly affects the time scale for the water transport. Additionally, the influence of preferential flow paths on the discharge distribution could be found due to the heterogenieties caused by the filling and compaction process of the sandy soil.

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.

Anisotropic capillary barrier for waste site surface covers

DOEpatents

Stormont, J.C.

1996-08-27

Waste sites are capped or covered upon closure. The cover structure incorporates a number of different layers each having a contributory function. One such layer is the barrier layer. Traditionally the barriers have been compacted soil and geosynthetics. These types of barriers have not been successfully implemented in unsaturated ground conditions like those found in dry climates. Capillary barriers have been proposed as barrier layers in dry environments, but the divergence length of these barriers has been found to be inadequate. An alternative to the capillary barrier is a anisotropic capillary barrier. An anisotropic capillary barrier has an increased divergence length which results in more water being diverted laterally preventing the majority of water from percolating in a downward direction through the barrier. 10 figs.

Anisotropic capillary barrier for waste site surface covers

DOEpatents

Stormont, John C.

1996-01-01

Waste sites are capped or covered upon closure. The cover structure incorporates a number of different layers each having a contributory function. One such layer is the barrier layer. Traditionally the barriers have been compacted soil and geosynthetics. These types of barriers have not been successfully implemented in unsaturated ground conditions like those found in dry climates. Capillary barriers have been proposed as barrier layers in dry environments, but the divergence length of these barriers has been found to be inadequate. An alternative to the capillary barrier is a anisotropic capillary barrier. An anisotropic capillary barrier has an increased divergence length which results in more water being diverted laterally preventing the majority of water from percolating in a downward direction through the barrier.

Water Drainage from Unsaturated Soils in a Centrifuge Permeameter

NASA Astrophysics Data System (ADS)

Ornelas, G.; McCartney, J.; Zhang, M.

2013-12-01

This study involves an analysis of water drainage from an initially saturated silt layer in a centrifuge permeameter to evaluate the hydraulic properties of the soil layer in unsaturated conditions up to the point where the water phase becomes discontinuous. These properties include the soil water retention curve (SWRC) and the hydraulic conductivity function (HCF). The hydraulic properties of unsaturated silt are used in soil-atmosphere interaction models that take into account the role of infiltration and evaporation of water from soils due to atmospheric interaction. These models are often applied in slope stability analyses, landfill cover design, aquifer recharge analyses, and agricultural engineering. The hydraulic properties are also relevant to recent research concerning geothermal heating and cooling, as they can be used to assess the insulating effects of soil around underground heat exchangers. This study employs a high-speed geotechnical centrifuge to increase the self-weight of a compacted silt specimen atop a filter plate. Under a centrifuge acceleration of N times earth's gravity, the concept of geometric similitude indicates that the water flow process in a small-scale soil layer will be similar to those in a soil layer in the field that is N times thicker. The centrifuge acceleration also results in an increase in the hydraulic gradient across the silt specimen, which causes water to flow out of the pores following Darcy's law. The drainage test was performed until the rate of liquid water flow out of the soil layer slowed to a negligible level, which corresponds to the transition point at which further water flow can only occur due to water vapor diffusion following Fick's law. The data from the drainage test in the centrifuge were used to determine the SWRC and HCF at different depths in the silt specimen, which compared well with similar properties defined using other laboratory tests. The transition point at which liquid water flow stopped (and Darcy's law is no longer valid) was at a relatively high degree of saturation of 0.8. This finding is important as many water flow analyses in the literature assume that Darcy's law is valid over a much wider range of degrees of saturation, an error that potentially may lead to overestimates of water flow in unsaturated soil layers.

Competition between reaction-induced expansion and creep compaction during gypsum formation: Experimental and numerical investigation

NASA Astrophysics Data System (ADS)

Skarbek, R. M.; Savage, H. M.; Spiegelman, M. W.; Kelemen, P. B.; Yancopoulos, D.

2017-12-01

Deformation and cracking caused by reaction-driven volume increase is an important process in many geological settings, however the conditions controlling these processes are poorly understood. The interaction of rocks with reactive fluids can change permeability and reactive surface area, leading to a large variety of feedbacks. Gypsum is an ideal material to study these processes. It forms rapidly at room temperature via bassanite hydration, and is commonly used as an analogue for rocks in high-temperature, high-pressure conditions. We conducted uniaxial strain experiments to study the effects of applied axial load on deformation and fluid flow during the formation of gypsum from bassanite. While hydration of bassanite to gypsum involves a solid volume increase, gypsum exhibits significant creep compaction when in contact with water. These two volume changing processes occur simultaneously during fluid flow through bassanite. We cold-pressed bassanite powder to form cylinders 2.5 cm in height and 1.2 cm in diameter. Samples were compressed with a static axial load of 0.01 to 4 MPa. Water infiltrated initially unsaturated samples through the bottom face and the height of the samples was recorded as a measure of the total volume change. We also performed experiments on pure gypsum samples to constrain the amount of creep observed in tests on bassanite hydration. At axial loads < 0.15 MPa, volume increase due to the reaction dominates and samples exhibit monotonic expansion. At loads > 1 MPa, creep in the gypsum dominates and samples exhibit monotonic compaction. At intermediate loads, samples exhibit alternating phases of compaction and expansion due to the interplay of the two volume changing processes. We observed a change from net compaction to net expansion at an axial load of 0.250 MPa. We explain this behavior with a simple model that predicts the strain evolution, but does not take fluid flow into account. We also implement a 1D poro-visco-elastic model of the imbibition process that includes the reaction and gypsum creep. We use the results of these models, with models of the creep rate in gypsum, to estimate the temperature dependence of the axial load where total strain transitions from compaction to expansion. Our results have implications for the depth dependence of reaction induced volume changes in the Earth.

Hydraulic conductivity of a sandy soil at low water content after compaction by various methods

USGS Publications Warehouse

Nimmo, John R.; Akstin, Katherine C.

1988-01-01

To investigate the degree to which compaction of a sandy soil influences its unsaturated hydraulic conductivity K, samples of Oakley sand (now in the Delhi series; mixed, thermic, Typic Xeropsamments) were packed to various densities and K was measured by the steady-state centrifuge method. The air-dry, machine packing was followed by centrifugal compression with the soil wet to about one-third saturation. Variations in (i) the impact frequency and (ii) the impact force during packing, and (iii) the amount of centrifugal force applied after packing, produced a range of porosity from 0.333 to 0.380. With volumetric water content θ between 0.06 and 0.12, K values were between 7 × 10−11 and 2 × 10−8 m/s. Comparisons of K at a single θ value for samples differing in porosity by about 3% showed as much as fivefold variation for samples prepared by different packing procedures, while there generally was negligible variation (within experimental error of 8%) where the porosity difference resulted from a difference in centrifugal force. Analysis involving capillary-theory models suggests that the differences in K can be related to differences in pore-space geometry inferred from water retention curves measured for the various samples.

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.

Quantitative chemical imaging with background-free multiplex coherent anti-Stokes Raman scattering by dual-soliton Stokes pulses

PubMed Central

Chen, Kun; Wu, Tao; Wei, Haoyun; Zhou, Tian; Li, Yan

2016-01-01

Coherent anti-Stokes Raman microscopy (CARS) is a quantitative, chemically specific, and label-free optical imaging technique for studying inhomogeneous systems. However, the complicating influence of the nonresonant response on the CARS signal severely limits its sensitivity and specificity and especially limits the extent to which CARS microscopy has been used as a fully quantitative imaging technique. On the basis of spectral focusing mechanism, we establish a dual-soliton Stokes based CARS microspectroscopy and microscopy scheme capable of quantifying the spatial information of densities and chemical composition within inhomogeneous samples, using a single fiber laser. Dual-soliton Stokes scheme not only removes the nonresonant background but also allows robust acquisition of multiple characteristic vibrational frequencies. This all-fiber based laser source can cover the entire fingerprint (800-2200 cm−1) region with a spectral resolution of 15 cm−1. We demonstrate that quantitative degree determination of lipid-chain unsaturation in the fatty acids mixture can be achieved by the characterization of C = C stretching and CH2 deformation vibrations. For microscopy purposes, we show that the spatially inhomogeneous distribution of lipid droplets can be further quantitatively visualized using this quantified degree of lipid unsaturation in the acyl chain for contrast in the hyperspectral CARS images. The combination of compact excitation source and background-free capability to facilitate extraction of quantitative composition information with multiplex spectral peaks will enable wider applications of quantitative chemical imaging in studying biological and material systems. PMID:27867704

Measurement of the open porosity of agricultural soils with acoustic waves

NASA Astrophysics Data System (ADS)

Luong, Jeanne; Mercatoris, Benoit; Destain, Marie-France

2015-04-01

The space between agricultural soil aggregates is defined as structural porosity. It plays important roles in soil key functions that an agricultural soil performs in the global ecosystem. Porosity is one of the soil properties that affect plant growth along with soil texture, aggregate size, aeration and water holding capacity (Alaoui et al. 2011). Water supplies regulation of agricultural soil is related to the number of very small pores present in a soil due to the effect of capillarity. Change of porosity also affect the evaporation of the water on the surface (Le Maitre et al. 2014). Furthermore, soil is a habitat for soils organisms, and most living organisms, including plant roots and microorganisms require oxygen. These organisms breathe easier in a less compacted soil with a wide range of pores sizes. Soil compaction by agricultural engine degrades soil porosity. At the same time, fragmentation with tillage tools, creation of cracks due to wetting/drying and freezing/thawing cycles and effects of soil fauna can regenerate soil porosity. Soil compaction increases bulk density since soil grains are rearranged decreasing void space and bringing them into closer contact (Hamza & Anderson 2005). Drainage is reduced, erosion is facilitated and crop production decreases in a compacted soil. Determining soil porosity, giving insight on the soil compaction, with the aim to provide advices to farmers in their soil optimization towards crop production, is thus an important challenge. Acoustic wave velocity has been correlated to the porosity and the acoustic attenuation to the water content (Oelze et al. 2002). Recent studies have shown some correlations between the velocity of acoustic waves, the porosity and the stress state of soil samples (Lu et al. 2004; Lu 2005; Lu & Sabatier 2009), concluding that the ultrasonic waves are a promising tool for the rapid characterisation of unsaturated porous soils. Propagation wave velocity tends to decrease in a high porous soil, since there are more voids filled with air and water, increasing the viscous losses. Fellah et al. (2003) showed that porosity can be determined from phase speed and reflection coefficient. The propagation of acoustic waves in soil is investigated to develop a rapid method for the quantification of the porosity level of agricultural soils. In the present contribution, correlations are determined between the acoustic signatures of agricultural soil in function of its structural properties. In laboratory, compression tests are performed on unsaturated soil samples to reproduce different porosity levels. Ultrasonic pulses are sent through the considered samples. The propagated signals are treated in both time and frequency domains in order to determine the speed of the phase velocity and the reflection. Porosity is then determined and compared with water content measured by gravimetric method. Alaoui, A., Lipiec, J. & Gerke, H.H., 2011. A review of the changes in the soil pore system due to soil deformation: A hydrodynamic perspective. Soil and Tillage Research, 115-116, pp.1-15. Fellah Z.E.A., Berger S., Lauriks W., Depollier C., Aristegui C., Chapelon J.Y., 2003. Measuring the porosity and the tortuosity of porous materials via reflected waves at oblique incidence. The Journal of the Acoustical Society of America 113 (5), pp 2424-2433 Hamza, M.A. & Anderson, W.K., 2005. Soil compaction in cropping systems. Soil and Tillage Research, 82(2), pp.121-145. Lu, Z., 2005. Role of hysteresis in propagating acousitcs waves in soils. Geophysical Research Letter, pp.32:1-4. Lu, Z., Hickey, C.J. & Sabatier, J.M., 2004. Effects of compaction on the acoustic velocity in soils. Soil Science Society of America Journal, 68(1), pp.7-16. Lu, Z. & Sabatier, J.M., 2009. Effects of soil water potential and moisture content on sound speed. Soil Science Society of America Journal, 73(5), pp.1614-1625. Le Maitre, D.C., Kotzee, I.M. & O'Farrell, P.J., 2014. Impacts of land-cover change on the water flow regulation ecosystem service: Invasive alien plants, fire and their policy implications. Land Use Policy, 36, pp.171-181. Oelze, M.L., O'Briena, W.D. & Darmody, R.G., 2002. Measurement of attenuation and speed of sound in soils. Soil. Sci. Soc. Am. J.

Understanding the THMC evolution of bentonite barrier — modeling an in situ test for bentonite backfilled engineered barrier system

NASA Astrophysics Data System (ADS)

Zheng, L.; Xu, H.; Rutqvist, J.; Birkholzer, J. T.

2016-12-01

The most common buffer material for engineered barrier system (EBS) is compacted bentonite, which features low permeability and high retardation of radionuclide transport. The safety functions of EBS bentonite include limiting transport in the near field; damping the shear movement of the host rock; preventing the sinking of canisters, limiting pressure on the canister and rock, and reducing microbial activity. To assess whether EBS bentonite can maintain these favorable features when undergoing heating from the waste package and hydration from the host rock, we need a thorough understanding of the thermal, hydrological, mechanical, and chemical evolution of bentonite under disposal conditions. The FEBEX (Full-scale Engineered Barrier EXperiment) in situ test was dismantled after 18 years' heating and hydration. The comprehensive THMC data obtained in the test provide a unique opportunity to validate coupled THMC models and deepen our understanding of the THMC evolution in bentonite. In this presentation, coupled THMC models were developed for the in situ test. Water content data obtained after dismantling and relative humidity data measured real time showed that the hydration of bentonite is slower than predicted by the typical Darcy flow model. Including Non-Darcian flow into the model however leads a significant underestimation of the relative humidity data. The reason could be that the calibration of relative permeability (and retention curve) already encompasses the nonlinear relationship between gradient and flux for bentonite, which would obviate the consideration of Non-Darcian flow in the model. THMC models that take into account the porosity and permeability changes due to mechanical processes match reasonably well all the THM data. However, they did not provide a desirable fit of the measured Cl concentration profile, further calibration of porosity/permeability changes over the course of hydration and swelling and considering thermal osmosis eventually lead to a model that sufficiently explain all the THMC data. Model results also showed that transport processes, i.e. advection and diffusion, control the concentration profile of conservative species (Cl for example) and play a major role in shaping the profile of most reactive species except pH and bicarbonate.

Implementation of Controlled Traffic in the Canadian Prairies: Soil and Plant Dynamics under Simulated and Field Conditions

NASA Astrophysics Data System (ADS)

Guenette, Kris; Hernandez-Ramirez, Guillermo

2017-04-01

Achieving resiliency in agroecosystems may be accomplished through the incorporation of contemporary management systems and the diversification of crop rotations with pulse crops, such as controlled traffic farming (CTF) and faba beans (Vicia faba L.). As these practices become more common in the Canadian Prairies, it is imperative to have a well-rounded understanding of how faba beans interact with the soil-plant-atmosphere continuum in conditions found in contemporary management systems. Simulated field conditions emulated soil compaction found in both the trafficked and un-trafficked areas of a CTF system, in which the presence of high water availability was shown to offset the negative results of large applications of compactive effort. Furthermore, low water availability exacerbated differences in plant responses between compaction treatments. The simulated treatment of 1.2 gcm-3 coupled with high water content yielded the most optimal results for most measured parameters, with a contrasting detrimental treatment of 1.4 gcm-3 at low water availability. The simulated field conditions were further bridged through an analysis of two commercial sites in Alberta, Canada that compared both trafficked and un-trafficked soil properties. Soil properties such as available nitrogen (AN), pH, soil total nitrogen (STN), soil organic carbon (SOC), bulk density, macroporosity, soil quality S-Index, plant available water capacity (PAWC) and unsaturated hydraulic conductivity (Km) were analysed and compared among trafficked and un-trafficked areas. The measured soil physical and hydraulic properties of bulk density, macroporosity, S-Index, PAWC and Km were shown to be heavily influenced by the CTF traffic regime, while soil nutrient properties of AN, pH, STN SOC were determined to be dependent on both management and landscape features.

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.

A new kind of low-inductance transformer type magnetic switch (TTMS) with coaxial cylindrical conductors

NASA Astrophysics Data System (ADS)

Zhang, Yu; Liu, Jinliang

2013-02-01

As important devices for voltage boosting and switching, respectively, pulse transformer and magnetic switch are widely used in pulsed power technology. In this paper, a new kind of transformer type magnetic switch (TTMS) with coaxial cylindrical conductors is put forward to combine the functions of voltage boosting and switching in one power device. As a compact combination device of discrete pulse transformer and magnetic switch, the compact TTMS decreases the required volume of magnetic cores in a large scale. The primary windings of the TTMS have a parallel combination structure so that the TTMS which only has 3 turns of secondary windings has a step-up ratio at 1:9. Before the magnetic core saturates, the TTMS has low unsaturated inductances of windings and good pulse response characteristics, so it can be used to substitute the Marx generator to charge the pulse forming line (PFL) at the ranges of several hundred kV and several hundred ns. After the core saturates, the cylindrical conductors can decrease the saturated inductance of the secondary windings of TTMS to a level less than 400 nH. As a result, the proposed TTMS can be used as the boosting transformer and main switch of helical Blumlein PFL to form the quasi-square voltage pulse on the 160 Ω load with a short pulse rise time only at 60 ns.

A new kind of low-inductance transformer type magnetic switch (TTMS) with coaxial cylindrical conductors.

PubMed

Zhang, Yu; Liu, Jinliang

2013-02-01

As important devices for voltage boosting and switching, respectively, pulse transformer and magnetic switch are widely used in pulsed power technology. In this paper, a new kind of transformer type magnetic switch (TTMS) with coaxial cylindrical conductors is put forward to combine the functions of voltage boosting and switching in one power device. As a compact combination device of discrete pulse transformer and magnetic switch, the compact TTMS decreases the required volume of magnetic cores in a large scale. The primary windings of the TTMS have a parallel combination structure so that the TTMS which only has 3 turns of secondary windings has a step-up ratio at 1:9. Before the magnetic core saturates, the TTMS has low unsaturated inductances of windings and good pulse response characteristics, so it can be used to substitute the Marx generator to charge the pulse forming line (PFL) at the ranges of several hundred kV and several hundred ns. After the core saturates, the cylindrical conductors can decrease the saturated inductance of the secondary windings of TTMS to a level less than 400 nH. As a result, the proposed TTMS can be used as the boosting transformer and main switch of helical Blumlein PFL to form the quasi-square voltage pulse on the 160 Ω load with a short pulse rise time only at 60 ns.

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

Considerations on sample holder design and custom-made non-polarizable electrodes for Spectral Induced Polarization measurements on unsaturated soils

NASA Astrophysics Data System (ADS)

Kaouane, C.; Chouteau, M. C.; Fauchard, C.; Cote, P.

2014-12-01

Spectral Induced Polarization (SIP) is a geophysical method sensitive to water content, saturation and grain size distribution. It could be used as an alternative to nuclear probes to assess the compaction of soils in road works. To evaluate the potential of SIP as a practical tool, we designed an experiment for complex conductivity measurements on unsaturated soil samples.Literature presents a large variety of sample holders and designs, each depending on the context. Although we might find some precise description about the sample holder, exact replication is not always possible. Furthermore, the potential measurements are often done using custom-made Ag/AgCl electrodes and very few indications are given on their reliability with time and temperature. Our objective is to perform complex conductivity measurements on soil samples compacted in a PVC cylindrical mould (10 cm-long, 5 cm-diameter) according to geotechnical standards. To expect homogeneous current density, electrical current is transmitted through the sample via chambers filled with agar gel. Agar gel is a good non-polarizable conductor within the frequency range (1 mHz -20kHz). Its electrical properties are slightly known. We measured increasing of agar-agar electrical conductivity in time. We modelled the influence of this variation on the measurement. If the electrodes are located on the sample, it is minimized. Because of the dimensions at stake and the need for simple design, potential electrodes are located outside the sample, hence the gel contributes to the measurements. Since the gel is fairly conductive, we expect to overestimate the sample conductivity. Potential electrodes are non-polarizable Ag/AgCl electrodes. To avoid any leakage, the KCl solution in the electrodes is replaced by saturated KCl-agar gel. These electrodes are low cost and show a low, stable, self-potential (<1mV). In addition, the technique of making electrode can be easily reproduced and storage and maintenance are simple. We measured a variation of less than 1 mS/m of the electrolyte conductivity during the time of measurement (~1h40) for a conductivity range 25-100 mS/m, showing no ionic contamination of the solution by the electrodes. An improvement to the cell design would be to control the internal temperature of the sample.

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.

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.

Modeling early in situ wetting of a compacted bentonite buffer installed in low permeable crystalline bedrock

NASA Astrophysics Data System (ADS)

Dessirier, B.; Frampton, A.; Fransson, À.; Jarsjö, J.

2016-08-01

The repository concept for geological disposal of spent nuclear fuel in Sweden and Finland is planned to be constructed in sparsely fractured crystalline bedrock and with an engineered bentonite buffer to embed the waste canisters. An important stage in such a deep repository is the postclosure phase following the deposition and the backfilling operations when the initially unsaturated buffer material gets hydrated by the groundwater delivered by the natural bedrock. We use numerical simulations to interpret observations on buffer wetting gathered during an in situ campaign, the Bentonite Rock Interaction Experiment, in which unsaturated bentonite columns were introduced into deposition holes in the floor of a 417 m deep tunnel at the Äspö Hard Rock Laboratory in Sweden. Our objectives are to assess the performance of state-of-the-art flow models in reproducing the buffer wetting process and to investigate to which extent dependable predictions of buffer wetting times and saturation patterns can be made based on information collected prior to buffer insertion. This would be important for preventing insertion into unsuitable bedrock environments. Field data and modeling results indicate the development of a de-saturated zone in the rock and show that in most cases, the presence or absence of fractures and flow heterogeneity are more important factors for correct wetting predictions than the total inflow. For instance, for an equal open-hole inflow value, homogeneous inflow yields much more rapid buffer wetting than cases where fractures are represented explicitly thus creating heterogeneous inflow distributions.

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.

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.

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

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.

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.

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...

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...

Natural (Mineral, Vegetable, Coconut, Essential) Oils and Contact Dermatitis.

PubMed

Verallo-Rowell, Vermén M; Katalbas, Stephanie S; Pangasinan, Julia P

2016-07-01

Natural oils include mineral oil with emollient, occlusive, and humectant properties and the plant-derived essential, coconut, and other vegetable oils, composed of triglycerides that microbiota lipases hydrolyze into glycerin, a potent humectant, and fatty acids (FAs) with varying physico-chemical properties. Unsaturated FAs have high linoleic acid used for synthesis of ceramide-I linoleate, a barrier lipid, but more pro-inflammatory omega-6:-3 ratios above 10:1, and their double bonds form less occlusive palisades. VCO FAs have a low linoleic acid content but shorter and saturated FAs that form a more compact palisade, more anti-inflammatory omega-6:-3 ratio of 2:1, close to 7:1 of olive oil, which disrupts the skin barrier, otherwise useful as a penetration enhancer. Updates on the stratum corneum illustrate how this review on the contrasting actions of NOs provide information on which to avoid and which to select for barrier repair and to lower inflammation in contact dermatitis genesis.

Implementation of a physically based water percolation routine in the Crocus/SURFEX (V7.3) snowpack model

NASA Astrophysics Data System (ADS)

D'Amboise, Christopher J. L.; Müller, Karsten; Oxarango, Laurent; Morin, Samuel; Schuler, Thomas V.

2017-09-01

We present a new water percolation routine added to the one-dimensional snowpack model Crocus as an alternative to the empirical bucket routine. This routine solves the Richards equation, which describes flow of water through unsaturated porous snow governed by capillary suction, gravity and hydraulic conductivity of the snow layers. We tested the Richards routine on two data sets, one recorded from an automatic weather station over the winter of 2013-2014 at Filefjell, Norway, and the other an idealized synthetic data set. Model results using the Richards routine generally lead to higher water contents in the snow layers. Snow layers often reached a point at which the ice crystals' surface area is completely covered by a thin film of water (the transition between pendular and funicular regimes), at which feedback from the snow metamorphism and compaction routines are expected to be nonlinear. With the synthetic simulation 18 % of snow layers obtained a saturation of > 10 % and 0.57 % of layers reached saturation of > 15 %. The Richards routine had a maximum liquid water content of 173.6 kg m-3 whereas the bucket routine had a maximum of 42.1 kg m-3. We found that wet-snow processes, such as wet-snow metamorphism and wet-snow compaction rates, are not accurately represented at higher water contents. These routines feed back on the Richards routines, which rely heavily on grain size and snow density. The parameter sets for the water retention curve and hydraulic conductivity of snow layers, which are used in the Richards routine, do not represent all the snow types that can be found in a natural snowpack. We show that the new routine has been implemented in the Crocus model, but due to feedback amplification and parameter uncertainties, meaningful applicability is limited. Updating or adapting other routines in Crocus, specifically the snow compaction routine and the grain metamorphism routine, is needed before Crocus can accurately simulate the snowpack using the Richards routine.

Mechanics of rainfall-induced flow failure in unsaturated shallow slopes (Invited)

NASA Astrophysics Data System (ADS)

Buscarnera, G.

2013-12-01

The increase in pore water pressure due to rain infiltration can be a dominant component in the activation of slope instabilities. This work shows an application of the theory of material stability to the triggering analysis of this important class of natural hazards. The goal is to identify the mechanisms through which the process of rain infiltration promotes instabilities of the flow-type in the soil covers. The interplay between increase in pore water pressure and failure mechanisms is investigated at material point level. To account for multiple failure mechanisms, the second-order energy input is linked to the controllability theory and used to define different types of stability indices, each associated with a specific mode of slope failure. It is shown that the theory can be used to assess both shear failure and static liquefaction in saturated and unsaturated soil covers. In particular, it is shown that these instability modes are regulated by the hydro-mechanical characteristics of the soil covers, as well as by their mutual coupling. This finding discloses the importance of the constitutive functions that simulate the interaction between the response of the solid skeleton and the fluid-retention characteristics of the soil. As a consequence, they suggest that even material properties that are not be to directly associated with the shearing resistance (e.g., the potential for wetting compaction) may play a role in the initiation of catastrophic slope failures. According to the proposed interpretation, the process of pore pressure increase can be seen as the trigger of uncontrolled strains, which can anticipate the onset of frictional failure and promote a solid-to-fluid transition.

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

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...

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).

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.

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.

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...

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.

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.

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.

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

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.

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.

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

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.

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.

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.

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.

Trans-Fats Inhibit Autophagy Induced by Saturated Fatty Acids.

PubMed

Sauvat, Allan; Chen, Guo; Müller, Kevin; Tong, Mingming; Aprahamian, Fanny; Durand, Sylvère; Cerrato, Giulia; Bezu, Lucillia; Leduc, Marion; Franz, Joakim; Rockenfeller, Patrick; Sadoshima, Junichi; Madeo, Frank; Kepp, Oliver; Kroemer, Guido

2018-04-01

Depending on the length of their carbon backbone and their saturation status, natural fatty acids have rather distinct biological effects. Thus, longevity of model organisms is increased by extra supply of the most abundant natural cis-unsaturated fatty acid, oleic acid, but not by that of the most abundant saturated fatty acid, palmitic acid. Here, we systematically compared the capacity of different saturated, cis-unsaturated and alien (industrial or ruminant) trans-unsaturated fatty acids to provoke cellular stress in vitro, on cultured human cells expressing a battery of distinct biosensors that detect signs of autophagy, Golgi stress and the unfolded protein response. In contrast to cis-unsaturated fatty acids, trans-unsaturated fatty acids failed to stimulate signs of autophagy including the formation of GFP-LC3B-positive puncta, production of phosphatidylinositol-3-phosphate, and activation of the transcription factor TFEB. When combined effects were assessed, several trans-unsaturated fatty acids including elaidic acid (the trans-isomer of oleate), linoelaidic acid, trans-vaccenic acid and palmitelaidic acid, were highly efficient in suppressing autophagy and endoplasmic reticulum stress induced by palmitic, but not by oleic acid. Elaidic acid also inhibited autophagy induction by palmitic acid in vivo, in mouse livers and hearts. We conclude that the well-established, though mechanistically enigmatic toxicity of trans-unsaturated fatty acids may reside in their capacity to abolish cytoprotective stress responses induced by saturated fatty acids. Copyright © 2018 German Center for Neurodegenerative Diseases (DZNE). Published by Elsevier B.V. All rights reserved.

A simple method to assess unsaturated zone time lag in the travel time from ground surface to receptor.

PubMed

Sousa, Marcelo R; Jones, Jon P; Frind, Emil O; Rudolph, David L

2013-01-01

In contaminant travel from ground surface to groundwater receptors, the time taken in travelling through the unsaturated zone is known as the unsaturated zone time lag. Depending on the situation, this time lag may or may not be significant within the context of the overall problem. A method is presented for assessing the importance of the unsaturated zone in the travel time from source to receptor in terms of estimates of both the absolute and the relative advective times. A choice of different techniques for both unsaturated and saturated travel time estimation is provided. This method may be useful for practitioners to decide whether to incorporate unsaturated processes in conceptual and numerical models and can also be used to roughly estimate the total travel time between points near ground surface and a groundwater receptor. This method was applied to a field site located in a glacial aquifer system in Ontario, Canada. Advective travel times were estimated using techniques with different levels of sophistication. The application of the proposed method indicates that the time lag in the unsaturated zone is significant at this field site and should be taken into account. For this case, sophisticated and simplified techniques lead to similar assessments when the same knowledge of the hydraulic conductivity field is assumed. When there is significant uncertainty regarding the hydraulic conductivity, simplified calculations did not lead to a conclusive decision. Copyright © 2012 Elsevier B.V. All rights reserved.

40 CFR 721.642 - Amines, N-(C14-18 and C16-16 unsaturated alkyl)] dipropylene-tri-, tripropylenetetra-, and...

Code of Federal Regulations, 2010 CFR

2010-07-01

... substances amines, N-(C14-18 and C16-18 unsaturated alkyl)] dipropylenetri-, (PMN P-94-1244... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amines, N-(C14-18 and C16-16... Amines, N-(C14-18 and C16-16 unsaturated alkyl)] dipropylene-tri-, tripropylenetetra-, and...

Involvement of Lipid Metabolism in the Action of Phospholipase A2 Neurotoxins

DTIC Science & Technology

1993-12-03

saturated or unsaturated fatty acid on phospholipid hydrolysis d) determine effects of BSA...either unsaturated (18:2) or saturated (18:0) fatty acids . A major problem encountered in our studies at 100 nM toxin concentrations that we have now...examined. In contrast to the liberation of unsaturated fatty acids , the total (pellet plus supernatant) saturated fatty acids produced was greater for

Creep model of unsaturated sliding zone soils and long-term deformation analysis of landslides

NASA Astrophysics Data System (ADS)

Zou, Liangchao; Wang, Shimei; Zhang, Yeming

2015-04-01

Sliding zone soil is a special soil layer formed in the development of a landslide. Its creep behavior plays a significant role in long-term deformation of landslides. Due to rainfall infiltration and reservoir water level fluctuation, the soils in the slide zone are often in unsaturated state. Therefore, the investigation of creep behaviors of the unsaturated sliding zone soils is of great importance for understanding the mechanism of the long-term deformation of a landslide in reservoir areas. In this study, the full-process creep curves of the unsaturated soils in the sliding zone in different net confining pressure, matric suctions and stress levels were obtained from a large number of laboratory triaxial creep tests. A nonlinear creep model for unsaturated soils and its three-dimensional form was then deduced based on the component model theory and unsaturated soil mechanics. This creep model was validated with laboratory creep data. The results show that this creep model can effectively and accurately describe the nonlinear creep behaviors of the unsaturated sliding zone soils. In order to apply this creep model to predict the long-term deformation process of landslides, a numerical model for simulating the coupled seepage and creep deformation of unsaturated sliding zone soils was developed based on this creep model through the finite element method (FEM). By using this numerical model, we simulated the deformation process of the Shuping landslide located in the Three Gorges reservoir area, under the cycling reservoir water level fluctuation during one year. The simulation results of creep displacement were then compared with the field deformation monitoring data, showing a good agreement in trend. The results show that the creeping deformations of landslides have strong connections with the changes of reservoir water level. The creep model of unsaturated sliding zone soils and the findings obtained by numerical simulations in this study are conducive to reveal the mechanisms of the dynamic process of landslide deformation, and serve as an important basis for the prediction and evaluation of landslides.

Complex binding of the FabR repressor of bacterial unsaturated fatty acid biosynthesis to its cognate promoters.

PubMed

Feng, Youjun; Cronan, John E

2011-04-01

Two transcriptional regulators, the FadR activator and the FabR repressor, control biosynthesis of unsaturated fatty acids in Escherichia coli. FabR represses expression of the two genes, fabA and fabB, required for unsaturated fatty acid synthesis and has been reported to require the presence of an unsaturated thioester (of either acyl carrier protein or CoA) in order to bind the fabA and fabB promoters in vitro. We report in vivo experiments in which unsaturated fatty acid synthesis was blocked in the absence of exogenous unsaturated fatty acids in a ΔfadR strain and found that the rates of transcription of fabA and fabB were unaffected by the lack of unsaturated thioesters. To examine the discrepancy between our in vivo results and the prior in vitro results we obtained active, natively folded forms of the E. coli and Vibrio cholerae FabRs by use of an in vitro transcription-translation system. We report that FabR bound the intact promoter regions of both fabA and fabB in the absence of unsaturated acyl thioesters, but bound the two promoters differently. Native FabR bound the fabA promoter region provided that the canonical FabR binding site is extended by inclusion of flanking sequences that overlap the neighbouring FadR binding site. In contrast, although binding to the fabB operator also required a flanking sequence, a non-specific sequence could suffice. However, unsaturated thioesters did allow FabR binding to the minimal FabR operator sites of both promoters which otherwise were not bound. Thus unsaturated thioester ligands were not essential for FabR/target DNA interaction, but acted to enhance binding. The gel mobility shift data plus in vivo expression data indicate that despite the remarkably similar arrangements of promoter elements, FadR predominately regulates fabA expression whereas FabR is the dominant regulator of fabB expression. We also report that E. coli fabR expression is not autoregulated. Complementation, qRT-PCR and fatty acid composition analyses demonstrated that V. cholerae FabR was a functional repressor of unsaturated fatty acid synthesis. However, in contrast to E. coli, gel mobility shift assays indicated that neither E. coli nor V. cholerae FabRs bound the V. cholerae fabB promoter, although both proteins efficiently bound the V. cholerae fabA promoter. This asymmetry was shown to be due to the lack of a FabR binding site within the V. cholerae fabB promoter region. © 2011 Blackwell Publishing Ltd.

Macromolecular metal carboxylates

NASA Astrophysics Data System (ADS)

Dzhardimalieva, G. I.; Pomogailo, A. D.

2008-03-01

Data on the synthesis and physicochemical studies of salts of mono- or dibasic unsaturated carboxylic acids and unsaturated metal oxo-carboxylates are generalised and described systematically. The structures and properties of the COO group in various compounds and characteristic features of the structures of carboxylate complexes are analysed. The main routes and kinetics of polymerisation transformations of unsaturated metal carboxylates are considered. The attention is focused on the effect of the metal ion on the monomer reactivity and the polymer morphology and structure. The possibility of stereochemical control of radical polymerisation of unsaturated metal carboxylates is demonstrated. The electronic, magnetic, optical, absorption and thermal properties of metal (co)polymers and nanocomposites and their main applications are considered.

Intravenous iron-dextran: studies on unsaturated iron-binding capacity

PubMed Central

Cox, J. S. G.; Moss, G. F.; Bremner, I.; Reason, Janet

1968-01-01

A method is described for measuring the plasma unsaturated iron-binding capacity in the presence of very high concentrations of iron as iron-dextran. The procedure utilizes 59Fe to label the apotransferrin with subsequent separation of ionic iron from transferrin-bound iron on an ion exchange or Sephadex G.25 column. The unsaturated iron-binding capacity has been measured in rabbits and dogs after intravenous injection of iron-dextran and in human subjects after total dose infusion of iron-dextran. No evidence of saturation of the unsaturated iron-binding capacity was found even when the plasma iron values were greater than 40,000 μg Fe/100 ml. PMID:5697365

Olefin separation membrane and process

DOEpatents

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

1997-01-01

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

Unsaturated flow characterization utilizing water content data collected within the capillary fringe

USGS Publications Warehouse

Baehr, Arthur; Reilly, Timothy J.

2014-01-01

An analysis is presented to determine unsaturated zone hydraulic parameters based on detailed water content profiles, which can be readily acquired during hydrological investigations. Core samples taken through the unsaturated zone allow for the acquisition of gravimetrically determined water content data as a function of elevation at 3 inch intervals. This dense spacing of data provides several measurements of the water content within the capillary fringe, which are utilized to determine capillary pressure function parameters via least-squares calibration. The water content data collected above the capillary fringe are used to calculate dimensionless flow as a function of elevation providing a snapshot characterization of flow through the unsaturated zone. The water content at a flow stagnation point provides an in situ estimate of specific yield. In situ determinations of capillary pressure function parameters utilizing this method, together with particle-size distributions, can provide a valuable supplement to data libraries of unsaturated zone hydraulic parameters. The method is illustrated using data collected from plots within an agricultural research facility in Wisconsin.

Exploration of a mechanism for the production of highly unsaturated fatty acids in Scenedesmus sp. at low temperature grown on oil crop residue based medium.

PubMed

Lu, Qian; Li, Jun; Wang, Jinghan; Li, Kun; Li, Jingjing; Han, Pei; Chen, Paul; Zhou, Wenguang

2017-11-01

The ability of algae to produce lipids comprising of unsaturated fatty acids varies with strains and culture conditions. This study investigates the effect of temperature on the production of unsaturated fatty acids in Scenedesmus sp. grown on oil crop residue based medium. At low temperature (10°C), synthesis of lipids compromising of high contents of unsaturated fatty acids took place primarily in the early stage while protein accumulation mainly occurred in the late stage. This stepwise lipid-protein synthesis process was found to be associated with the contents of acetyl-CoA and α-KG in the algal cells. A mechanism was proposed and tested through simulation experiments which quantified the carbon flux allocation in algal cells at different cultivation stages. It is concluded that low culture temperature such as 10°C is suitable for the production of lipids comprising of unsaturated fatty acids. Copyright © 2017 Elsevier Ltd. All rights reserved.

Deuterium separation by infrared-induced addition reaction

DOEpatents

Marling, John B.

1977-01-01

A method for deuterium enrichment by the infrared-induced addition reaction of a deuterium halide with an unsaturated aliphatic compound. A gaseous mixture of a hydrogen halide feedstock and an unsaturated aliphatic compound, particularly an olefin, is irradiated to selectively vibrationally excite the deuterium halide contained therein. The excited deuterium halide preferentially reacts with the unsaturated aliphatic compound to produce a deuterated addition product which is removed from the reaction mixture.

Iron-catalyzed regio- and stereoselective substitution of gamma,delta-epoxy-alpha,beta-unsaturated esters and amides with Grignard reagents.

PubMed

Hata, Takeshi; Bannai, Rie; Otsuki, Mamoru; Urabe, Hirokazu

2010-03-05

When gamma,delta-epoxy-alpha,beta-unsaturated esters or amides were treated with 2 equiv of Grignard reagents in the presence of 10-24 mol % FeCl(2), regio- and stereoselective substitution of the epoxide moiety with the Grignard reagent occurred to give exclusively delta-hydroxy-gamma-alkyl or aryl-alpha,beta-unsaturated esters or amides in good yields.

Copper-Catalyzed Enantioselective Henry Reaction of β,γ-Unsaturated α-Ketoesters with Nitromethane in Water.

PubMed

Li, Yanan; Huang, Yekai; Gui, Yang; Sun, Jianan; Li, Jindong; Zha, Zhenggen; Wang, Zhiyong

2017-12-01

A highly enantioselective Henry reaction of β,γ-unsaturated α-ketoesters with nitromethane in water by virtue of chiral copper complexes has been developed. A series of unsaturated β-nitro-α-hydroxy esters bearing tetrasubstituted carbon stereocenters were obtained exclusively with high yields and excellent enantioselectivities. This method could avoid tedious anaerobic anhydrous manipulation and reduce the environmental pollution caused by organic solvents.

Measurement and modeling of unsaturated hydraulic conductivity

USGS Publications Warehouse

Perkins, Kim S.; Elango, Lakshmanan

2011-01-01

The unsaturated zone plays an extremely important hydrologic role that influences water quality and quantity, ecosystem function and health, the connection between atmospheric and terrestrial processes, nutrient cycling, soil development, and natural hazards such as flooding and landslides. Unsaturated hydraulic conductivity is one of the main properties considered to govern flow; however it is very difficult to measure accurately. Knowledge of the highly nonlinear relationship between unsaturated hydraulic conductivity (K) and volumetric water content is required for widely-used models of water flow and solute transport processes in the unsaturated zone. Measurement of unsaturated hydraulic conductivity of sediments is costly and time consuming, therefore use of models that estimate this property from more easily measured bulk-physical properties is common. In hydrologic studies, calculations based on property-transfer models informed by hydraulic property databases are often used in lieu of measured data from the site of interest. Reliance on database-informed predicted values with the use of neural networks has become increasingly common. Hydraulic properties predicted using databases may be adequate in some applications, but not others. This chapter will discuss, by way of examples, various techniques used to measure and model hydraulic conductivity as a function of water content, K. The parameters that describe the K curve obtained by different methods are used directly in Richards’ equation-based numerical models, which have some degree of sensitivity to those parameters. This chapter will explore the complications of using laboratory measured or estimated properties for field scale investigations to shed light on how adequately the processes are represented. Additionally, some more recent concepts for representing unsaturated-zone flow processes will be discussed.

Fatty Acid Structure and Degradation Analysis in Fingerprint Residues

NASA Astrophysics Data System (ADS)

Pleik, Stefanie; Spengler, Bernhard; Schäfer, Thomas; Urbach, Dieter; Luhn, Steven; Kirsch, Dieter

2016-09-01

GC-MS investigations were carried out to elucidate the aging behavior of unsaturated fatty acids in fingerprint residues and to identify their degradation products in aged samples. For this purpose, a new sample preparation technique for fingerprint residues was developed that allows producing N-methyl- N-trimethylsilyl-trifluoroacetamide (MSTFA) derivatives of the analyzed unsaturated fatty acids and their degradation products. MSTFA derivatization catalyzed by iodotrimethylsilane enables the reliable identification of aldehydes and oxoacids as characteristic MSTFA derivatives in GCMS. The obtained results elucidate the degradation pathway of unsaturated fatty acids. Our study of aged fingerprint residues reveals that decanal is the main degradation product of the observed unsaturated fatty acids. Furthermore, oxoacids with different chain lengths are detected as specific degradation products of the unsaturated fatty acids. The detection of the degradation products and their chain length is a simple and effective method to determine the double bond position in unsaturated compounds. We can show that the hexadecenoic and octadecenoic acids found in fingerprint residues are not the pervasive fatty acids Δ9-hexadecenoic (palmitoleic acid) and Δ9-octadecenoic (oleic acid) acid but Δ6-hexadecenoic acid (sapienic acid) and Δ8-octadecenoic acid. The present study focuses on the structure identification of human sebum-specific unsaturated fatty acids in fingerprint residues based on the identification of their degradation products. These results are discussed for further investigations and method developments for age determination of fingerprints, which is still a tremendous challenge because of several factors affecting the aging behavior of individual compounds in fingerprints.

Fatty Acid Structure and Degradation Analysis in Fingerprint Residues.

PubMed

Pleik, Stefanie; Spengler, Bernhard; Schäfer, Thomas; Urbach, Dieter; Luhn, Steven; Kirsch, Dieter

2016-09-01

GC-MS investigations were carried out to elucidate the aging behavior of unsaturated fatty acids in fingerprint residues and to identify their degradation products in aged samples. For this purpose, a new sample preparation technique for fingerprint residues was developed that allows producing N-methyl-N-trimethylsilyl-trifluoroacetamide (MSTFA) derivatives of the analyzed unsaturated fatty acids and their degradation products. MSTFA derivatization catalyzed by iodotrimethylsilane enables the reliable identification of aldehydes and oxoacids as characteristic MSTFA derivatives in GCMS. The obtained results elucidate the degradation pathway of unsaturated fatty acids. Our study of aged fingerprint residues reveals that decanal is the main degradation product of the observed unsaturated fatty acids. Furthermore, oxoacids with different chain lengths are detected as specific degradation products of the unsaturated fatty acids. The detection of the degradation products and their chain length is a simple and effective method to determine the double bond position in unsaturated compounds. We can show that the hexadecenoic and octadecenoic acids found in fingerprint residues are not the pervasive fatty acids Δ9-hexadecenoic (palmitoleic acid) and Δ9-octadecenoic (oleic acid) acid but Δ6-hexadecenoic acid (sapienic acid) and Δ8-octadecenoic acid. The present study focuses on the structure identification of human sebum-specific unsaturated fatty acids in fingerprint residues based on the identification of their degradation products. These results are discussed for further investigations and method developments for age determination of fingerprints, which is still a tremendous challenge because of several factors affecting the aging behavior of individual compounds in fingerprints. Graphical Abstract ᅟ.

Determination of Matric Suction and Saturation Degree for Unsaturated Soils, Comparative Study - Numerical Method versus Analytical Method

NASA Astrophysics Data System (ADS)

Chiorean, Vasile-Florin

2017-10-01

Matric suction is a soil parameter which influences the behaviour of unsaturated soils in both terms of shear strength and permeability. It is a necessary aspect to know the variation of matric suction in unsaturated soil zone for solving geotechnical issues like unsaturated soil slopes stability or bearing capacity for unsaturated foundation ground. Mathematical expression of the dependency between soil moisture content and it’s matric suction (soil water characteristic curve) has a powerful character of nonlinearity. This paper presents two methods to determine the variation of matric suction along the depth included between groundwater level and soil level. First method is an analytical approach to emphasize one direction steady state unsaturated infiltration phenomenon that occurs between the groundwater level and the soil level. There were simulated three different situations in terms of border conditions: precipitations (inflow conditions on ground surface), evaporation (outflow conditions on ground surface), and perfect equilibrium (no flow on ground surface). Numerical method is finite element method used for steady state, two-dimensional, unsaturated infiltration calculus. Regarding boundary conditions there were simulated identical situations as in analytical approach. For both methods, was adopted the equation proposed by van Genuchten-Mualen (1980) for mathematical expression of soil water characteristic curve. Also for the unsaturated soil permeability prediction model was adopted the equation proposed by van Genuchten-Mualen. The fitting parameters of these models were adopted according to RETC 6.02 software in function of soil type. The analyses were performed in both methods for three major soil types: clay, silt and sand. For each soil type were concluded analyses for three situations in terms of border conditions applied on soil surface: inflow, outflow, and no flow. The obtained results are presented in order to highlight the differences/similarities between the methods and the advantages / disadvantages of each one.

Documentation of the Unsaturated-Zone Flow (UZF1) Package for modeling Unsaturated Flow Between the Land Surface and the Water Table with MODFLOW-2005

USGS Publications Warehouse

Niswonger, Richard G.; Prudic, David E.; Regan, R. Steven

2006-01-01

Percolation of precipitation through unsaturated zones is important for recharge of ground water. Rain and snowmelt at land surface are partitioned into different pathways including runoff, infiltration, evapotranspiration, unsaturated-zone storage, and recharge. A new package for MODFLOW-2005 called the Unsaturated-Zone Flow (UZF1) Package was developed to simulate water flow and storage in the unsaturated zone and to partition flow into evapotranspiration and recharge. The package also accounts for land surface runoff to streams and lakes. A kinematic wave approximation to Richards? equation is solved by the method of characteristics to simulate vertical unsaturated flow. The approach assumes that unsaturated flow occurs in response to gravity potential gradients only and ignores negative potential gradients; the approach further assumes uniform hydraulic properties in the unsaturated zone for each vertical column of model cells. The Brooks-Corey function is used to define the relation between unsaturated hydraulic conductivity and water content. Variables used by the UZF1 Package include initial and saturated water contents, saturated vertical hydraulic conductivity, and an exponent in the Brooks-Corey function. Residual water content is calculated internally by the UZF1 Package on the basis of the difference between saturated water content and specific yield. The UZF1 Package is a substitution for the Recharge and Evapotranspiration Packages of MODFLOW-2005. The UZF1 Package differs from the Recharge Package in that an infiltration rate is applied at land surface instead of a specified recharge rate directly to ground water. The applied infiltration rate is further limited by the saturated vertical hydraulic conductivity. The UZF1 Package differs from the Evapotranspiration Package in that evapotranspiration losses are first removed from the unsaturated zone above the evapotranspiration extinction depth, and if the demand is not met, water can be removed directly from ground water whenever the depth to ground water is less than the extinction depth. The UZF1 Package also differs from the Evapotranspiration Package in that water is discharged directly to land surface whenever the altitude of the water table exceeds land surface. Water that is discharged to land surface, as well as applied infiltration in excess of the saturated vertical hydraulic conductivity, may be routed directly as inflow to specified streams or lakes if these packages are active; otherwise, this water is removed from the model. The UZF1 Package was tested against the U.S. Geological Survey's Variably-Saturated Two-Dimensional Flow and Transport Model for a vertical unsaturated flow problem that includes evapotranspiration losses. This report also includes an example in which MODFLOW-2005 with the UZF1 Package was used to simulate a realistic surface-water/ground-water flow problem that includes time and space variable infiltration, evapotranspiration, runoff, and ground-water discharge to land surface and to streams. Another simpler problem is presented so that the user may use the input files as templates for new problems and to verify proper code installation.

Rhodium-catalyzed asymmetric hydroboration of γ,δ-unsaturated amide derivatives: δ-borylated amides.

PubMed

Hoang, G L; Zhang, S; Takacs, J M

2018-05-08

γ,δ-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed δ-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the γ-borylation of γ,δ-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal in the sense of π-facial selectivity.

40 CFR 180.1284 - Ammonium salts of higher fatty acids (C8-C18 saturated; C8-C12 unsaturated); exemption from the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Ammonium salts of higher fatty acids... Ammonium salts of higher fatty acids (C8-C18 saturated; C8-C12 unsaturated); exemption from the requirement of a tolerance. Ammonium salts of C8-C18 saturated and C8-C12 unsaturated higher fatty acids are...

40 CFR 180.1284 - Ammonium salts of higher fatty acids (C8-C18 saturated; C8-C12 unsaturated); exemption from the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Ammonium salts of higher fatty acids... Ammonium salts of higher fatty acids (C8-C18 saturated; C8-C12 unsaturated); exemption from the requirement of a tolerance. Ammonium salts of C8-C18 saturated and C8-C12 unsaturated higher fatty acids are...

Sediment properties and water movement through shallow unsaturated alluvium at an arid site for disposal of low-level radioactive waste near Beatty, Nye County, Nevada

USGS Publications Warehouse

Fischer, Jeffrey M.

1992-01-01

A commercial disposal facility for low-level radioactive waste has been in operation near Beatty, Nevada, since 1962. The facility is in the arid Amargosa Desert where wastes are buried in trenches excavated into unsaturated alluvial sediments. Thick unsaturated zones in arid environments offer many potential advantages for disposal of radioactive wastes, but little is known about the natural movement of water near such facilities. Thus, a study was begun in 1982 to better define the direction and rates of water movement through the unsaturated zone in undisturbed sediments near the disposal facility. This report discusses the analyses of data collected between 1983 and 1988.

Olefin separation membrane and process

DOEpatents

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

1997-09-23

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

Two applications of the Recently Developed UZF-MT3DMS Model for Evaluating Nonpoint-Source Fluxes (Invited)

NASA Astrophysics Data System (ADS)

Morway, E. D.; Niswonger, R. G.; Nishikawa, T.

2013-12-01

The solute-transport model MT3DMS was modified to simulate transport in the unsaturated-zone by incorporating the additional flow terms calculated by the Unsaturated-Zone Flow (UZF) package developed for MODFLOW. Referred to as UZF-MT3DMS, the model simulates advection and dispersion of conservative and reactive solutes in unsaturated and saturated porous media. Significant time savings are realized owing to the efficiency of the kinematic -wave approximation used by the UZF1 package relative to Richards' equation-based approaches, facilitating the use of automated parameter-estimation routines wherein thousands of model runs may be required. Currently, UZF-MT3DMS is applied to two real-world applications of existing MODFLOW and MT3DMS models retro-fitted to use the UZF1 package for simulating the unsaturated component of the sub-surface system. In the first application, two regional-scale investigations located in Colorado's Lower Arkansas River Valley (LARV) are developed to evaluate the extent and severity of unsaturated-zone salinization contributing to crop yield loss. Preliminary results indicate root zone concentrations over both regions are at or above salinity-thresholds of most crop types grown in the LARV. Regional-scale modeling investigations of salinization found in the literature commonly use lumped-parameter models rather than physically-based distributed-parameter models. In the second application, located near Joshua Tree, CA, nitrate loading to the underlying unconfined aquifer from domestic septic systems is evaluated. Due to the region's thick unsaturated-zone and correspondingly long unsaturated-zone residence times (multi-decade), UZF-MT3DMS enabled direct simulation of spatially-varying concentration break-through curves at the water table.

Base flow recession from unsaturated-saturated porous media considering lateral unsaturated discharge and aquifer compressibility

NASA Astrophysics Data System (ADS)

Liang, Xiuyu; Zhan, Hongbin; Zhang, You-Kuan; Schilling, Keith

2017-09-01

Unsaturated flow is an important process in base flow recessions and its effect is rarely investigated. A mathematical model for a coupled unsaturated-saturated flow in a horizontally unconfined aquifer with time-dependent infiltrations is presented. The effects of the lateral discharge of the unsaturated zone and aquifer compressibility are specifically taken into consideration. Semianalytical solutions for hydraulic heads and discharges are derived using Laplace transform and Cosine transform. The solutions are compared with solutions of the linearized Boussinesq equation (LB solution) and the linearized Laplace equation (LL solution), respectively. A larger dimensionless constitutive exponent κD (a smaller retention capacity) of the unsaturated zone leads to a smaller discharge during the infiltration period and a larger discharge after the infiltration. The lateral discharge of the unsaturated zone is significant when κD≤1, and becomes negligible when κD≥100. The compressibility of the aquifer has a nonnegligible impact on the discharge at early times. For late times, the power index b of the recession curve -dQ/dt˜ aQb, is 1 and independent of κD, where Q is the base flow and a is a constant lumped aquifer parameter. For early times, b is approximately equal to 3 but it approaches infinity when t→0. The present solution is applied to synthetic and field cases. The present solution matched the synthetic data better than both the LL and LB solutions, with a minimum relative error of 16% for estimate of hydraulic conductivity. The present solution was applied to the observed streamflow discharge in Iowa, and the estimated values of the aquifer parameters were reasonable.

A Preliminary Design of a Calibration Chamber for Evaluating the Stability of Unsaturated Soil Slope

NASA Astrophysics Data System (ADS)

Hsu, H.-H.

2012-04-01

The unsaturated soil slopes, which have ground water tables and are easily failure caused by heavy rainfalls, are widely distributed in the arid and semi-arid areas. For analyzing the stability of slope, in situ tests are the direct methods to obtain the test site characteristics. The cone penetration test (CPT) is a popular in situ test method. Some of the CPT empirical equations established from calibration chamber tests. The CPT performed in calibration chamber was commonly used clean quartz sand as testing material in the past. The silty sand is observed in many actual slopes. Because silty sand is relatively compressible than quartz sand, it is not suitable to apply the correlations between soil properties and CPT results built from quartz sand to silty sand. The experience on CPT calibration in silty sand has been limited. CPT calibration tests were mostly performed in dry or saturated soils. The condition around cone tip during penetration is assumed to be fully drained or fully undrained, yet it was observed to be partially drained for unsaturated soils. Because of the suction matrix has a great effect on the characteristics of unsaturated soils, they are much sensitive to the water content than saturated soils. The design of an unsaturated calibration chamber is in progress. The air pressure is supplied from the top plate and the pore water pressure is provided through the high air entry value ceramic disks located at the bottom plate of chamber cell. To boost and uniform distribute the unsaturated effect, four perforated burettes are installed onto the ceramic disks and stretch upwards to the midheight of specimen. This paper describes design concepts, illustrates this unsaturated calibration chamber, and presents the preliminary test results.

The Soil Foam Drainage Equation - an alternative model for unsaturated flow in porous media

NASA Astrophysics Data System (ADS)

Assouline, Shmuel; Lehmann, Peter; Hoogland, Frouke; Or, Dani

2017-04-01

The analogy between the geometry and dynamics of wet foam drainage and gravity drainage of unsaturated porous media expands modeling capabilities for capillary flows and supplements the standard Richards equation representation. The governing equation for draining foam (or a soil variant termed the soil foam drainage equation - SFDE) obviates the need for macroscopic unsaturated hydraulic conductivity function by an explicit account of diminishing flow pathway sizes as the medium gradually drains. Potential advantages of the proposed drainage foam formalism include direct description of transient flow without requiring constitutive functions; evolution of capillary cross sections that provides consistent description of self-regulating internal fluxes (e.g., towards field capacity); and a more intuitive geometrical picture of capillary flow across textural boundaries. We will present new and simple analytical expressions for drainage rates and volumes from unsaturated porous media subjected to different boundary conditions that are in good agreement with the numerical solution of the SFDE and experimental results. The foam drainage methodology expands the range of tools available for describing and quantifying unsaturated flows and provides geometrically tractable links between evolution of liquid configuration and flow dynamics in unsaturated porous media. The resulting geometrical representation of capillary drainage could improve understanding of colloid and pathogen transport. The explicit geometrical interpretation of flow pathways underlying the hydraulic functions used by the Richards equation offers new insights that benefit both approaches.

Pumping-Induced Unsaturated Regions Beneath a Perennial River

NASA Astrophysics Data System (ADS)

Su, G. W.; Jasperse, J.; Seymour, D.; Constantz, J.; Delaney, C.; Zhou, Q.

2006-12-01

The development of an unsaturated region beneath a streambed during groundwater pumping near streams reduces the capacity of the pumping system, changes flow paths, and alters the types of biological transformations in the streambed sediments. To investigate the formation of an unsaturated region beneath the streambed during near-stream groundwater pumping, a three-dimensional, multi-phase flow model was developed using TOUGH2 of the region near two horizontal collector wells operated by the Sonoma County Water Agency along the Russian River near Forestville, California. The simulations focus on the impact of streambed permeability on the development of an unsaturated region since streambed permeability controls the flux of river water entering and recharging the aquifer. The results indicate that as the streambed permeability decreases relative to the aquifer permeability, the size of the unsaturated region beneath the streambed increases. The simulations also demonstrate that the streambed permeabilities over which the aquifer beneath the streambed is unsaturated and able to extract water at the specified rate of 3200 m3/hr occurs over a relatively narrow range of values. Field measurements of streambed flow velocities, volumetric water content, and temperatures near the collector wells are also presented and compared with the simulation results. This work was supported by the Sonoma County Water Agency, through U.S. Department of Energy Contract No. DE-AC03-76SF00098.

High-fat feeding reduces endothelium-dependent vasodilation in rats: differential mechanisms for saturated and unsaturated fatty acids?

PubMed

Song, Guang-Yao; Gao, Yu; Di, Yu-Wei; Pan, Li-Li; Zhou, Yu; Ye, Ji-Ming

2006-08-01

1. Chronic feeding with a high-fat diet can cause metabolic syndrome in rodents similar to humans, but the role of saturated versus unsaturated fats in vascular tension remains unclear. 2. The present study shows that rats on a diet rich in either saturated or unsaturated fat had higher blood pressure compared with chow-fed rats (approximately 130 vs 100 mmHg, respectively), along with hyperlipidaemia and insulin resistance. Compared with responses of phenylephrine-preconstricted artery segments from chow-fed rats, vasorelaxation of isolated renal arteries from high-fat fed rats was reduced substantially (> 50%) in response to acetylcholine (0.01-10 micromol/L) and moderately to nitroprusside (>or=1 micromol/L) at low concentrations. Acetylcholine-induced vasorelaxation of arteries from high-fat fed rats was also more sensitive to inhibition by the nitric oxide (NO) synthase inhibitors NG-nitro-L-arginine and methylene blue. 3. In human umbilical vein endothelial cells, the production of NO and endothelin-1 was significantly inhibited by unsaturated fatty acids. In comparison, saturated fatty acids stimulated endothelin-1 production without altering NO production. 4. The data indicate that both saturated and unsaturated high-fat feeding may result in an increase in blood pressure owing to reduced endothelium-dependent vasorelaxation in the arterial system. The impaired endothelium-dependent vasorelaxation induced by saturated and unsaturated fatty acids may involve different mechanisms.

Screening of Chlorinated Paraffins and Unsaturated Analogues in Commercial Mixtures: Confirmation of Their Occurrences in the Atmosphere.

PubMed

Li, Tong; Gao, Shixiong; Ben, Yujie; Zhang, Hong; Kang, Qiyue; Wan, Yi

2018-02-20

Characterizing the detailed compositions of chlorinated paraffins (CPs) commercial mixtures is crucial to understand their environmental sources, fates, and potential risks. In this study, dichloromethane (DCM)-enhanced UPLC-ESI-QTOFMS analysis combined with characteristic isotope chlorine peaks is applied to screen all CPs and their structural analogues in the three most commonly produced CP commercial mixtures (CP-42, CP-52, and CP-70). Mass fractions of total short-chain CPs (SCCPs), medium-chain CPs (MCCPs) and long-chain CPs (LCCPs) ranged from 0.64 to 31.9%, 0.64 to 21.8%, and 0.04 to 43.9%, respectively, in the three commercial mixtures. 113 unsaturated SCCPs, MCCPs, and LCCPs were identified in the commercial mixtures. The detailed mass percentages of saturated and unsaturated CPs with carbon numbers of 10-30, chlorine numbers of 5-28, and unsaturated degrees of 0-7 were characterized in all commercial mixtures. Occurrences of the predominant saturated and unsaturated CPs were further confirmed in air samples collected in Guangdong Province, one of the major CP production areas in China, over one year. The profiles of the detected compounds indicated that LCCPs in air samples might come mainly from the production and usage of CP-52, and unsaturated C 24-29 -LCCPs were specifically originated from CP-70 used in the area.

Kinetics of the gas-phase reaction between ozone and three unsaturated oxygenated compounds: Ethyl 3,3-dimethyl acrylate, 2-methyl-2-pentenal and 6-methyl-5-hepten-2-one at atmospheric pressure

NASA Astrophysics Data System (ADS)

Gaona Colmán, Elizabeth; Blanco, María B.; Barnes, Ian; Teruel, Mariano A.

2015-05-01

Rate coefficients for the gas-phase reactions of O3 molecules with three unsaturated oxygenated compounds have been determined using the relative kinetic technique in an environmental chamber with FTIR detection of the reactants at (298 ± 2) K in 760 Torr total pressure of synthetic air. The following rate coefficients (in units of 10-17 cm3 molecule-1 s-1) were determined: ethyl 3,3-dimethyl acrylate (0.82 ± 0.19), 2-methyl-2-pentenal (0.71 ± 0.16) and 6-methyl-5-hepten-2-one (26 ± 7). The different reactivity of the unsaturated oxygenated compounds toward O3 is discussed in terms of their chemical structure. In addition, a correlation between the reactivity of structurally different unsaturated compounds (alkenes and unsaturated oxygenated VOCs, such as ethers, esters, aldehydes, ketones and alcohols) toward O3 molecules and the HOMO (Highest Occupied Molecular Orbital) of the compounds is presented. Using the kinetic parameters determined in this work, residence times of these unsaturated compounds in the atmosphere with respect to reaction with O3 have been calculated. In urban and rural areas the main sink of 6-methyl-5-hepten-2-one is reaction with O3 molecules with a residence time in the order of few minutes.

Dose-dependent DNA adduct formation by cinnamaldehyde and other food-borne α,β-unsaturated aldehydes predicted by physiologically based in silico modelling.

PubMed

Kiwamoto, R; Ploeg, D; Rietjens, I M C M; Punt, A

2016-03-01

Genotoxicity of α,β-unsaturated aldehydes shown in vitro raises a concern for the use of the aldehydes as food flavourings, while at low dose exposures the formation of DNA adducts may be prevented by detoxification. Unlike many α,β-unsaturated aldehydes for which in vivo data are absent, cinnamaldehyde was shown to be not genotoxic or carcinogenic in vivo. The present study aimed at comparing dose-dependent DNA adduct formation by cinnamaldehyde and 18 acyclic food-borne α,β-unsaturated aldehydes using physiologically based kinetic/dynamic (PBK/D) modelling. In rats, cinnamaldehyde was predicted to induce higher DNA adducts levels than 6 out of the 18 α,β-unsaturated aldehydes, indicating that these 6 aldehydes may also test negative in vivo. At the highest cinnamaldehyde dose that tested negative in vivo, cinnamaldehyde was predicted to form at least three orders of magnitude higher levels of DNA adducts than the 18 aldehydes at their respective estimated daily intake. These results suggest that for all the 18 α,β-unsaturated aldehydes DNA adduct formation at doses relevant for human dietary exposure may not raise a concern. The present study illustrates a possible use of physiologically based in silico modelling to facilitate a science-based comparison and read-across on the possible risks posed by DNA reactive agents. Copyright © 2015 Elsevier B.V. All rights reserved.

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns.

PubMed

Dousset, S; Thevenot, M; Pot, V; Simunek, J; Andreux, F

2007-12-07

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

NASA Astrophysics Data System (ADS)

Dousset, S.; Thevenot, M.; Pot, V.; Šimunek, J.; Andreux, F.

2007-12-01

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.

Field investigation into unsaturated flow and transport in a fault: Model analyses

USGS Publications Warehouse

Liu, H.-H.; Salve, R.; Wang, J.-S.; Bodvarsson, G.S.; Hudson, D.

2004-01-01

Results of a fault test performed in the unsaturated zone of Yucca Mountain, Nevada, were analyzed using a three-dimensional numerical model. The fault was explicitly represented as a discrete feature and the surrounding rock was treated as a dual-continuum (fracture-matrix) system. Model calibration against seepage and water-travel-velocity data suggests that lithophysal cavities connected to fractures can considerably enhance the effective fracture porosity and therefore retard water flow in fractures. Comparisons between simulation results and tracer concentration data also indicate that matrix diffusion is an important mechanism for solute transport in unsaturated fractured rock. We found that an increased fault-matrix and fracture-matrix interface areas were needed to match the observed tracer data, which is consistent with previous studies. The study results suggest that the current site-scale model for the unsaturated zone of Yucca Mountain may underestimate radionuclide transport time within the unsaturated zone, because an increased fracture-matrix interface area and the increased effective fracture porosity arising from lithophysal cavities are not considered in the current site-scale model. ?? 2004 Published by Elsevier B.V.

Time-lapse gravity data for monitoring and modeling artificial recharge through a thick unsaturated zone

USGS Publications Warehouse

Kennedy, Jeffrey R.; Ferre, Ty P.A.; Creutzfeldt, Benjamin

2016-01-01

Groundwater-level measurements in monitoring wells or piezometers are the most common, and often the only, hydrologic measurements made at artificial recharge facilities. Measurements of gravity change over time provide an additional source of information about changes in groundwater storage, infiltration, and for model calibration. We demonstrate that for an artificial recharge facility with a deep groundwater table, gravity data are more sensitive to movement of water through the unsaturated zone than are groundwater levels. Groundwater levels have a delayed response to infiltration, change in a similar manner at many potential monitoring locations, and are heavily influenced by high-frequency noise induced by pumping; in contrast, gravity changes start immediately at the onset of infiltration and are sensitive to water in the unsaturated zone. Continuous gravity data can determine infiltration rate, and the estimate is only minimally affected by uncertainty in water-content change. Gravity data are also useful for constraining parameters in a coupled groundwater-unsaturated zone model (Modflow-NWT model with the Unsaturated Zone Flow (UZF) package).

Synergies between Unsaturated Zn/Cu Doping Sites in Carbon Dots Provide New Pathways for Photocatalytic Oxidation

DOE PAGES

Wu, Wenting; Zhang, Qinggang; Wang, Ruiqin; ...

2017-12-07

Unsaturated metal species (UMS) confined in nanomaterials play important roles for electron transfer in a wide range of catalytic reactions. However, the limited fabrication methods of UMS restrict their wider catalytic applications. Here in this paper, we report on the synergy of unsaturated Zn and Cu dopants confined in carbon dots (ZnCu-CDs) to produce enhanced electron transfer and photooxidation processes in the doped CDs. The Zn/Cu species chelate with the carbon matrix mainly through Cu-O(N)-Zn-O(N)-Cu complexes. Within this structure, Cu 2+ acts as a mild oxidizer that facilely increases the unsaturated Zn content and also precisely tunes the unsaturated Znmore » valence state to Zn d+, where d is between 1 and 2, instead of Zn. With the help of UMS, electron-transfer pathways are produced, enhancing both the electron donating (7.0 times) and-accepting (5.3 times) abilities relative to conventional CDs. Because of these synergistic effects, the photocatalytic efficiency of CDs in photooxidation reactions is shown to improve more than 5-fold.« less

Time-lapse gravity data for monitoring and modeling artificial recharge through a thick unsaturated zone

NASA Astrophysics Data System (ADS)

Kennedy, Jeffrey; Ferré, Ty P. A.; Creutzfeldt, Benjamin

2016-09-01

Groundwater-level measurements in monitoring wells or piezometers are the most common, and often the only, hydrologic measurements made at artificial recharge facilities. Measurements of gravity change over time provide an additional source of information about changes in groundwater storage, infiltration, and for model calibration. We demonstrate that for an artificial recharge facility with a deep groundwater table, gravity data are more sensitive to movement of water through the unsaturated zone than are groundwater levels. Groundwater levels have a delayed response to infiltration, change in a similar manner at many potential monitoring locations, and are heavily influenced by high-frequency noise induced by pumping; in contrast, gravity changes start immediately at the onset of infiltration and are sensitive to water in the unsaturated zone. Continuous gravity data can determine infiltration rate, and the estimate is only minimally affected by uncertainty in water-content change. Gravity data are also useful for constraining parameters in a coupled groundwater-unsaturated zone model (Modflow-NWT model with the Unsaturated Zone Flow (UZF) package).

Comparison of surfactant lipids between pleural and pulmonary lining fluids.

PubMed

Mills, P C; Chen, Y; Hills, Y C; Hills, B A

2006-01-01

Saturated phospholipids (PCs), particularly dipalmitoylphosphatidylcholine (DPPC), predominate in surfactant lining the alveoli, although little is known about the relationship between saturated and unsaturated PCs on the outer surface of the lung, the pleura. Seven healthy cats were anesthetized and a bronchoalveolar lavage (BAL) was performed, immediately followed by a pleural lavage (PL). Lipid was extracted from lavage fluid and then analyzed for saturated, primarily dipalmitoylphosphatidylcholine (DPPC), and unsaturated PC species using high-performance liquid chromatography (HPLC) with combined fluorescence and ultraviolet detection. Dilution of epithelial lining fluid (ELF) in lavage fluids was corrected for using the urea method. The concentration of DPPC in BAL fluid (85.3+/-15.7 microg/mL) was significantly higher (P=0.021) than unsaturated PCs ( approximately 40 microg/mL). However, unsaturated PCs ( approximately 34 microg/mL), particularly stearoyl-linoleoyl-phosphatidylcholine (SLPC; 17.4+/-6.8), were significantly higher (P=0.021) than DPPC (4.3+/-1.8 microg/mL) in PL fluid. These results show that unsaturated PCs appear functionally more important in the pleural cavity, which may have implications for surfactant replenishment following pleural disease or thoracic surgery.

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.

UNSATURATED AMINO ACIDS V.

PubMed Central

Shapira, Jacob; Dittmer, Karl

1961-01-01

Shapira, Jacob (Department of Chemistry, Florida State University, Tallahassee) and Karl Dittmer. Unsaturated amino acids. V. Microbiological properties of some halogenated olefinic amino acids. J. Bacteriol. 82:640–647. 1961.—It has been shown previously that several amino acid analogues containing unsaturated linkages were inhibitors of the growth of Escherichia coli and Saccharomyces cerevisiae. This paper reports the results obtained when a series of unsaturated halogen-containing amino acids was examined. The cis isomer of ω-chloroallylglycine showed the greatest toxicity yet found in this series of unsaturated amino acids toward E. coli, whereas the trans-isomer was usually far less toxic. The major effect of cis-ω-chloroallylglycine in E. coli appeared to be to extend the lag phase before the normal rate of growth began. A wide variety of amino acids was capable of partially or completely preventing the toxicity of low levels of these compounds. At higher levels, relatively few amino acids (primarily valine, leucine, and glutamic acid) were effective. In E. coli, cis-ω-chloroallylglycine showed an unusual [Formula: see text] relationship with both glutamic acid and valine over a wide range in concentration. PMID:13911278

Alteration in the contents of unsaturated fatty acids in dnaA mutants of Escherichia coli.

PubMed

Suzuki, E; Kondo, T; Makise, M; Mima, S; Sakamoto, K; Tsuchiya, T; Mizushima, T

1998-04-01

DnaA protein, the initiator of chromosomal DNA replication in Escherichia coli, has a high affinity for acidic phospholipids containing unsaturated fatty acids. We have examined here the fatty acid composition of phospholipids in dnaA mutants. A temperature-sensitive dnaA46 mutant showed a lower level of unsaturation of fatty acids (ratio of unsaturated to saturated fatty acids) at 42 degrees C (non-permissive temperature) and at 37 degrees C (semi-permissive temperature), but not at 28 degrees C (permissive temperature), compared with the wild-type strain. Plasmid complementation analysis revealed that the dnaA46 mutation is responsible for the phenotype. Other temperature-sensitive dnaA mutants showed similar results. On the other hand, a cold-sensitive dnaAcos mutant, in which over-initiation of DNA replication occurs at low temperature (28 degrees C), showed a higher level of unsaturation of fatty acids at 28 degrees C. Based on these observations, we discuss the role of phospholipids in the regulation of the activity of DnaA protein.

Autoxidation of unsaturated lipids in food emulsion.

PubMed

Sun, Yue-E; Wang, Wei-Dong; Chen, Hong-Wei; Li, Chao

2011-05-01

Unsaturated lipids having various physiological roles are of significance in biochemistry, nutrition, medicine, and food. However, the susceptibility of lipids to oxidation is a major cause of quality deterioration in food emulsions. The reaction mechanism and factors that influence oxidation are appreciably different for emulsified lipids and bulk lipids. This article gives a brief overview of the current knowledge on autoxidation of oil-in-water food emulsions, especially those that contain unsaturated lipids, which are important in the food industry. Autoxidation of unsaturated lipids in oil-in-water emulsion is discussed, and so also their oxidation mechanism, the major factors influencing oxidation, determination measures, research status, and the problems encountered in recent years. Some effective strategies for controlling lipid oxidation in food emulsion have been presented in this review.

Biscarbene palladium(II) complexes. reactivity of saturated versus unsaturated N-heterocyclic carbenes.

PubMed

Fu, Ching-Feng; Lee, Chun-Chin; Liu, Yi-Hung; Peng, Shie-Ming; Warsink, Stefan; Elsevier, Cornelis J; Chen, Jwu-Ting; Liu, Shiuh-Tzung

2010-03-15

A series of designed palladium biscarbene complexes including saturated and unsaturated N-heterocyclic carbene (NHC) moieties have been prepared by the carbene transfer methods. All of these complexes have been characterized by (1)H and (13)C NMR spectroscopy as well as X-ray diffraction analysis. The reactivity of Pd-C((saturated NHC)) is distinct from that of Pd-C((unsaturated NHC)). The Pd-C((saturated NHC)) bonds are fairly stable toward reagents such as CF(3)COOH, AgBF(4) and I(2), whereas Pd-C((unsaturated NHC)) bonds are readily cleaved under the similar conditions. Notably, the catalytically activity of these palladium complexes on Suzuki-Miyaura coupling follows the order: (sat-NHC)(2)PdCl(2) > (sat-NHC)(unsat-NHC)PdCl(2 )> (unsat-NHC)(2)PdCl(2).

Three-dimensional saturated-unsaturated flow with axial symmetry to a partially penetrating well in a compressible unconfined aquifer

NASA Astrophysics Data System (ADS)

Tartakovsky, Guzel D.; Neuman, Shlomo P.

2007-01-01

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. Three-dimensional, axially symmetric 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 or, equivalently, 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. According to Kroszynski and Dagan, aquifers that are not excessively shallow have values of κD (their parameter a) much greater than 10. We find that in such typical cases, unsaturated flow has little impact on early and late dimensionless time drawdown a short 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. Delayed drainage from the unsaturated zone becomes less and less important as κD increases; as κD → ∞, this effect dies out, and drawdown is controlled entirely by delayed decline in the water table as in the model of Neuman. The unsaturated zone has a major impact on drawdown at intermediate time and a significant impact at early and late times, in the atypical case of κD ≤ 1, becoming the dominant factor as κD approaches zero (the soil water retention capacity becomes very large and/or saturated thickness becomes insignificant). Our new solution was used to analyze field data from a pumping test conducted by Moench et al. (2001) in a glacial outwash deposit at Cape Cod, Massachusetts. The solution was fitted individually and simultaneously to time-drawdown data from 20 piezometers and observation wells and simultaneously to data from three piezometers in each of two clusters at various depths and distances from the pumping well, with very good results. Our parameter estimates of hydraulic conductivities from the simultaneous fit are similar to those obtained previously by Moench (2004), but our estimates of specific yield and storage are smaller and larger, respectively, while our estimate of κ is not comparable with his estimates of three empirical parameters.

Rh(III)-Catalyzed Decarboxylative Coupling of Acrylic Acids with Unsaturated Oxime Esters: Carboxylic Acids Serve as Traceless Activators

PubMed Central

2015-01-01

α,β-Unsaturated carboxylic acids undergo Rh(III)-catalyzed decarboxylative coupling with α,β-unsaturated O-pivaloyl oximes to provide substituted pyridines in good yield. The carboxylic acid, which is removed by decarboxylation, serves as a traceless activating group, giving 5-substituted pyridines with very high levels of regioselectivity. Mechanistic studies rule out a picolinic acid intermediate, and an isolable rhodium complex sheds further light on the reaction mechanism. PMID:24512241

Vapor port and groundwater sampling well

DOEpatents

Hubbell, Joel M.; Wylie, Allan H.

1996-01-01

A method and apparatus has been developed for combining groundwater monitoring wells with unsaturated-zone vapor sampling ports. The apparatus allows concurrent monitoring of both the unsaturated and the saturated zone from the same well at contaminated areas. The innovative well design allows for concurrent sampling of groundwater and volatile organic compounds (VOCs) in the vadose (unsaturated) zone from a single well, saving considerable time and money. The sample tubes are banded to the outer well casing during installation of the well casing.

Vapor port and groundwater sampling well

DOEpatents

Hubbell, J.M.; Wylie, A.H.

1996-01-09

A method and apparatus have been developed for combining groundwater monitoring wells with unsaturated-zone vapor sampling ports. The apparatus allows concurrent monitoring of both the unsaturated and the saturated zone from the same well at contaminated areas. The innovative well design allows for concurrent sampling of groundwater and volatile organic compounds (VOCs) in the vadose (unsaturated) zone from a single well, saving considerable time and money. The sample tubes are banded to the outer well casing during installation of the well casing. 10 figs.

Estimating Unsaturated Zone N Fluxes and Travel Times to Groundwater at Watershed Scales

NASA Astrophysics Data System (ADS)

Liao, L.; Green, C. T.; Harter, T.; Nolan, B. T.; Juckem, P. F.; Shope, C. L.

2016-12-01

Nitrate concentrations in groundwater vary at spatial and temporal scales. Local variability depends on soil properties, unsaturated zone properties, hydrology, reactivity, and other factors. For example, the travel time in the unsaturated zone can cause contaminant responses in aquifers to lag behind changes in N inputs at the land surface, and variable leaching-fractions of applied N fertilizer to groundwater can elevate (or reduce) concentrations in groundwater. In this study, we apply the vertical flux model (VFM) (Liao et al., 2012) to address the importance of travel time of N in the unsaturated zone and its fraction leached from the unsaturated zone to groundwater. The Fox-Wolf-Peshtigo basins, including 34 out of 72 counties in Wisconsin, were selected as the study area. Simulated concentrations of NO3-, N2 from denitrification, O2, and environmental tracers of groundwater age were matched to observations by adjusting parameters for recharge rate, unsaturated zone travel time, fractions of N inputs leached to groundwater, O2 reduction rate, O2 threshold for denitrification, denitrification rate, and dispersivity. Correlations between calibrated parameters and GIS parameters (land use, drainage class and soil properties etc.) were evaluated. Model results revealed a median of recharge rate of 0.11 m/yr, which is comparable with results from three independent estimates of recharge rates in the study area. The unsaturated travel times ranged from 0.2 yr to 25 yr with median of 6.8 yr. The correlation analysis revealed that relationships between VFM parameters and landscape characteristics (GIS parameters) were consistent with expected relationships. Fraction N leached was lower in the vicinity of wetlands and greater in the vicinity of crop lands. Faster unsaturated zone transport in forested areas was consistent with results of studies showing rapid vertical transport in forested soils. Reaction rate coefficients correlated with chemical indicators such as Fe and P concentrations. Overall, the results demonstrate applicability of the VFM at a regional scale, as well as potential to generate N transport estimates continuously across regions based on statistical relationships between VFM model parameters and GIS parameters.

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.

Preliminary Interpretation of a Radionuclide and Colloid Tracer Test in a Granodiorite Shear Zone at the Grimsel Test Site, Switzerland

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

Reimus, Paul W.

2012-08-30

In February and March 2012, a tracer test involving the injection of a radionuclide-colloid cocktail was conducted in the MI shear zone at the Grimsel Test Site, Switzerland, as part of the Colloids Formation and Migration (CFM) project. The colloids were derived from FEBEX bentonite, which is mined in Spain and is being considered as a potential waste package backfill in a Spanish nuclear waste repository. The tracer test, designated test 12-02 (second test in 2012), involved the injection of the tracer cocktail into borehole CFM 06.002i2 and extraction from the Pinkel surface packer at the main access tunnel wallmore » approximately 6.1 m from the injection interval. The test configuration is depicted in Figure 1. This configuration has been used in several conservative tracer tests and two colloid-homologue tracer tests since 2007, and it is will be employed in an upcoming test involving the emplacement of a radionuclide-doped bentonite plug into CFM 06.002i2 to evaluate the swelling and erosion of the bentonite and the transport of bentonite colloids and radionuclides from the source to the extraction point at the tunnel wall. Interpretive analyses of several of the previous tracer tests, from 09-01 through 12-02 were provided in two previous Used Fuel Disposition Program milestone reports (Arnold et al., 2011; Kersting et al., 2012). However, only the data for the conservative tracer Amino-G Acid was previously analyzed from test 12-02 because the other tracer data from this test were not available at the time. This report documents the first attempt to quantitatively analyze the radionuclide and colloid breakthrough curves from CFM test 12-02. This report was originally intended to also include an experimental assessment of colloid-facilitated transport of uranium by bentonite colloids in the Grimsel system, but this assessment was not conducted because it was reported by German collaborators at the Karlsruhe Institute of Technology (KIT) that neither uranium nor neptunium adsorbed appreciably to FEBEX bentonite colloids in Grimsel groundwater (Huber et al., 2011). The Grimsel groundwater has a relatively high pH of {approx}9, so the lack of uranium and neptunium adsorption to clay is not surprising given the tendency for these actinides to form very stable negative or neutrally-charged uranyl- or calcium-uranyl-carbonate complexes at these pH, particularly in a water that is effectively saturated with respect to calcite. It was also observed in testing conducted at LANL earlier in 2012 that uranium did not adsorb measurably to Grimsel granodiorite in a synthetic Grimsel groundwater at pH {approx}8.5 (Kersting et al., 2012). Thus, the planned experimental work was not pursued because all the available information clearly pointed to an expected result that uranium transport would not be facilitated by clay colloids in the Grimsel system.« less

An updated model of induced airflow in the unsaturated zone

USGS Publications Warehouse

Baehr, Arthur L.; Joss, Craig J.

1995-01-01

Simulation of induced movement of air in the unsaturated zone provides a method to determine permeability and to design vapor extraction remediation systems. A previously published solution to the airflow equation for the case in which the unsaturated zone is separated from the atmosphere by a layer of lower permeability (such as a clay layer) has been superseded. The new solution simulates airflow through the layer of lower permeability more rigorously by defining the leakage in terms of the upper boundary condition rather than by adding a leakage term to the governing airflow equation. This note presents the derivation of the new solution. Formulas for steady state pressure, specific discharge, and mass flow in the domain are obtained for the new model and for the case in which the unsaturated zone is in direct contact with the atmosphere.

Conversion of Cn-Unsaturated into Cn-2-Saturated LCFA Can Occur Uncoupled from Methanogenesis in Anaerobic Bioreactors.

PubMed

Cavaleiro, Ana J; Pereira, Maria Alcina; Guedes, Ana P; Stams, Alfons J M; Alves, M Madalena; Sousa, Diana Z

2016-03-15

Fat, oils, and grease present in complex wastewater can be readily converted to methane, but the energy potential of these compounds is not always recyclable, due to incomplete degradation of long chain fatty acids (LCFA) released during lipids hydrolysis. Oleate (C18:1) is generally the dominant LCFA in lipid-containing wastewater, and its conversion in anaerobic bioreactors results in palmitate (C16:0) accumulation. The reason why oleate is continuously converted to palmitate without further degradation via β-oxidation is still unknown. In this work, the influence of methanogenic activity in the initial conversion steps of unsaturated LCFA was studied in 10 bioreactors continuously operated with saturated or unsaturated C16- and C18-LCFA, in the presence or absence of the methanogenic inhibitor bromoethanesulfonate (BrES). Saturated Cn-2-LCFA accumulated both in the presence and absence of BrES during the degradation of unsaturated Cn-LCFA, and represented more than 50% of total LCFA. In the presence of BrES further conversion of saturated intermediates did not proceed, not even when prolonged batch incubation was applied. As the initial steps of unsaturated LCFA degradation proceed uncoupled from methanogenesis, accumulation of saturated LCFA can be expected. Analysis of the active microbial communities suggests a role for facultative anaerobic bacteria in the initial steps of unsaturated LCFA biodegradation. Understanding this role is now imperative to optimize methane production from LCFA.

Transport of citrate-coated silver nanoparticles in unsaturated sand

NASA Astrophysics Data System (ADS)

Kumahor, Samuel; Hron, Pavel; Metreveli, George; Schaumann, Gabriele; Vogel, Hans-Jörg

2015-04-01

Chemical factors and physical constraints lead to coupled effects during particle transport in unsaturated porous media. Unlike for saturated transport, studies on unsaturated transport as typical for soil are currently scarce. We investigated the mobility of citrate-coated Ag NPs in unsaturated sand (grain diameter: 0.1-0.3 mm). For three flux rates and a given pore-water ionic strength (1 mM KNO3), the citrate-coated Ag NPs were less mobile at pH = 5 compared to pH = 9. The classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory suggests unfavorable deposition conditions at both, the air-water interface and solid-water interface. Breakthrough curves measured under quasi-steady state unsaturated flow showed retardation of the citrate-coated Ag NPs compared to inert solute (KBr). After flushing with nanoparticle-free 1 mM KNO3 solution (pH-adjusted), retention was much lower in deeper depths compared to the surface where the particles entered the flow field. The results show a non-linear dependence of nanoparticle (NP) mobility on flux rate and water content. Especially the observed retardation similar to equilibrium sorption is in contrast to observations under saturated flow conditions. A convection-dispersion and reaction model that combines a reversible equilibrium process and a non-equilibrium interaction process reproduced the measured breakthrough curves reasonably well. From comparison between saturated and unsaturated experiments we conclude that the air-water interface is responsible for the reversible equilibrium process while the water-solid interface accounts for irreversible soption.

Transport of elemental mercury in the unsaturated zone from a waste disposal site in an arid region

USGS Publications Warehouse

Walvoord, Michelle Ann; Andraski, Brian J.; Krabbenhoft, D.P.; Striegl, Robert G.

2008-01-01

Mercury contained in buried landfill waste may be released via upward emission to the atmosphere or downward leaching to groundwater. Data from the US Geological Survey’s Amargosa Desert Research Site (ADRS) in arid southwestern Nevada reveal another potential pathway of Hg release: long-distance (102 m) lateral migration of elemental Hg (Hg0) through the unsaturated zone. Gas collected from multiple depths from two instrumented boreholes that sample the entire 110-m unsaturated zone thickness and are located 100 and 160 m away from the closest waste burial trench exhibit gaseous Hg concentrations of up to 33 and 11 ng m−3, respectively. The vertical distribution of gaseous Hg in the borehole closest to the disposal site shows distinct subsurface peaks in concentration at depths of 1.5 and 24 m that cannot be explained by radial diffusive transport through a heterogeneous layered unsaturated zone. The inability of current models to explain gaseous Hg distribution at the ADRS highlights the need to advance the understanding of gas-phase contaminant transport in unsaturated zones to attain a comprehensive model of landfill Hg release.

2-Nonenal newly found in human body odor tends to increase with aging.

PubMed

Haze, S; Gozu, Y; Nakamura, S; Kohno, Y; Sawano, K; Ohta, H; Yamazaki, K

2001-04-01

Human body odor consists of various kinds of odor components. Here, we have investigated the changes in body odor associated with aging. The body odor of subjects between the ages of 26 and 75 was analyzed by headspace gas chromatography/mass spectrometry. 2-Nonenal, an unsaturated aldehyde with an unpleasant greasy and grassy odor, was detected only in older subjects (40 y or older). Furthermore, analysis of skin surface lipids revealed that omega7 unsaturated fatty acids and lipid peroxides also increased with aging and that there were positive correlations between the amount of 2-nonenal in body odor and the amount of omega7 unsaturated fatty acids or lipid peroxides in skin surface lipids. 2-Nonenal was generated only when omega7 unsaturated fatty acids were degraded by degradation tests in which some main components of skin surface lipids were oxidatively decomposed using lipid peroxides as initiator of an oxidative chain reaction. The results indicate that 2-nonenal is generated by the oxidative degradation of omega7 unsaturated fatty acids, and suggest that 2-nonenal may be involved in the age-related change of body odor.

TRPA1-dependent reversible opening of tight junction by natural compounds with an α,β-unsaturated moiety and capsaicin.

PubMed

Kanda, Yusuke; Yamasaki, Youhei; Sasaki-Yamaguchi, Yoshie; Ida-Koga, Noriko; Kamisuki, Shinji; Sugawara, Fumio; Nagumo, Yoko; Usui, Takeo

2018-02-02

The delivery of hydrophilic macromolecules runs into difficulties such as penetration of the cell membrane lipid bilayer. Our prior experiment demonstrated that capsaicin induces the reversible opening of tight junctions (TJs) and enhances the delivery of hydrophilic macromolecules through a paracellular route. Herein, we screened paracellular permeability enhancers other than capsaicin. As TJ opening by capsaicin is associated with Ca 2+ influx, we first screened the compounds that induce Ca 2+ influx in layered MDCK II cells, and then we determined the compounds' abilities to open TJs. Our results identified several natural compounds with α,β-unsaturated moiety. A structure-activity relationship (SAR) analysis and the results of pretreatment with reducing reagent DTT suggested the importance of α,β-unsaturated moiety. We also examined the underlying mechanisms, and our findings suggest that the actin reorganization seen in capsaicin treatment is important for the reversibility of TJ opening. Furthermore, our analyses revealed that TRPA1 is involved in the Ca 2+ influx and TJ permeability increase not only by an α,β-unsaturated compound but also by capsaicin. Our results indicate that the α,β-unsaturated moiety can be a potent pharmacophore for TJ opening.

Impact of Microorganisms on Unsatured Flow within Fractures

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

Daphne L. Stoner; Robert D. Stedtfeld; Tina L. Tyler

An experiment is described in which a groundwater bacterium, Sphingomonas sp., influenced the dynamics of unsaturated flow at a fracture intersection. A washed cell suspension increased by three-fold the length of time that water pooled at the fracture intersection. On the other hand, the addition of growth substrates resulted in cell growth and the conversion from intermittent to continuous flow behavior at the fracture intersection. The results suggest that microbial properties and processes need to be included with other important variables for understanding unsaturated flow in fractured geomatrices.

Polymeric matrix materials for infrared metamaterials

DOEpatents

Dirk, Shawn M; Rasberry, Roger D; Rahimian, Kamyar

2014-04-22

A polymeric matrix material exhibits low loss at optical frequencies and facilitates the fabrication of all-dielectric metamaterials. The low-loss polymeric matrix material can be synthesized by providing an unsaturated polymer, comprising double or triple bonds; partially hydrogenating the unsaturated polymer; depositing a film of the partially hydrogenated polymer and a crosslinker on a substrate; and photopatterning the film by exposing the film to ultraviolet light through a patterning mask, thereby cross-linking at least some of the remaining unsaturated groups of the partially hydrogenated polymer in the exposed portions.

Thermal history of the unsaturated zone at Yucca Mountain, Nevada, USA

USGS Publications Warehouse

Whelan, J.F.; Neymark, L.A.; Moscati, R.J.; Marshall, B.D.; Roedder, E.

2008-01-01

Secondary calcite, silica and minor amounts of fluorite deposited in fractures and cavities record the chemistry, temperatures, and timing of past fluid movement in the unsaturated zone at Yucca Mountain, Nevada, the proposed site of a high-level radioactive waste repository. The distribution and geochemistry of these deposits are consistent with low-temperature precipitation from meteoric waters that infiltrated at the surface and percolated down through the unsaturated zone. However, the discovery of fluid inclusions in calcite with homogenization temperatures (Th) up to ???80 ??C was construed by some scientists as strong evidence for hydrothermal deposition. This paper reports the results of investigations to test the hypothesis of hydrothermal deposition and to determine the temperature and timing of secondary mineral deposition. Mineral precipitation temperatures in the unsaturated zone are estimated from calcite- and fluorite-hosted fluid inclusions and calcite ??18O values, and depositional timing is constrained by the 207Pb/235U ages of chalcedony or opal in the deposits. Fluid inclusion Th from 50 samples of calcite and four samples of fluorite range from ???35 to ???90 ??C. Calcite ??18O values range from ???0 to ???22??? (SMOW) but most fall between 12 and 20???. The highest Th and the lowest ??18O values are found in the older calcite. Calcite Th and ??18O values indicate that most calcite precipitated from water with ??18O values between -13 and -7???, similar to modern meteoric waters. Twenty-two 207Pb/235U ages of chalcedony or opal that generally postdate elevated depositional temperatures range from ???9.5 to 1.9 Ma. New and published 207Pb/235U and 230Th/Uages coupled with the Th values and estimates of temperature from calcite ??18O values indicate that maximum unsaturated zone temperatures probably predate ???10 Ma and that the unsaturated zone had cooled to near-present-day temperatures (24-26 ??C at a depth of 250 m) by 2-4 Ma. The evidence of elevated temperatures persisting in ash flow tuffs adjacent to parent calderas for as much as ???8 Ma is a new finding, but consistent with thermal modeling. Simulations using the HEAT code demonstrate that prolonged cooling of the unsaturated zone is consistent with magmatic heat inputs and deep-seated (sub-water table) hydrothermal activity generated by the large magma body ???8 km to the north that produced the 15-11 Ma ash flows and ash falls that make up Yucca Mountain. The evidence discussed in this and preceding papers strongly supports unsaturated zone deposition of the secondary minerals from descending meteoric waters. Although depositional temperatures reflect conductive (and possibly vapor-phase convective) heating of the unsaturated zone related to regional magmatic sources until perhaps 6 Ma, depositional conditions similar to the present-day unsaturated zone have prevailed for at least the past 2-4 Ma.

Fate and Transport of CL-20 and RDX in Unsaturated Laboratory Columns

NASA Astrophysics Data System (ADS)

Lemond, L. A.; Gamerdinger, A. P.; Szecsody, J. E.

2005-05-01

This research examines the fate and transport of two explosive compounds, Hexanitrohexaazaisowurtzitane (CL-20) and Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in unsaturated laboratory columns. The transport and fate of these compounds were studied under saturated and unsaturated conditions in three natural soils: coarse sand, sandy loam, and a silt loam. Unsaturated column experiments were conducted using an ultra-centrifugation method. Sorption and degradation parameters were determined by moment analysis and hydrodynamic parameters were assessed with a two-region flow model. Differences in these parameters were evaluated as a function of water content. The fate and transport of CL-20 is highly dependent on 1) the soil type and 2) the compound's residence time in the soil and 3) water content of the media. Sorption of CL-20 was rate-limited. CL-20 degradation in saturated columns produced a half-life of as much as 22hr, but in unsaturated columns the degradation rate increased considerably, producing a half life of as little as 2hr. The fate and transport of RDX are also affected by the soil type, but sorption appeared to be instantaneous. Degradation of RDX was negligible. Our results suggest that at very low water content immobile water regions may become (at least in effect) isolated water regions and significantly alter the retardation of the tracer. In the sandy loam, there was as much as a 20-fold over-prediction of the retardation factor in the unsaturated saturated columns when predicted by Kd values derived from saturated columns. In the coarse sand, Kd values derived from saturated columns over-predicted retardation in the unsaturated columns by as much as 30%. In the silt loam, retardation factors were over-predicted by as much as 80%. At very low water contents, predictions of tracer behavior become very difficult because of changes in the flow regime that cannot be directly accounted for.

Unsaturated fatty acids promote bioaccessibility and basolateral secretion of carotenoids and α-tocopherol by Caco-2 cells.

PubMed

Failla, Mark L; Chitchumronchokchai, Chureeporn; Ferruzzi, Mario G; Goltz, Shellen R; Campbell, Wayne W

2014-06-01

Bioavailability of carotenoids and tocopherols from foods is determined by the efficiency of transfer from food/meal to mixed micelles during digestion, incorporation into chylomicrons for trans-epithelial transport to lymphatic/blood system, and distribution to target tissues. Fats and oils are important factors for facilitating the absorption of lipophilic compounds. However, dietary fats and oils are composed of various types of saturated and unsaturated fatty acids which may differentially impact the bioavailability of carotenoids and tocopherols from foods. We have investigated the effects of several common commercial lipids on bioavailability using an in vitro digestion model and Caco-2 human intestinal cells. Meals consisted of mixed salad vegetables containing a single test lipid. Micellarization and cellular uptake of β-carotene (βC) and lycopene (LYC) during small intestinal digestion was increased by lipids rich in unsaturated fatty acids: soybean oil > olive > canola > butter. In contrast, type of lipid minimally affected the bioaccessibility of lutein (LUT) and zeaxanthin (ZEA). To examine the influence of type of dietary triglyceride on uptake and basolateral secretion of carotenoids, Caco-2 cells grown on Transwell membranes were incubated with micellar mixtures of fatty acids (1.0 mM) mimicking the types and ratio of saturated to unsaturated (mono- + poly-unsaturated) fatty acids (FA) present in butter (70 : 30), olive oil (7 : 93) and soybean oil (11 : 89). Cells were exposed to micelles containing βC, LUT, α-tocopherol (α-TC) and a mixture of test fatty acids. Uptake and basolateral secretion of βC, LUT and α-TC were greater in cells pre-treated with mixtures enriched in unsaturated compared to saturated FA and these effects were mediated by increased assembly and secretion of chylomicrons. These results suggest that dietary fats/oils rich in unsaturated fatty acids promote carotenoid and α-TC bioavailability by enhancing their micellarization during digestion and intestinal transport.

Effect of fatty acids on self-assembly of soybean lecithin systems.

PubMed

Godoy, C A; Valiente, M; Pons, R; Montalvo, G

2015-07-01

With the increasing interest in natural formulations for drug administration and functional foods, it is desirable a good knowledge of the phase behavior of lecithin/fatty acid formulations. Phase structure and properties of ternary lecithin/fatty acids/water systems are studied at 37°C, making emphasis in regions with relatively low water and fatty acid content. The effect of fatty acid saturation degree on the phase microstructure is studied by comparing a fully saturated (palmitic acid, C16:0), monounsaturated (oleic acid, C18:1), and diunsaturated (linoleic acid, C18:2) fatty acids. Phase determinations are based on a combination of polarized light microscopy and small-angle X-ray scattering measurements. Interestingly, unsaturated (oleic acid and linoleic acid) fatty acid destabilizes the lamellar bilayer. Slight differences are observed between the phase diagrams produced by the unsaturated ones: small lamellar, medium cubic and large hexagonal regions. A narrow isotropic fluid region also appears on the lecithin-fatty acid axis, up to 8wt% water. In contrast, a marked difference in phase microsctructure was observed between unsaturated and saturated systems in which the cubic and isotropic fluid phases are not formed. These differences are, probably, a consequence of the high Krafft point of the C16 saturated chains that imply rather rigid chains. However, unsaturated fatty acids result in more flexible tails. The frequent presence of, at least, one unsaturated chain in phospholipids makes it very likely a better mixing situation than in the case of more rigid chains. This swelling potential favors the formation of reverse hexagonal, cubic, and micellar phases. Both unsaturated fatty acid systems evolve by aging, with a reduction of the extension of reverse hexagonal phase and migration of the cubic phase to lower fatty acid and water contents. The kinetic stability of the systems seems to be controlled by the unsaturation of fatty acids. Copyright © 2015 Elsevier B.V. All rights reserved.

Eco-friendly polyethylene glycol promoted Michael addition reactions of α,β-unsaturated carbonyl compounds

EPA Science Inventory

Abstract- Intra- and inter-nucleophilic addition reactions of different unsaturated compounds were found to be highly effective without any additives in PEG-400 as a recyclable reaction medium under neutral conditions.

[Relationship between the culture medium and the fatty acid composition of diphtheria and non-pathogenic corynebacteria].

PubMed

Vasiurenko, Z P; Siniak, K M

1977-04-01

The gasochromatic method was applied to the study of the cellular fatty acids composition in diphtheria and nonpathogenic corynebacteria (diphtheroids and psendo diptheria bacillus). Marked differences in the content of unsaturated fatty acids were revealed in them. Thus, palmito leic acid served the preponderant unsaturated fatty acid in Corynebacteria diphtheriae, and unsaturated fatty acids with 18 carbon atoms (octadeconoic and linoleic)--in nonpathogenic corynebacteria. The mentioned changes permit use this sign as differential. When grown on Loeffler's medium all the corynebacteria under study had a similar fatty acid composition characterized by the prevalence of unsaturated fatty acids with 18 carbon atoms. On the basis of studying the fatty acid spectrum of the nutrient media used it is supposed that one of the factors determining the revealed dependence of the corynebacterial fatty acid composition on the culture medium was the fatty acid composition of the latter.

Programming a hillslope water movement model on the MPP

NASA Technical Reports Server (NTRS)

Devaney, J. E.; Irving, A. R.; Camillo, P. J.; Gurney, R. J.

1987-01-01

A physically based numerical model was developed of heat and moisture flow within a hillslope on a parallel architecture computer, as a precursor to a model of a complete catchment. Moisture flow within a catchment includes evaporation, overland flow, flow in unsaturated soil, and flow in saturated soil. Because of the empirical evidence that moisture flow in unsaturated soil is mainly in the vertical direction, flow in the unsaturated zone can be modeled as a series of one dimensional columns. This initial version of the hillslope model includes evaporation and a single column of one dimensional unsaturated zone flow. This case has already been solved on an IBM 3081 computer and is now being applied to the massively parallel processor architecture so as to make the extension to the one dimensional case easier and to check the problems and benefits of using a parallel architecture machine.

Multicomponent Pt-Based Zigzag Nanowires as Selectivity Controllers for Selective Hydrogenation Reactions.

PubMed

Bai, Shuxing; Bu, Lingzheng; Shao, Qi; Zhu, Xing; Huang, Xiaoqing

2018-06-22

The selective hydrogenation of α, β-unsaturated aldehyde is an extremely important transformation, while developing efficient catalysts with desirable selectivity to highly value-added products is challenging, mainly due to the coexistence of two conjugated unsaturated functional groups. Herein, we report that a series of Pt-based zigzag nanowires (ZNWs) can be adopted as selectivity controllers for α, β-unsaturated aldehyde hydrogenation, where the excellent unsaturated alcohol (UOL) selectivity (>95%) and high saturated aldehyde (SA) selectivity (>94%) are achieved on PtFe ZNWs and PtFeNi ZNWs+AlCl 3 , respectively. The excellent UOL selectivity of PtFe ZNWs is attributed to the lower electron density of the surface Pt atoms, while the high SA selectivity of PtFeNi ZNWs+AlCl 3 is due to synergy between PtFeNi ZNWs and AlCl 3 , highlighting the importance of Pt-based NWs with precisely controlled surface and composition for catalysis and beyond.

Saturated-unsaturated flow in a compressible leaky-unconfined aquifer

NASA Astrophysics Data System (ADS)

Mishra, Phoolendra K.; Vesselinov, Velimir V.; Kuhlman, Kristopher L.

2012-06-01

An analytical solution is developed for three-dimensional flow towards a partially penetrating large-diameter well in an unconfined aquifer bounded below by a leaky aquitard of finite or semi-infinite extent. The analytical solution is derived using Laplace and Hankel transforms, then inverted numerically. Existing solutions for flow in leaky unconfined aquifers neglect the unsaturated zone following an assumption of instantaneous drainage due to Neuman. We extend the theory of leakage in unconfined aquifers by (1) including water flow and storage in the unsaturated zone above the water table, and (2) allowing the finite-diameter pumping well to partially penetrate the aquifer. The investigation of model-predicted results shows that aquitard leakage leads to significant departure from the unconfined solution without leakage. The investigation of dimensionless time-drawdown relationships shows that the aquitard drawdown also depends on unsaturated zone properties and the pumping-well wellbore storage effects.

Natural weathering in dry disposed ash dump: Insight from chemical, mineralogical and geochemical analysis of fresh and unsaturated drilled cores.

PubMed

Akinyemi, S A; Akinlua, A; Gitari, W M; Khuse, N; Eze, P; Akinyeye, R O; Petrik, L F

2012-07-15

Some existing alternative applications of coal fly ash such as cement manufacturing; road construction; landfill; and concrete and waste stabilisation use fresh ash directly collected from coal-fired power generating stations. Thus, if the rate of usage continues, the demand for fresh ash for various applications will exceed supply and use of weathered dry disposed ash will become necessary alternative. As a result it's imperative to understand the chemistry and pH behaviour of some metals inherent in dry disposed fly ash. The bulk chemical composition as determined by XRF analysis showed that SiO2, Al2O3 and Fe2O3 were the major oxides in fresh ash and unsaturated weathered ashes. The unsaturated weathered ashes are relatively depleted in CaO, Fe2O3, TiO2, SiO2, Na2O and P2O5 due to dissolution and hydrolysis caused by chemical interaction with ingressing CO2 from the atmosphere and infiltrating rain water. Observed accumulations of Fe2O3, TiO2, CaO, K2O, Na2O and SO3 and Zn, Zr, Sr, Pb, Ni, Cr and Co in the lower layers indicate progressive downward movement through the ash dump though at a slow rate. The bulk mineralogy of unsaturated weathered dry disposed ash, as determined by XRD analysis, revealed quartz and mullite as the major crystalline phases; while anorthite, hematite, enstatite, lime, calcite, and mica were present as minor mineral phases. Pore water chemistry revealed a low concentration of readily soluble metals in unsaturated weathered ashes in comparison with fresh ash, which shows high leachability. This suggests that over time the precipitation of transient minor secondary mineral phases; such as calcite and mica might retard residual metal release from unsaturated weathered ash. Chloride and sulphate species of the water soluble extracts of weathered ash are at equilibrium with Na+ and K+; these demonstrate progressive leaching over time and become supersaturated at the base of unsaturated weathered ash. This suggests that the ash dump does not encapsulate the salt or act as a sustainable salt sink due to over time reduction in pore water pH. The leaching behaviours of Ca, Mg, Na+, K+, Se, Cr and Sr are controlled by the pH of the leachant in both fresh and unsaturated weathered ash. Other trace metals like As, Mo and Pb showed amphoteric behaviour with respect to the pH of the leachant. The precipitation of minor quantities of secondary mineral phases in the unsaturated weathered ash has significant effects on the acid susceptibility and leaching patterns of chemical species in comparison with fresh ash. The unsaturated weathered ash had lower buffering capacity at neutral pH (7.94-8.00) compared to fresh (unweathered) ash. This may be due to the initial high leaching/flushing of soluble basic buffering constituents from fly ash after disposal. The overall results of the acid susceptibility tests suggest that both fresh ash and unsaturated weathered ash would release a large percentage of their chemical species when in contact with slightly acidified rain. Proper management of ash dumps is therefore essential to safeguard the environmental risks of water percolation in different fly ashes behaviour. Copyright © 2012 Elsevier Ltd. All rights reserved.

Liposomes composed of unsaturated lipids for membrane modification of human erythrocytes.

PubMed

Stoll, Christoph; Holovati, Jelena L; Acker, Jason P; Wolkers, Willem F

2011-01-01

Previous studies have shown that certain saturated lipids protect red blood cells (RBCs) during hypothermic storage but provide little protection during freezing or freeze-drying, whereas various unsaturated lipids destabilize RBCs during hypothermic storage but protect during freezing and freeze-drying. The protective effect of liposomes has been attributed to membrane modifications. We have previously shown that cholesterol exchange and lipid transfer between liposomes composed of saturated lipids and RBCs critically depends on the length of the lipid acyl chains. In this study the effect of unsaturated lipids with differences in their number of unsaturated bonds (18:0/18:1, 18:1/18:1, 18:2/18:2) on RBC membrane properties has been studied. RBCs were incubated in the presence of liposomes and both the liposomal and RBC fraction were analyzed by Fourier transform infrared spectroscopy (FTIR) after incubation. The liposomes caused an increase in RBC membrane conformational disorder at suprazero temperatures. The fluidizing effect of the liposomes on the RBC membranes, however, was found to be similar for the different lipids irrespective of their unsaturation level. The gel to liquid crystalline phase transition temperature of the liposomes increased after incubation with RBCs. RBC membrane fluidity increased linearly during the first 8 hours of incubation in the presence of liposomes. The increase in RBC membrane fluidity was found to be temperature dependent and displayed Arrhenius behaviour between 20 and 40°C, with an activation energy of 88 kJ mol⁻¹. Taken together, liposomes composed of unsaturated lipids increase RBC membrane conformational disorder, which could explain their cryoprotective action.

Estimating the timing and location of shallow rainfall-induced landslides using a model for transient, unsaturated infiltration

USGS Publications Warehouse

Baum, Rex L.; Godt, Jonathan W.; Savage, William Z.

2010-01-01

Shallow rainfall-induced landslides commonly occur under conditions of transient infiltration into initially unsaturated soils. In an effort to predict the timing and location of such landslides, we developed a model of the infiltration process using a two-layer system that consists of an unsaturated zone above a saturated zone and implemented this model in a geographic information system (GIS) framework. The model links analytical solutions for transient, unsaturated, vertical infiltration above the water table to pressure-diffusion solutions for pressure changes below the water table. The solutions are coupled through a transient water table that rises as water accumulates at the base of the unsaturated zone. This scheme, though limited to simplified soil-water characteristics and moist initial conditions, greatly improves computational efficiency over numerical models in spatially distributed modeling applications. Pore pressures computed by these coupled models are subsequently used in one-dimensional slope-stability computations to estimate the timing and locations of slope failures. Applied over a digital landscape near Seattle, Washington, for an hourly rainfall history known to trigger shallow landslides, the model computes a factor of safety for each grid cell at any time during a rainstorm. The unsaturated layer attenuates and delays the rainfall-induced pore-pressure response of the model at depth, consistent with observations at an instrumented hillside near Edmonds, Washington. This attenuation results in realistic estimates of timing for the onset of slope instability (7 h earlier than observed landslides, on average). By considering the spatial distribution of physical properties, the model predicts the primary source areas of landslides.

Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA

USGS Publications Warehouse

Hancock, T.C.; Sandstrom, M.W.; Vogel, J.R.; Webb, R.M.T.; Bayless, E.R.; Barbash, J.E.

2008-01-01

Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to > 0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0–4.9 μmol m−2 yr−1) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM).

Reduction of unsaturated compounds under interstellar conditions: chemoselective reduction of C≡C and C=C bonds over C=O functional group

NASA Astrophysics Data System (ADS)

Jonusas, Mindaugas; Guillemin, Jean-Claude; Krim, Lahouari

2017-07-01

The knowledge of the H-addition reactions on unsaturated organic molecules bearing a triple or a double carbon-carbon bond such as propargyl or allyl alcohols and a CO functional group such as propynal, propenal or propanal may play an important role in the understanding of the chemical complexity of the interstellar medium. Why different aldehydes like methanal, ethanal, propynal and propanal are present in dense molecular clouds while the only alcohol detected in those cold regions is methanol? In addition, ethanol has only been detected in hot molecular cores. Are those saturated and unsaturated aldehyde and alcohol species chemically linked in molecular clouds through solid phase H-addition surface reactions or are they formed through different chemical routes? To answer such questions, we have investigated a hydrogenation study of saturated and unsaturated aldehydes and alcohols at 10 K. We prove through this experimental study that while pure unsaturated alcohol ices bombarded by H atoms lead to the formation of the corresponding fully or partially saturated alcohols, surface H-addition reactions on unsaturated aldehyde ices exclusively lead to the formation of fully saturated aldehyde. Such results show that in addition to a chemoselective reduction of C≡C and C=C bonds over the C=O group, there is no link between aldehydes and their corresponding alcohols in reactions involving H atoms in dense molecular clouds. Consequently, this could be one of the reasons why some aldehydes such as propanal are abundant in dense molecular clouds in contrast to the non-detection of alcohol species larger than methanol.

CHEMFLO: ONE-DIMENSIONAL WATER AND CHEMICAL MOVEMENT IN UNSATURATED SOILS

EPA Science Inventory

An interactive software system was developed to enable decision-makers, regulators, policy-makers, scientists, consultants, and students to simulate the movement of waterand chemicals in unsaturated soils. Water movement is modeled using Richards (1931) - equation. Chemical trans...

Comparison of different filter methods for data assimilation in the unsaturated zone

NASA Astrophysics Data System (ADS)

Lange, Natascha; Berkhahn, Simon; Erdal, Daniel; Neuweiler, Insa

2016-04-01

The unsaturated zone is an important compartment, which plays a role for the division of terrestrial water fluxes into surface runoff, groundwater recharge and evapotranspiration. For data assimilation in coupled systems it is therefore important to have a good representation of the unsaturated zone in the model. Flow processes in the unsaturated zone have all the typical features of flow in porous media: Processes can have long memory and as observations are scarce, hydraulic model parameters cannot be determined easily. However, they are important for the quality of model predictions. On top of that, the established flow models are highly non-linear. For these reasons, the use of the popular Ensemble Kalman filter as a data assimilation method to estimate state and parameters in unsaturated zone models could be questioned. With respect to the long process memory in the subsurface, it has been suggested that iterative filters and smoothers may be more suitable for parameter estimation in unsaturated media. We test the performance of different iterative filters and smoothers for data assimilation with a focus on parameter updates in the unsaturated zone. In particular we compare the Iterative Ensemble Kalman Filter and Smoother as introduced by Bocquet and Sakov (2013) as well as the Confirming Ensemble Kalman Filter and the modified Restart Ensemble Kalman Filter proposed by Song et al. (2014) to the original Ensemble Kalman Filter (Evensen, 2009). This is done with simple test cases generated numerically. We consider also test examples with layering structure, as a layering structure is often found in natural soils. We assume that observations are water content, obtained from TDR probes or other observation methods sampling relatively small volumes. Particularly in larger data assimilation frameworks, a reasonable balance between computational effort and quality of results has to be found. Therefore, we compare computational costs of the different methods as well as the quality of open loop model predictions and the estimated parameters. Bocquet, M. and P. Sakov, 2013: Joint state and parameter estimation with an iterative ensemble Kalman smoother, Nonlinear Processes in Geophysics 20(5): 803-818. Evensen, G., 2009: Data assimilation: The ensemble Kalman filter. Springer Science & Business Media. Song, X.H., L.S. Shi, M. Ye, J.Z. Yang and I.M. Navon, 2014: Numerical comparison of iterative ensemble Kalman filters for unsaturated flow inverse modeling. Vadose Zone Journal 13(2), 10.2136/vzj2013.05.0083.

On the performance of capillary barriers as landfill cover

NASA Astrophysics Data System (ADS)

Kämpf, M.; Montenegro, H.

Landfills and waste heaps require an engineered surface cover upon closure. The capping system can vary from a simple soil cover to multiple layers of earth and geosynthetic materials. Conventional design features a compacted soil layer, which suffers from drying out and cracking, as well as root and animal intrusion. Capillary barriers consisting of inclined fine-over-coarse soil layers are investigated as an alternative cover system. Under unsaturated conditions, the textural contrast delays vertical drainage by capillary forces. The moisture that builds up above the contact will flow downdip along the interface of the layers. Theoretical studies of capillary barriers have identified the hydraulic properties of the layers, the inclination angle, the length of the field and the infiltration rate as the fundamental characteristics of the system. However, it is unclear how these findings can lead to design criteria for capillary barriers. To assess the uncertainty involved in such approaches, experiments have been carried out in a 8 m long flume and on large scale test sites (40 m x 15 m). In addition, the ability of a numerical model to represent the relevant flow processes in capillary barriers has been examined.

UNSODA UNSATURATED SOIL HYDRAULIC DATABASE USER'S MANUAL VERSION 1.0

EPA Science Inventory

This report contains general documentation and serves as a user manual of the UNSODA program. UNSODA is a database of unsaturated soil hydraulic properties (water retention, hydraulic conductivity, and soil water diffusivity), basic soil properties (particle-size distribution, b...

BIODEGRADATION OF HYDROCARBON VAPORS IN THE UNSATURATED ZONE

EPA Science Inventory

The time-averaged concentration of hydrocarbon and oxygen vapors were measured in the unsaturated zone above the residually contaminated capillary fringe at the U.S. Coast Guard Air Station in Traverse City, Michigan. Total hydrocarbon and oxygen vapor concentrations were observe...

Vadose zone microbiology

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

Kieft, Thomas L.; Brockman, Fred J.

2001-01-17

The vadose zone is defined as the portion of the terrestrial subsurface that extends from the land surface downward to the water table. As such, it comprises the surface soil (the rooting zone), the underlying subsoil, and the capillary fringe that directly overlies the water table. The unsaturated zone between the rooting zone and the capillary fringe is termed the "intermediate zone" (Chapelle, 1993). The vadose zone has also been defined as the unsaturated zone, since the sediment pores and/or rock fractures are generally not completely water filled, but instead contain both water and air. The latter characteristic results inmore » the term "zone of aeration" to describe the vadose zone. The terms "vadose zone," "unsaturated zone", and "zone of aeration" are nearly synonymous, except that the vadose zone may contain regions of perched water that are actually saturated. The term "subsoil" has also been used for studies of shallow areas of the subsurface immediately below the rooting zone. This review focuses almost exclusively on the unsaturated region beneath the soil layer since there is already an extensive body of literature on surface soil microbial communities and process, e.g., Paul and Clark (1989), Metting (1993), Richter and Markowitz, (1995), and Sylvia et al. (1998); whereas the deeper strata of the unsaturated zone have only recently come under scrutiny for their microbiological properties.« less

The Basicity of Unsaturated Hydrocarbons as probed by H-Bond Acceptor Ability. Bifurcated N–H+⋯π Hydrogen Bonding

PubMed Central

Stoyanov, Evgenii S.; Stoyanova, Irina V.; Reed, Christopher A.

2009-01-01

The competitive substitution of the anion in contact ion pairs of the type [Oct3NH+]B(C6F5)4− by unsaturated hydrocarbons L in accordance with the equilibrium Oct3NH+⋯Anion− + nL ↔ [Oct3NH+⋯Ln]Anion− has been studied in CCl4 solution. On the basis of equilibrium constants K and shifts of νNH to low frequency, it is established that complexed Oct3NH+⋯Ln cations with n = 1 and 2 are formed, having unidentate and bifurcated N–H+⋯π hydrogen bonds, respectively. Bifurcated H-bonds to unsaturated hydrocarbons have not been observed previously. The unsaturated hydro-carbons studied include benzene and methylbenzenes, fused-ring aromatics, alkenes, conjugated dienes, and alkynes. From the magnitude of the red shifts in N-H stretching frequencies, ΔνNH, a new scale for ranking the π-basicity of unsaturated hydrocarbons is proposed: fused-ring aromatics ≤ benzene < toluene < xylene < mesitylene < durene < conjugated dienes ∼ 1-alkynes < pentamethylbenzene < hexamethyl-benzene < internal alkynes ∼ cyclo-alkenes < 1-methylcycloalkenes. This scale is relevant to the discussion of π complexes for incipient protonation reactions and to understanding N–H+⋯π hydrogen bonding in proteins and molecular crystals. PMID:18637650

Diene Hydroacylation from the Alcohol or Aldehyde Oxidation Level via Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation: Synthesis of β,γ-Unsaturated Ketones

PubMed Central

Shibahara, Fumitoshi; Bower, John F.; Krische, Michael J.

2011-01-01

Under the conditions of ruthenium catalyzed transfer hydrogenation, isoprene couples to benzylic and aliphatic alcohols 1a–1g to deliver β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. Under identical conditions, aldehydes 2a–2g couple to isoprene to provide an identical set of β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. As demonstrated by the coupling of butadiene, myrcene and 1,2-dimethylbutadiene to representative alcohols 1b, 1c and 1e, diverse acyclic dienes participate in transfer hydrogenative coupling to form β,γ-unsaturated ketones. In all cases, complete branch-regioselectivity is observed and, with the exception of adduct 3j, isomerization to the conjugated enone is not detected. Thus, formal intermolecular diene hydroacylation is achieved from the alcohol or aldehyde oxidation level. In earlier studies employing a related ruthenium catalyst, acyclic dienes were coupled to carbonyl partners from the alcohol or aldehyde oxidation level to furnish branched homoallylic alcohols. Thus, under transfer hydrogenative coupling conditions, all oxidations levels of substrate (alcohol or aldehyde) and product (homoallyl alcohol or β,γ-unsaturated ketone) are accessible. PMID:18841895

ENGINEERING ISSUE: IN SITU BIOREMEDIATION OF CONTAMINATED UNSATURATED SUBSURFACE SOILS

EPA Science Inventory

An emerging technology for the remediation of unsaturated subsurface soils involves the use of microorganisms to degrade contaminants which are present in such soils. Understanding the processes which drive in situ bioremediation, as well as the effectiveness and efficiency of th...

Experimental investigations on mechanical behavior of unsaturated subgrade soil with lime stabilization and fiber reinforcement : final report.

DOT National Transportation Integrated Search

2003-11-01

In the present report, experimental investigations on mechanical behavior of unsaturated subgrade soil : with fiber reinforcement and lime stabilization were conducted. : The soil samples were collected from the soil/aggregate laboratory at the Maryl...

78 FR 28586 - Certain New Chemicals; Receipt and Status Information

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-15

... chemical. unsaturated, from fermentation. P-13-0319 3/1/2013 5/29/2013 CBI (G) Industrial (G) Glycerides, feedstock C14 18, C16-C18 chemical. unsaturated, from fermentation. P-13-0320 3/1/2013 5/29/2013 Nippon...

A GENERAL MASS-CONSERVATIVE NUMERICAL SOLUTION FOR THE UNSATURATED FLOW EQUATION

EPA Science Inventory

Numerical approximations based on different forms of the governing partial differential equation can lead to significantly different results for unsaturated flow problems. Numerical solution based on the standard h-based form of Richards equation generally yields poor results, ch...

Hydraulic Properties of Unsaturated Soils

USDA-ARS?s Scientific Manuscript database

Many agrophysical applications require knowledge of the hydraulic properties of unsaturated soils. These properties reflect the ability of a soil to retain or transmit water and its dissolved constituents. The objective of this work was to develop an entry for the Encyclopedia of Agrophysics that w...

Two-carbon homologation of aldehydes and ketones to a,ß-unsaturated aldehydes

USDA-ARS?s Scientific Manuscript database

Phosphonate reagents were developed for the two-carbon homologation of aldehydes or ketones to unbranched- or methyl-branched a,ß-unsaturated aldehydes. The phosphonate reagents, diethyl methylformyl-2-phosphonate dimethylhydrazone and diethyl ethylformyl-2-phosphonate dimethylhydrazone, contained a...

Groundwater recharge dynamics in unsaturated fractured chalk: a case study

NASA Astrophysics Data System (ADS)

Cherubini, Claudia; Pastore, Nicola; Giasi, Concetta I.; Allegretti, Nicolaetta M.

2016-04-01

The heterogeneity of the unsaturated zone controls its hydraulic response to rainfall and the extent to which pollutants are delayed or attenuated before reaching groundwater. It plays therefore a very important role in the recharge of aquifers and the transfer of pollutants because of the presence of temporary storage zones and preferential flows. A better knowledge of the physical processes in the unsaturated zone would allow an improved assessment of the natural recharge in a heterogeneous aquifer and of its vulnerability to surface-applied pollution. The case study regards the role of the thick unsaturated zone of the Cretaceous chalk aquifer in Picardy (North of France) that controls the hydraulic response to rainfall. In the North Paris Basin, much of the recharge must pass through a regional chalk bed that is composed of a porous matrix with embedded fractures. Different types of conceptual models have been formulated to explain infiltration and recharge processes in the unsaturated fractured rock. The present study analyses the episodic recharge in fractured Chalk aquifer using the kinematic diffusion theory to predict water table fluctuation in response to rainfall. From an analysis of the data, there is the evidence of 1) a seasonal behavior characterized by a constant increase in the water level during the winter/spring period and a recession period, 2) a series of episodic behaviors during the summer/autumn. Kinematic diffusion models are useful for predict preferential fluxes and dynamic conditions. The presented approach conceptualizes the unsaturated flow as a combination of 1) diffusive flow refers to the idealized portion of the pore space of the medium within the flow rate is driven essentially by local gradient of potential; 2) preferential flow by which water moves across macroscopic distances through conduits of macropore length.

Lipid droplets induced by secreted phospholipase A2 and unsaturated fatty acids protect breast cancer cells from nutrient and lipotoxic stress.

PubMed

Jarc, Eva; Kump, Ana; Malavašič, Petra; Eichmann, Thomas O; Zimmermann, Robert; Petan, Toni

2018-03-01

Cancer cells driven by the Ras oncogene scavenge unsaturated fatty acids (FAs) from their environment to counter nutrient stress. The human group X secreted phospholipase A 2 (hGX sPLA 2 ) releases FAs from membrane phospholipids, stimulates lipid droplet (LD) biogenesis in Ras-driven triple-negative breast cancer (TNBC) cells and enables their survival during starvation. Here we examined the role of LDs, induced by hGX sPLA 2 and unsaturated FAs, in protection of TNBC cells against nutrient stress. We found that hGX sPLA 2 releases a mixture of unsaturated FAs, including ω-3 and ω-6 polyunsaturated FAs (PUFAs), from TNBC cells. Starvation-induced breakdown of LDs induced by low micromolar concentrations of unsaturated FAs, including PUFAs, was associated with protection from cell death. Interestingly, adipose triglyceride lipase (ATGL) contributed to LD breakdown during starvation, but it was not required for the pro-survival effects of hGX sPLA 2 and unsaturated FAs. High micromolar concentrations of PUFAs, but not OA, induced oxidative stress-dependent cell death in TNBC cells. Inhibition of triacylglycerol (TAG) synthesis suppressed LD biogenesis and potentiated PUFA-induced cell damage. On the contrary, stimulation of LD biogenesis by hGX sPLA 2 and suppression of LD breakdown by ATGL depletion reduced PUFA-induced oxidative stress and cell death. Finally, lipidomic analyses revealed that sequestration of PUFAs in LDs by sPLA 2 -induced TAG remodelling and retention of PUFAs in LDs by inhibition of ATGL-mediated TAG lipolysis protect from PUFA lipotoxicity. LDs are thus antioxidant and pro-survival organelles that guard TNBC cells against nutrient and lipotoxic stress and emerge as attractive targets for novel therapeutic interventions. Copyright © 2017 Elsevier B.V. All rights reserved.

Protective Effect of Unsaturated Fatty Acids on Palmitic Acid-Induced Toxicity in Skeletal Muscle Cells is not Mediated by PPARδ Activation.

PubMed

Tumova, Jana; Malisova, Lucia; Andel, Michal; Trnka, Jan

2015-10-01

Unsaturated free fatty acids (FFA) are able to prevent deleterious effects of saturated FFA in skeletal muscle cells although the mechanisms involved are still not completely understood. FFA act as endogenous ligands of peroxisome proliferator-activated receptors (PPAR), transcription factors regulating the expression of genes involved in lipid metabolism. The aim of this study was to determine whether activation of PPARδ, the most common PPAR subtype in skeletal muscle, plays a role in mediating the protective effect of unsaturated FFA on saturated FFA-induced damage in skeletal muscle cells and to examine an impact on mitochondrial respiration. Mouse C2C12 myotubes were treated for 24 h with different concentrations of saturated FFA (palmitic acid), unsaturated FFA (oleic, linoleic and α-linolenic acid), and their combinations. PPARδ agonist GW501516 and antagonist GSK0660 were also used. Both mono- and polyunsaturated FFA, but not GW501516, prevented palmitic acid-induced cell death. Mono- and polyunsaturated FFA proved to be effective activators of PPARδ compared to saturated palmitic acid; however, in combination with palmitic acid their effect on PPARδ activation was blocked and stayed at the levels observed for palmitic acid alone. Unsaturated FFA at moderate physiological concentrations as well as GW501516, but not palmitic acid, mildly uncoupled mitochondrial respiration. Our results indicate that although unsaturated FFA are effective activators of PPARδ, their protective effect on palmitic acid-induced toxicity is not mediated by PPARδ activation and subsequent induction of lipid regulatory genes in skeletal muscle cells. Other mechanisms, such as mitochondrial uncoupling, may underlie their effect.

The effects of poly-unsaturated fatty acids on the physiology of hibernation in a South American marsupial, Dromiciops gliroides.

PubMed

Contreras, Carolina; Franco, Marcela; Place, Ned J; Nespolo, Roberto F

2014-11-01

Many mammals hibernate, which is a profound lethargic state of several weeks or months during winter, that represents a transitory episode of hetherothermy. As with other cases of dormancy, the main benefit of hibernation seems to be energy saving. However, the depth and duration of torpor can be experimentally modified by the composition of food, especially by fattyacid composition. In eutherians, diets rich in unsaturated fatty acids (i.e., fatty acids with at least one double bond) lengthen torpor, reduce metabolism and permit hibernation at lower temperatures. Here we studied whether diets varying in fatty acid composition have an effect on the physiology of hibernation in a South American marsupial, Dromiciops gliroides. We designed a factorial experiment where thermal acclimation (two levels: natural versus constant temperature) was combined with diet acclimation: saturated (i.e., diets with high concentration of saturated fatty acids) versus unsaturated (i.e., diets with high concentration of unsaturated fatty acids). We measured energy metabolism in active and torpid individuals, as well as torpor duration, and a suite of 12 blood biochemical parameters. After a cafeteria test, we found that D. gliroides did not show any preference for a given diet. Also, we did not find effects of diet on body temperature during torpor, or its duration. However, saturated diets, combined with high temperatures provoked a disproportionate increase in fat utilization, leading to body mass reduction. Those animals were more active, and metabolized more fats than those fed with a high proportion of unsaturated fatty acids (="unsaturated diets"). These results contrast with previous studies, which showed a significant effect of fatty acid composition of diets on food preferences and torpor patterns in mammals. Copyright © 2014 Elsevier Inc. All rights reserved.

Effect of Selection for High Activity-Related Metabolism on Membrane Phospholipid Fatty Acid Composition in Bank Voles.

PubMed

Stawski, Clare; Valencak, Teresa G; Ruf, Thomas; Sadowska, Edyta T; Dheyongera, Geoffrey; Rudolf, Agata; Maiti, Uttaran; Koteja, Paweł

2015-01-01

Endothermy, high basal metabolic rates (BMRs), and high locomotor-related metabolism were important steps in the evolution of mammals. It has been proposed that the composition of membrane phospholipid fatty acids plays an important role in energy metabolism and exercise muscle physiology. In particular, the membrane pacemaker theory of metabolism suggests that an increase in cell membrane fatty acid unsaturation would result in an increase in BMR. We aimed to determine whether membrane phospholipid fatty acid composition of heart, liver, and gastrocnemius muscles differed between lines of bank voles selected for high swim-induced aerobic metabolism-which also evolved an increased BMR-and unselected control lines. Proportions of fatty acids significantly differed among the organs: liver was the least unsaturated, whereas the gastrocnemius muscles were most unsaturated. However, fatty acid proportions of the heart and liver did not differ significantly between selected and control lines. In gastrocnemius muscles, significant differences between selection directions were found: compared to control lines, membranes of selected voles were richer in saturated C18:0 and unsaturated C18:2n-6 and C18:3n-3, whereas the pattern was reversed for saturated C16:0 and unsaturated C20:4n-6. Neither unsaturation index nor other combined indexes of fatty acid proportions differed between lines. Thus, our results do not support the membrane pacemaker hypothesis. However, the differences between selected and control lines in gastrocnemius muscles reflect chain lengths rather than number of double bonds and are probably related to differences in locomotor activity per se rather than to differences in the basal or routine metabolic rate.

Involvement of the CasK/R two-component system in optimal unsaturation of the Bacillus cereus fatty acids during low-temperature growth.

PubMed

Diomandé, Sara Esther; Nguyen-the, Christophe; Abee, Tjakko; Tempelaars, Marcel H; Broussolle, Véronique; Brillard, Julien

2015-11-20

Bacillus cereus sensu lato is composed of a set of ubiquitous strains including human pathogens that can survive a range of food processing conditions, grow in refrigerated food, and sometimes cause food poisoning. We previously identified the two-component system CasK/R that plays a key role in cold adaptation. To better understand the CasK/R-controlled mechanisms that support low-temperature adaptation, we performed a transcriptomic analysis on the ATCC 14579 strain and its isogenic ∆casK/R mutant grown at 12°C. Several genes involved in fatty acid (FA) metabolism were downregulated in the mutant, including desA and desB encoding FA acyl-lipid desaturases that catalyze the formation of a double-bond on the FA chain in positions ∆5 and ∆10, respectively. A lower proportion of FAs presumably unsaturated by DesA was observed in the ΔcasK/R strain compared to the parental strain while no difference was found for FAs presumably unsaturated by DesB. Addition of phospholipids from egg yolk lecithin rich in unsaturated FAs, to growth medium, abolished the cold-growth impairment of ΔcasK/R suggesting that exogenous unsaturated FAs can support membrane-level modifications and thus compensate for the decreased production of these FAs in the B. cereus ∆casK/R mutant during growth at low temperature. Our findings indicate that CasK/R is involved in the regulation of FA metabolism, and is necessary for cold adaptation of B. cereus unless an exogenous source of unsaturated FAs is available. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

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

Preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters

DOEpatents

Gogate, Makarand Ratnakar; Spivey, James Jerry; Zoeller, Joseph Robert

1998-01-01

Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

Preparation of {alpha},{beta}-unsaturated carboxylic acids and esters

DOEpatents

Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.

1998-09-15

Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

Selective α-arylation of α,β-unsaturated imides mediated by a visible light photoredox catalyst.

PubMed

Ando, Yuki; Kamatsuka, Takuto; Shinokubo, Hiroshi; Miyake, Yoshihiro

2017-08-10

Visible light-mediated α-arylation of α,β-unsaturated imides is achieved via aminium radicals generated from diarylalkylamines using a photoredox catalyst. On the basis of emission quenching experiments, a plausible pathway of the reaction is discussed.

Nutrition Research.

DTIC Science & Technology

1983-10-01

occurring" sugars 48% Refined and processed sugars 10% Total Fat Saturated fat 10% Poly-unsaturated fat 10% Mono-unsaturated fat 10% 30% Protein 12% 300% i 3...2120 Coffee, Black 2125 Coffee, Decaffeinated 2150 Coleslaw, French or CKD Salad Dressing 2540 Cream Puffs/Eclairs with Custard Filling 2715 Doughnut

Bacterial uptake of antibiotics in model unsaturated systems

NASA Astrophysics Data System (ADS)

Zhang, W.; Chen, Z.; Zhang, Y.; Zhao, Z.; Wang, G.; Gao, Y.; Boyd, S. A.; Zhu, D.; Li, H.

2016-12-01

Anthropogenic antibiotics are ubiquitously present in the environment due to large uses in human medicine and animal agriculture, and are causing unintended consequence to human and ecosystem health. Bacterial uptake of antibiotics could exert selection pressure on antibiotic resistance development among bacteria population. Therefore, understanding environmental factors controlling bioavailability of antibiotics to bacteria is critical to better assessing exposure risks and developing mitigation strategies. Nonetheless, conventional bioavailability assays are often performed in water-saturated systems that do not represent unsaturated soils where most bacteria live, therefore neglecting soil water as a controlling factor in determining the extent of antibiotic bacterial uptake. Therefore, we propose to study bacterial uptake of antibiotics in model unsaturated systems using GFP-tagged Escherichia coli bioreporter for tetracyclines. Our preliminary studies demonstrated the important role of water content (or water matric potential) in determining the bioavailability of antibiotics, and complex interactions of water potential, tetracycline diffusion, and E. coli growth. Therefore, unsaturated processes are important for understanding antibiotic resistance development and developing mitigation strategies.

Supplementation with bypass fat in silvopastoral systems diminishes the ratio of milk saturated/unsaturated fatty acids.

PubMed

Mahecha, L; Angulo, J; Salazar, B; Cerón, M; Gallo, J; Molina, C H; Molina, E J; Suárez, J F; Lopera, J J; Olivera, M

2008-04-01

This study was conducted to evaluate if supplementing bypass fat to cows under silvopastoral systems, increases the concentration of unsaturated fatty acids in milk, thus improving the saturated/ unsaturated ratio without a negative effect on total milk yield in fat or protein. Two concentrations of two different sources of bypass fat were evaluated for 40 days, each in a group of 24 multiparous Lucerna (Colombian breed) cows. A cross-over design of 8 Latin squares 3 x 3 was used. The variables submitted to analysis were body condition, daily milk production and milk composition. Body condition, milk yield and milk quality were not different but there was a significant decrease in the amount of saturated fatty acid in both experiments while the unsaturated fat increased significantly in experiment 1 and remained stable in experiment 2. Results, such as these have as far as we know, not been reported previously and they provide an approach for the improvement of milk as a "functional food".

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

Wu, Wenting; Zhang, Qinggang; Wang, Ruiqin

Unsaturated metal species (UMS) confined in nanomaterials play important roles for electron transfer in a wide range of catalytic reactions. However, the limited fabrication methods of UMS restrict their wider catalytic applications. Here in this paper, we report on the synergy of unsaturated Zn and Cu dopants confined in carbon dots (ZnCu-CDs) to produce enhanced electron transfer and photooxidation processes in the doped CDs. The Zn/Cu species chelate with the carbon matrix mainly through Cu-O(N)-Zn-O(N)-Cu complexes. Within this structure, Cu 2+ acts as a mild oxidizer that facilely increases the unsaturated Zn content and also precisely tunes the unsaturated Znmore » valence state to Zn d+, where d is between 1 and 2, instead of Zn. With the help of UMS, electron-transfer pathways are produced, enhancing both the electron donating (7.0 times) and-accepting (5.3 times) abilities relative to conventional CDs. Because of these synergistic effects, the photocatalytic efficiency of CDs in photooxidation reactions is shown to improve more than 5-fold.« less

Synthesis and stereochemical analysis of β-nitromethane substituted γ-amino acids and peptides.

PubMed

Ganesh Kumar, Mothukuri; Mali, Sachitanand M; Gopi, Hosahudya N

2013-02-07

The high diastereoselectivity in the Michael addition of nitromethane to α,β-unsaturated γ-amino esters, crystal conformations of β-nitromethane substituted γ-amino acids and peptides are studied. Results suggest that the N-Boc protected amide NH, conformations of α,β-unsaturated γ-amino esters and alkyl side chains play a crucial role in dictating the high diastereoselectivity of nitromethane addition to E-vinylogous amino esters. Investigation of the crystal conformations of both α,β-unsaturated γ-amino esters and the Michael addition products suggests that an H-C(γ)-C(β)=C(α) eclipsed conformer of the unsaturated amino ester leads to the major (anti) product compared to that of an N-C(γ)-C(β)=C(α) eclipsed conformer. The major diastereomers were separated and subjected to the peptide synthesis. The single crystal analysis of the dipeptide containing β-nitromethane substituted γ-amino acids reveals a helical type of folded conformation with an isolated H-bond involving a nine-atom pseudocycle.

Integrated assessment on groundwater nitrate by unsaturated zone probing and aquifer sampling with environmental tracers.

PubMed

Yuan, Lijuan; Pang, Zhonghe; Huang, Tianming

2012-12-01

By employing chemical and isotopic tracers ((15)N and (18)O in NO(3)(-)), we investigated the main processes controlling nitrate distribution in the unsaturated zone and aquifer. Soil water was extracted from two soil cores drilled in a typical agricultural cropping area of the North China Plain (NCP), where groundwater was also sampled. The results indicate that evaporation and denitrification are the two major causes of the distribution of nitrate in soil water extracts in the unsaturated zone. Evaporation from unsaturated zone is evidenced by a positive correlation between chloride and nitrate, and denitrification by a strong linear relationship between [Formula: see text] and ln(NO(3)(-)/Cl). The latter is estimated to account for up to 50% of the nitrate loss from soil drainage. In the saturated zone, nitrate is reduced at varying extents (100 mg/L and 10 mg/L at two sites, respectively), largely by dilution of the aquifer water. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

Determination of unsaturation grade and trans isomers generated during thermal oxidation of edible oils and fats by FTIR

NASA Astrophysics Data System (ADS)

Moya Moreno, M. C. M.; Mendoza Olivares, D.; Amézquita López, F. J.; Gimeno Adelantado, J. V.; Bosch Reig, F.

1999-05-01

The oxidative deterioration of culinary oils and fats during episodes of heating associated with normal usage (80°C-300°C, 20-40 min) was monitored by FTIR spectroscopy. The thermal oxidation of polyunsaturated fatty acids during heating was studied by the determination of unsaturation percentage and trans isomers at various temperatures and heating times. Oils frequently used in food frying such as olive oil, sunflower oil, corn oil and seeds oil (sunflower, safflower and canola seed), and lard were studied. The Absorbance Correction Method is proposed to correct the spectral interference and allows the analytic use of signal which would not be initially valid for quantitative analysis. The results show that there is a decrease in unsaturation and an increase in trans isomers starting at 150°C and becomes more pronounced at temperatures around 250°C. This variation in unsaturation grade and conformation provides evidence of the transformation of essential polyunsaturated fatty acids and subsequent decrease in the oils' nutritional value.

Lewis base activation of Lewis acids: catalytic, enantioselective vinylogous aldol addition reactions.

PubMed

Denmark, Scott E; Heemstra, John R

2007-07-20

The generality of Lewis base catalyzed, Lewis acid mediated, enantioselective vinylogous aldol addition reactions has been investigated. The combination of silicon tetrachloride and chiral phosphoramides is a competent catalyst for highly selective additions of a variety of alpha,beta-unsaturated ketone-, 1,3-diketone-, and alpha,beta-unsaturated amide-derived dienolates to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded high enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although alpha,beta-unsaturated ketone-derived dienolate did not react with aliphatic aldehydes, alpha,beta-unsaturated amide-derived dienolates underwent addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivities achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride-chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated.

Effect of hydrothermal carbonization on storage process of woody pellets: Pellets' properties and aldehydes/ketones emission.

PubMed

Li, Hui; Wang, Siyuan; Huang, Zhongliang; Yuan, Xingzhong; Wang, Ziliang; He, Rao; Xi, Yanni; Zhang, Xuan; Tan, Mengjiao; Huang, Jing; Mo, Dan; Li, Changzhu

2018-07-01

Effect of hydrothermal carbonization (HTC) on the hydrochar pelletization and the aldehydes/ketones emission from pellets during storage was investigated. Pellets made from the hydrochar were stored in sealed apparatuses for sampling. The energy consumption during pelletization and the pellets' properties before/after storage, including dimension, density, moisture content, hardness, aldehyde/ketones emission amount/rate and unsaturated fatty acid amount, were analyzed. Compared with untreated-sawdust-pellets, the hydrochar-pellets required more energy consumption for pelletization, and achieved the improved qualities, resulting in the higher stability degree during storage. The species and amount of unsaturated fatty acids in the hydrochar-pellets were higher than those in the untreated-sawdust-pellets. The unsaturated fatty acids content in the hydrochar-pellets was decreased with increasing HTC temperature. Higher aldehydes/ketones emission amount and rates with a longer emission period were found for the hydrochar-pellets, associated with variations of structure and unsaturated fatty acid composition in pellets. Copyright © 2018 Elsevier Ltd. All rights reserved.

Aquifer Recharge Estimation In Unsaturated Porous Rock Using Darcian And Geophysical Methods.

NASA Astrophysics Data System (ADS)

Nimmo, J. R.; De Carlo, L.; Masciale, R.; Turturro, A. C.; Perkins, K. S.; Caputo, M. C.

2016-12-01

Within the unsaturated zone a constant downward gravity-driven flux of water commonly exists at depths ranging from a few meters to tens of meters depending on climate, medium, and vegetation. In this case a steady-state application of Darcy's law can provide recharge rate estimates.We have applied an integrated approach that combines field geophysical measurements with laboratory hydraulic property measurements on core samples to produce accurate estimates of steady-state aquifer recharge, or, in cases where episodic recharge also occurs, the steady component of recharge. The method requires (1) measurement of the water content existing in the deep unsaturated zone at the location of a core sample retrieved for lab measurements, and (2) measurement of the core sample's unsaturated hydraulic conductivity over a range of water content that includes the value measured in situ. Both types of measurements must be done with high accuracy. Darcy's law applied with the measured unsaturated hydraulic conductivity and gravitational driving force provides recharge estimates.Aquifer recharge was estimated using Darcian and geophysical methods at a deep porous rock (calcarenite) experimental site in Canosa, southern Italy. Electrical Resistivity Tomography (ERT) and Vertical Electrical Sounding (VES) profiles were collected from the land surface to water table to provide data for Darcian recharge estimation. Volumetric water content was estimated from resistivity profiles using a laboratory-derived calibration function based on Archie's law for rock samples from the experimental site, where electrical conductivity of the rock was related to the porosity and water saturation. Multiple-depth core samples were evaluated using the Quasi-Steady Centrifuge (QSC) method to obtain hydraulic conductivity (K), matric potential (ψ), and water content (θ) estimates within this profile. Laboratory-determined unsaturated hydraulic conductivity ranged from 3.90 x 10-9 to 1.02 x 10-5 m/s over a volumetric water content range from 0.1938 to 0.4311 m3/m3. Using these measured properties, the water content estimated from geophysical measurements has been used to identify the unsaturated hydraulic conductivity indicative of the steady component of the aquifer recharge rate at Canosa.

Response of deep groundwater to land use change in desert basins of the Trans-Pecos region, Texas, USA: Effects on infiltration, recharge, and nitrogen fluxes

USGS Publications Warehouse

Robertson, Wendy Marie; Böhlke, John Karl; Sharp, John M.

2017-01-01

Quantifying the effects of anthropogenic processes on groundwater in arid regions can be complicated by thick unsaturated zones with long transit times. Human activities can alter water and nutrient fluxes, but their impact on groundwater is not always clear. This study of basins in the Trans-Pecos region of Texas links anthropogenic land use and vegetation change with alterations to unsaturated zone fluxes and regional increases in basin groundwater NO3−concentrations. Median increases in groundwater NO3− (by 0.7–0.9 mg-N/l over periods ranging from 10 to 50+ years) occurred despite low precipitation (220–360 mm/year), high potential evapotranspiration (~1570 mm/year), and thick unsaturated zones (10–150+ m). Recent model simulations indicate net infiltration and groundwater recharge can occur beneath Trans-Pecos basin floors, and may have increased due to irrigation and vegetation change. These processes were investigated further with chemical and isotopic data from groundwater and unsaturated zone cores. Some unsaturated zone solute profiles indicate flushing of natural salt accumulations has occurred. Results are consistent with human-influenced flushing of naturally accumulated unsaturated zone nitrogen as an important source of NO3− to the groundwater. Regional mass balance calculations indicate the mass of natural unsaturated zone NO3− (122–910 kg-N/ha) was sufficient to cause the observed groundwater NO3− increases, especially if augmented locally with the addition of fertilizer N. Groundwater NO3− trends can be explained by small volumes of high NO3− modern recharge mixed with larger volumes of older groundwater in wells. This study illustrates the importance of combining long-term monitoring and targeted process studies to improve understanding of human impacts on recharge and nutrient cycling in arid regions, which are vulnerable to the effects of climate change and increasing human reliance on dryland ecosystems.

Microbial dispersal in unsaturated porous media: Characteristics of motile bacterial cell motions in unsaturated angular pore networks

NASA Astrophysics Data System (ADS)

Ebrahimi, Ali N.; Or, Dani

2014-09-01

The dispersal rates of self-propelled microorganisms affect their spatial interactions and the ecological functioning of microbial communities. Microbial dispersal rates affect risk of contamination of water resources by soil-borne pathogens, the inoculation of plant roots, or the rates of spoilage of food products. In contrast with the wealth of information on microbial dispersal in water replete systems, very little is known about their dispersal rates in unsaturated porous media. The fragmented aqueous phase occupying complex soil pore spaces suppress motility and limits dispersal ranges in unsaturated soil. The primary objective of this study was to systematically evaluate key factors that shape microbial dispersal in model unsaturated porous media to quantify effects of saturation, pore space geometry, and chemotaxis on characteristics of principles that govern motile microbial dispersion in unsaturated soil. We constructed a novel 3-D angular pore network model (PNM) to mimic aqueous pathways in soil for different hydration conditions; within the PNM, we employed an individual-based model that considers physiological and biophysical properties of motile and chemotactic bacteria. The effects of hydration conditions on first passage times in different pore networks were studied showing that fragmentation of aquatic habitats under dry conditions sharply suppresses nutrient transport and microbial dispersal rates in good agreement with limited experimental data. Chemotactically biased mean travel speed of microbial cells across 9 mm saturated PNM was ˜3 mm/h decreasing exponentially to 0.45 mm/h for the PNM at matric potential of -15 kPa (for -35 kPa, dispersal practically ceases and the mean travel time to traverse the 9 mm PNM exceeds 1 year). Results indicate that chemotaxis enhances dispersal rates by orders of magnitude relative to random (diffusive) motions. Model predictions considering microbial cell sizes relative to available liquid pathways sizes were in good agreement with experimental results for unsaturated soils. The new modeling platform enables quantitative consideration of key biophysical factors (e.g., pore space heterogeneities and hydration conditions) governing microbial interactions in 3-D soil pore spaces.

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

[Stereoselective synthesis of polyhydroxylated amines using (S)-pyroglutamic acid derivatives].

PubMed

Ikota, Nobuo

2014-01-01

Naturally occurring polyhydroxylated amines such as (+)-1-deoxynojirimycin, polyoxamic acid, anisomycin, (-)swainsonine, and alexine stereoisomers, which have interesting biological activities including glucosidase- and mannosidase-inhibitory activity, immunoregulatory activity, and antibacterial effects, were synthesized stereoselectively starting from (S)-pyroglutamic acid derivatives. α,β-Unsaturated lactams ((S)-5-hydroxymethyl-2-oxo-3-pyrroline derivatives), α,β-unsaturated δ-lactone ((S)-4-amino-2-penten-5-olide derivative), and E-olefin ((S,E)-methyl-4-amino-5-hydroxypent-2-enoate derivative) from (S)-pyroglutamic acid derivatives were dihydroxylated using OsO4 in the presence of N-methyl morpholine N-oxide (NMO) to afford various chiral building blocks with different configurations. The stereoselectivity of cis-dihydroxylation for α,β-unsaturated lactams and α,β-unsaturated δ-lactone was very high, while the stereoselectivity was low for E-olefin. Therefore, the double asymmetric induction of E-olefin using K2OsO4 with chiral ligands was successively applied to yield high stereoselectivity. (2R,3S)-2-Hydroxymethyl-3-hydroxypyrrolidine and Gaissman-Weiss lactone, important intermediates for the preparation of pyrrolizidine alkaloids, were synthesized from a (3R,4R,5R)-3,4-dihydroxy-5-hydroxymethyl-2-pyrrolidinone derivative derived from α,β-unsatulated lactam. (+)-1-Deoxynojirimycin was synthesized from a (2S,3R,4R)-methyl 4-amino-2,3,5-trihydroxypentanoate derivative of E-olefin. (-)-Swainsonine and its stereoisomers were synthesized from (2R,3S,4R)- or (2R,3R,4R)-2-hydroxymethyl-3,4-dihydroxypyrrolidine derivatives of α,β-unsaturated δ-lactone or α,β-unsaturated lactam. The key reaction was diastereoselective allylation of the aldehyde derived from the corresponding 2-hydroxymethylpyrrolidine derivatives with various allylation reagents. The high diastereoselectivity could be explained by cyclic chelate formation between metals and the α-aminocarbonyl group or β-alkoxycarbonyl group, in which the nucleophile approaches from the less hindered face. Four alexine stereoisomers were synthesized from (2R,3R,4S,5R)- and (2R,3R,4S,5S)-2,3-dihydroxymethyl-3,4-dihydroxyl pyrrolidine derivatives of α,β-unsaturated lactam.

Pumping Test Determination of Unsaturated Aquifer Properties

NASA Astrophysics Data System (ADS)

Mishra, P. K.; Neuman, S. P.

2008-12-01

Tartakovsky and Neuman [2007] presented a new analytical solution for flow to a partially penetrating well pumping at a constant rate from a compressible unconfined aquifer considering the unsaturated zone. In their solution three-dimensional, axially symmetric unsaturated flow is described by a linearized version of Richards' equation in which both hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value, the latter defining the interface between the saturated and unsaturated zones. Both exponential functions are characterized by a common exponent k having the dimension of inverse length, or equivalently a dimensionless exponent kd=kb where b is initial saturated thickness. The authors used their solution to analyze drawdown data from a pumping test conducted by Moench et al. [2001] in a Glacial Outwash Deposit at Cape Cod, Massachusetts. Their analysis yielded estimates of horizontal and vertical saturated hydraulic conductivities, specific storage, specific yield and k . Recognizing that hydraulic conductivity and water content seldom vary identically with incremental capillary pressure head, as assumed by Tartakovsky and Neuman [2007], we note that k is at best an effective rather than a directly measurable soil parameter. We therefore ask to what extent does interpretation of a pumping test based on the Tartakovsky-Neuman solution allow estimating aquifer unsaturated parameters as described by more common constitutive water retention and relative hydraulic conductivity models such as those of Brooks and Corey [1964] or van Genuchten [1980] and Mualem [1976a]? We address this question by showing how may be used to estimate the capillary air entry pressure head k and the parameters of such constitutive models directly, without a need for inverse unsaturated numerical simulations of the kind described by Moench [2003]. To assess the validity of such direct estimates we use maximum likelihood- based model selection criteria to compare the abilities of numerical models based on the STOMP code to reproduce observed drawdowns during the test when saturated and unsaturated aquifer parameters are estimated either in the above manner or by means of the inverse code PEST.

Effects of unsaturated zone on ground-water mounding

USGS Publications Warehouse

Sumner, D.M.; Rolston, D.E.; Marino, M.A.

1999-01-01

The design of infiltration basins used to dispose of treated wastewater or for aquifer recharge often requires estimation of ground-water mounding beneath the basin. However, the effect that the unsaturated zone has on water-table response to basin infiltration often has been overlooked in this estimation. A comparison was made between two methods used to estimate ground-water mounding-an analytical approach that is limited to the saturated zone and a numerical approach that incorporates both the saturated and the unsaturated zones. Results indicate that the error that is introduced by a method that ignores the effects of the unsaturated zone on ground-water mounding increases as the basin-loading period is shortened; as the depth to the water table increases, with increasing subsurface anisotropy; and with the inclusion of fine-textured strata. Additionally, such a method cannot accommodate the dynamic nature of basin infiltration, the finite transmission time of the infiltration front to the water table, or the interception of the basin floor by the capillary fringe.The design of infiltration basins used to dispose of treated wastewater or for aquifer recharge often requires estimation of ground-water mounding beneath the basin. However, the effect that the unsaturated zone has on water-table response to basin infiltration often has been overlooked in this estimation. A comparison was made between two methods used to estimate ground-water mounding - an analytical approach that is limited to the saturated zone and a numerical approach that incorporates both the saturated and the unsaturated zones. Results indicate that the error that is introduced by a method that ignores the effects of the unsaturated zone on ground-water mounding increases as the basin-loading period is shortened; as the depth to the water table increases, with increasing subsurface anisotropy; and with the inclusion of fine-textured strata. Additionally, such a method cannot accommodate the dynamic nature of basin infiltration, the finite transmission time of the infiltration front to the water, or the interception of the basin floor by the capillary fringe.

Fundamental role of the fostriecin unsaturated lactone and implications for selective protein phosphatase inhibition.

PubMed

Buck, Suzanne B; Hardouin, Christophe; Ichikawa, Satoshi; Soenen, Danielle R; Gauss, C-M; Hwang, Inkyu; Swingle, Mark R; Bonness, Kathy M; Honkanen, Richard E; Boger, Dale L

2003-12-24

Key derivatives and analogues of fostriecin were prepared and examined that revealed a fundamental role for the unsaturated lactone and confirmed the essential nature of the phosphate monoester. Thus, an identical 200-fold reduction in protein phosphatase 2A (PP2A) inhibition is observed with either the saturated lactone (7) or with an analogue that lacks the entire lactone (15). This 200-fold increase in PP2A inhibition attributable to the unsaturated lactone potentially may be due to reversible C269 alkylation within the PP beta12-beta13 active site loop accounting for PP2A/4 potency and selectivity.

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

PubMed Central

2015-01-01

Summary The conjugate addition reaction has been a useful tool in the formation of carbon–carbon bonds. The utility of this reaction has been demonstrated in the synthesis of many natural products, materials, and pharmacological agents. In the last three decades, there has been a significant increase in the development of asymmetric variants of this reaction. Unfortunately, conjugate addition reactions using α,β-unsaturated amides and lactams remain underdeveloped due to their inherently low reactivity. This review highlights the work that has been done on both diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams. PMID:25977728

Response to Germann's "Comment on 'theory for source-responsive and free-surface film modeling of unsaturated flow'"

USGS Publications Warehouse

Nimmo, J.R.

2010-01-01

Germann's (2010) comment helpfully presents supporting evidence that I have missed, notes items that need clarification or correction, and stimulates discussion of what is needed for improved theory of unsaturated flow. Several points from this comment relate not only to specific features of the content of my paper (Nimmo, 2010), but also to the broader question of what methodology is appropriate for developing an applied earth science. Accordingly, before addressing specific points that Germann identified, I present here some considerations of purpose and background relevant to evaluation of the unsaturated flow model of Nimmo (2010).

Synthesis of 2-acyl-1,4-diketones via the diacylation of {alpha},{beta}-unsaturated ketones

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

Li, N.S.; Yu, S.; Kabalka, G.W.

1998-08-17

The first example of a diacylation of the carbon-carbon double bond in {alpha},{beta}-unsaturated ketones is described. The reaction of acylcyanocuprate reagents with {alpha},{beta}-unsaturated ketones, followed by C-acylation, produces 2-acyl-1,4-diketones in good yields (50--89%). The 1,4-addition of organocuprate reagents to conjugated enones, followed by trapping of the enolate intermediates with various electrophiles, is one of the most useful synthetic reactions. However, to the best of the authors` knowledge, 1,4-acylation followed by trapping of the enolate intermediates with acid chloride has not been reported.

Process for making unsaturated hydrocarbons using microchannel process technology

DOEpatents

Tonkovich, Anna Lee [Dublin, OH; Yuschak, Thomas [Lewis Center, OH; LaPlante, Timothy J [Columbus, OH; Rankin, Scott [Columbus, OH; Perry, Steven T [Galloway, OH; Fitzgerald, Sean Patrick [Columbus, OH; Simmons, Wayne W [Dublin, OH; Mazanec, Terry Daymo, Eric

2011-04-12

The disclosed invention relates to a process for converting a feed composition comprising one or more hydrocarbons to a product comprising one or more unsaturated hydrocarbons, the process comprising: flowing the feed composition and steam in contact with each other in a microchannel reactor at a temperature in the range from about 200.degree. C. to about 1200.degree. C. to convert the feed composition to the product, the process being characterized by the absence of catalyst for converting the one or more hydrocarbons to one or more unsaturated hydrocarbons. Hydrogen and/or oxygen may be combined with the feed composition and steam.

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

Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

DOEpatents

Sugama, Toshifumi; Kukacka, Lawrence E.; Horn, William H.

1985-01-01

Quick setting polymer concrete compositions with excellent structural properties are disclosed; these polymer concrete compositions are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate, which may be wet, and with a source of bivalent metallic ions.

Method for conversion of .beta.-hydroxy carbonyl compounds

DOEpatents

Lilga, Michael A.; White, James F.; Holladay, Johnathan E.; Zacher, Alan H.; Muzatko, Danielle S.; Orth, Rick J.

2010-03-30

A process is disclosed for conversion of salts of .beta.-hydroxy carbonyl compounds forming useful conversion products including, e.g., .alpha.,.beta.-unsaturated carbonyl compounds and/or salts of .alpha.,.beta.-unsaturated carbonyl compounds. Conversion products find use, e.g., as feedstock and/or end-use chemicals.

Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

DOEpatents

Sugama, T.; Kukacka, L.E.; Horn, W.H.

1981-11-04

Quick setting polymer concrete compositions which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

Two-Carbon Homologation of Ketones to 3-Methyl Unsaturated Aldehydes

USDA-ARS?s Scientific Manuscript database

The usual scheme of two-carbon homologation of ketones to 3-methyl unsaturated aldehydes by Horner-Wadsworth-Emmons condensations with phosphonate esters, such as triethyl-2-phosphonoacetate, involves three steps. The phosphonate condensation step results in extension of the carbon chain by two carb...

Monitoring radionuclide contamination in the unsaturated zone - Lessons learned at the Amargosa Desert Research Site, Nye County, Nevada

USGS Publications Warehouse

Stonestrom, David A.; Abraham, Jared D.; Andraski, Brian J.; Baker, Ronald J.; Mayers, C. Justin; Michel, Robert L.; Prudic, David E.; Striegl, Robert G.; Walvoord, Michelle Ann

2004-01-01

Contaminant-transport processes are being investigated at the U.S. Geological Survey’s Amargosa Desert Research Site (A DRS), adjacent to the Nation’s first commercial disposal facility for low-level radioactive waste. Gases containing tritium and radiocarbon are migrating through a 110-m thick unsaturated zone from unlined trenches that received waste from 1962 to 1992. Results relevant to long- term monitoring of radionuclides are summarized as follows. Contaminant plumes have unexpected histories and spatial configurations due to uncertainties in the: (1) geologic framework, (2) biochemical reactions involving waste components, (3) interactions between plume components and unsaturated-zone materials, (4) disposal practices, and (5) physical transport processes. Information on plume dynamics depends on ex-situ wet-chemical techniques because in-situ sensors for the radionuclides of interest do not exist. As at other radioactive-waste disposal facilities, radionuclides at the ADRS are mixed with varying amounts of volatile organic compounds (VOCs). Carbon-dioxide and VOC anomalies provide proxies for radioactive contamination. Contaminants in the unsaturated zone migrate along preferential pathways. Effective monitoring thus requires accurate geologic characterization. Direct- current electrical-resistivity imaging successfully mapped geologic units controlling preferential transport at the ADRS. Direct sampling of water from the unsaturated zone is complex and time consuming. Sampling plant water is an efficient alternative for mapping shallow tritium contamination.

Cytochrome b5 Reductase 1 Triggers Serial Reactions that Lead to Iron Uptake in Plants.

PubMed

Oh, Young Jun; Kim, Hanul; Seo, Sung Hee; Hwang, Bae Geun; Chang, Yoon Seok; Lee, Junho; Lee, Dong Wook; Sohn, Eun Ju; Lee, Sang Joon; Lee, Youngsook; Hwang, Inhwan

2016-04-04

Rhizosphere acidification is essential for iron (Fe) uptake into plant roots. Plasma membrane (PM) H(+)-ATPases play key roles in rhizosphere acidification. However, it is not fully understood how PM H(+)-ATPase activity is regulated to enhance root Fe uptake under Fe-deficient conditions. Here, we present evidence that cytochrome b5 reductase 1 (CBR1) increases the levels of unsaturated fatty acids, which stimulate PM H(+)-ATPase activity and thus lead to rhizosphere acidification. CBR1-overexpressing (CBR1-OX) Arabidopsis thaliana plants had higher levels of unsaturated fatty acids (18:2 and 18:3), higher PM H(+)-ATPase activity, and lower rhizosphere pH than wild-type plants. By contrast, cbr1 loss-of-function mutant plants showed lower levels of unsaturated fatty acids and lower PM H(+)-ATPase activity but higher rhizosphere pH. Reduced PM H(+)-ATPase activity in cbr1 could be restored in vitro by addition of unsaturated fatty acids. Transcript levels of CBR1, fatty acids desaturase2 (FAD2), and fatty acids desaturase3 (FAD3) were increased under Fe-deficient conditions. We propose that CBR1 has a crucial role in increasing the levels of unsaturated fatty acids, which activate the PM H(+)-ATPase and thus reduce rhizosphere pH. This reaction cascade ultimately promotes root Fe uptake. Copyright © 2016 The Author. Published by Elsevier Inc. All rights reserved.

Preferential flow, diffuse flow, and perching in an interbedded fractured-rock unsaturated zone

NASA Astrophysics Data System (ADS)

Nimmo, John R.; Creasey, Kaitlyn M.; Perkins, Kim S.; Mirus, Benjamin B.

2017-03-01

Layers of strong geologic contrast within the unsaturated zone can control recharge and contaminant transport to underlying aquifers. Slow diffuse flow in certain geologic layers, and rapid preferential flow in others, complicates the prediction of vertical and lateral fluxes. A simple model is presented, designed to use limited geological site information to predict these critical subsurface processes in response to a sustained infiltration source. The model is developed and tested using site-specific information from the Idaho National Laboratory in the Eastern Snake River Plain (ESRP), USA, where there are natural and anthropogenic sources of high-volume infiltration from floods, spills, leaks, wastewater disposal, retention ponds, and hydrologic field experiments. The thick unsaturated zone overlying the ESRP aquifer is a good example of a sharply stratified unsaturated zone. Sedimentary interbeds are interspersed between massive and fractured basalt units. The combination of surficial sediments, basalts, and interbeds determines the water fluxes through the variably saturated subsurface. Interbeds are generally less conductive, sometimes causing perched water to collect above them. The model successfully predicts the volume and extent of perching and approximates vertical travel times during events that generate high fluxes from the land surface. These developments are applicable to sites having a thick, geologically complex unsaturated zone of substantial thickness in which preferential and diffuse flow, and perching of percolated water, are important to contaminant transport or aquifer recharge.

Effects of Unsaturated Zones on Baseflow Recession: Analytical Solution and Application

NASA Astrophysics Data System (ADS)

Zhan, H.; Liang, X.; Zhang, Y. K.

2017-12-01

Unsaturated flow is an important process in baseflow recessions and its effect is rarely investigated. A mathematical model for a coupled unsaturated-saturated flow in a horizontally unconfined aquifer with time-dependent infiltrations is presented. Semi-analytical solutions for hydraulic heads and discharges are derived using Laplace transform and Cosine transform. The solutions are compared with solutions of the linearized Boussinesq equation (LB solution) and the linearized Laplace equation (LL solution), respectively. The result indicates that a larger dimensionless constitutive exponent κD of the unsaturated zone leads to a smaller discharge during the infiltration period and a larger discharge after the infiltration. The lateral discharge of the unsaturated zone is significant when κD≤1, and becomes negligible when κD≥100. For late times, the power index b of the recession curve-dQ/dt aQb, is 1 and independent of κD, where Q is the baseflow and a is a constant lumped aquifer parameter. For early times, b is approximately equal to 3 but it approaches infinity when t→1. The present solution is applied to synthetic and field cases. The present solution matched the synthetic data better than both the LL and LB solutions, with a minimum relative error of 16% for estimate of hydraulic conductivity. The present solution was applied to the observed streamflow discharge in Iowa, and the estimated values of the aquifer parameters were reasonable.

Increased Degree of Unsaturation in the Lipid of Antifungal Cationic Amphiphiles Facilitates Selective Fungal Cell Disruption.

PubMed

Steinbuch, Kfir B; Benhamou, Raphael I; Levin, Lotan; Stein, Reuven; Fridman, Micha

2018-05-11

Antimicrobial cationic amphiphiles derived from aminoglycosides act through cell membrane permeabilization but have limited selectivity for microbial cell membranes. Herein, we report that an increased degree of unsaturation in the fatty acid segment of antifungal cationic amphiphiles derived from the aminoglycoside tobramycin significantly reduced toxicity to mammalian cells. A collection of tobramycin-derived cationic amphiphiles substituted with C 18 lipid chains varying in degree of unsaturation and double bond configuration were synthesized. All had potent activity against a panel of important fungal pathogens including strains with resistance to a variety of antifungal drugs. The tobramycin-derived cationic amphiphile substituted with linolenic acid with three cis double bonds (compound 6) was up to an order of magnitude less toxic to mammalian cells than cationic amphiphiles composed of lipids with a lower degree of unsaturation and than the fungal membrane disrupting drug amphotericin B. Compound 6 was 12-fold more selective (red blood cell hemolysis relative to antifungal activity) than compound 1, the derivative with a fully saturated lipid chain. Notably, compound 6 disrupted the membranes of fungal cells without affecting the viability of cocultured mammalian cells. This study demonstrates that the degree of unsaturation and the configuration of the double bond in lipids of cationic amphiphiles are important parameters that, if optimized, result in compounds with broad spectrum and potent antifungal activity as well as reduced toxicity toward mammalian cells.

Preferential flow, diffuse flow, and perching in an interbedded fractured-rock unsaturated zone

USGS Publications Warehouse

Nimmo, John R.; Creasey, Kaitlyn M; Perkins, Kimberlie; Mirus, Benjamin B.

2017-01-01

Layers of strong geologic contrast within the unsaturated zone can control recharge and contaminant transport to underlying aquifers. Slow diffuse flow in certain geologic layers, and rapid preferential flow in others, complicates the prediction of vertical and lateral fluxes. A simple model is presented, designed to use limited geological site information to predict these critical subsurface processes in response to a sustained infiltration source. The model is developed and tested using site-specific information from the Idaho National Laboratory in the Eastern Snake River Plain (ESRP), USA, where there are natural and anthropogenic sources of high-volume infiltration from floods, spills, leaks, wastewater disposal, retention ponds, and hydrologic field experiments. The thick unsaturated zone overlying the ESRP aquifer is a good example of a sharply stratified unsaturated zone. Sedimentary interbeds are interspersed between massive and fractured basalt units. The combination of surficial sediments, basalts, and interbeds determines the water fluxes through the variably saturated subsurface. Interbeds are generally less conductive, sometimes causing perched water to collect above them. The model successfully predicts the volume and extent of perching and approximates vertical travel times during events that generate high fluxes from the land surface. These developments are applicable to sites having a thick, geologically complex unsaturated zone of substantial thickness in which preferential and diffuse flow, and perching of percolated water, are important to contaminant transport or aquifer recharge.

Migration of contaminants through the unsaturated zone overlying the Hesbaye chalky aquifer in Belgium: a field investigation.

PubMed

Brouyère, Serge; Dassargues, Alain; Hallet, Vincent

2004-08-01

This paper presents the results of a detailed field investigation that was performed for studying groundwater recharge processes and solute downward migration mechanisms prevailing in the unsaturated zone overlying a chalk aquifer in Belgium. Various laboratory measurements were performed on core samples collected during the drilling of boreholes in the experimental site. In the field, experiments consisted of well logging, infiltration tests in the unsaturated zone, pumping tests in the saturated zone and tracer tests in both the saturated and unsaturated zones. Results show that gravitational flows govern groundwater recharge and solute migration mechanisms in the unsaturated zone. In the variably saturated chalk, the migration and retardation of solutes is strongly influenced by recharge conditions. Under intense injection conditions, solutes migrate at high speed along the partially saturated fissures, downward to the saturated zone. At the same time, they are temporarily retarded in the almost immobile water located in the chalk matrix. Under normal recharge conditions, fissures are inactive and solutes migrate slowly through the chalk matrix. Results also show that concentration dynamics in the saturated zone are related to fluctuations of groundwater levels in the aquifer. A conceptual model is proposed to explain the hydrodispersive behaviour of the variably saturated chalk. Finally, the vulnerability of the chalk to contamination issues occurring at the land surface is discussed.

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.

40 CFR 265.278 - Unsaturated zone (zone of aeration) monitoring.

Code of Federal Regulations, 2012 CFR

2012-07-01

... soils nearby; this background monitoring must be conducted before or in conjunction with the monitoring... a minimum: (1) Soil monitoring using soil cores, and (2) Soil-pore water monitoring using devices... demonstrate in his unsaturated zone monitoring plan that: (1) The depth at which soil and soil-pore water...

40 CFR 264.278 - Unsaturated zone monitoring.

Code of Federal Regulations, 2011 CFR

2011-07-01

... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not been...

40 CFR 264.278 - Unsaturated zone monitoring.

Code of Federal Regulations, 2014 CFR

2014-07-01

... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not been...

40 CFR 265.278 - Unsaturated zone (zone of aeration) monitoring.

Code of Federal Regulations, 2011 CFR

2011-07-01

... soils nearby; this background monitoring must be conducted before or in conjunction with the monitoring... a minimum: (1) Soil monitoring using soil cores, and (2) Soil-pore water monitoring using devices... demonstrate in his unsaturated zone monitoring plan that: (1) The depth at which soil and soil-pore water...

40 CFR 264.278 - Unsaturated zone monitoring.

Code of Federal Regulations, 2012 CFR

2012-07-01

... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not been...

40 CFR 264.278 - Unsaturated zone monitoring.

Code of Federal Regulations, 2013 CFR

2013-07-01

... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not been...

40 CFR 265.278 - Unsaturated zone (zone of aeration) monitoring.

Code of Federal Regulations, 2010 CFR

2010-07-01

... soils nearby; this background monitoring must be conducted before or in conjunction with the monitoring... a minimum: (1) Soil monitoring using soil cores, and (2) Soil-pore water monitoring using devices... demonstrate in his unsaturated zone monitoring plan that: (1) The depth at which soil and soil-pore water...

40 CFR 265.278 - Unsaturated zone (zone of aeration) monitoring.

Code of Federal Regulations, 2014 CFR

2014-07-01

... soils nearby; this background monitoring must be conducted before or in conjunction with the monitoring... a minimum: (1) Soil monitoring using soil cores, and (2) Soil-pore water monitoring using devices... demonstrate in his unsaturated zone monitoring plan that: (1) The depth at which soil and soil-pore water...

40 CFR 264.278 - Unsaturated zone monitoring.

Code of Federal Regulations, 2010 CFR

2010-07-01

... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not been...

40 CFR 265.278 - Unsaturated zone (zone of aeration) monitoring.

Code of Federal Regulations, 2013 CFR

2013-07-01

... soils nearby; this background monitoring must be conducted before or in conjunction with the monitoring... a minimum: (1) Soil monitoring using soil cores, and (2) Soil-pore water monitoring using devices... demonstrate in his unsaturated zone monitoring plan that: (1) The depth at which soil and soil-pore water...

LIPID CLASS DISTRIBUTION OF HIGHLY UNSATURATED LONG CHAIN FATTY ACIDS IN MARINE DINOFLAGELLATES.

EPA Science Inventory

The very long chain highly unsaturated C28 fatty acids, octacosaheptaenoic [28:7(n-6)] and octacosaoctaenoic acid [28:8(n-3)], were found to be associated with phospholipids, obtained by fractionation of total lipid extracts into distinct lipid classes, in 4 and 6, respectively, ...

One-pot preparation of unsaturated polyester nanocomposites containing functionalized graphene sheets via a novel solvent-exchange method

USDA-ARS?s Scientific Manuscript database

This paper reports a convenient one-pot method integrating a novel solvent-exchange method into in situ melt polycondensation to fabricate unsaturated polyester nanocomposites containing functionalized graphene sheets (FGS). A novel solvent-exchange method was first developed to prepare graphene oxi...

Sophorolipid-derived unsaturated and epoxy fatty acid estolides as plasticizers for poly(3-hydroxybutyrate)

USDA-ARS?s Scientific Manuscript database

Unsaturated and epoxy fatty acid estolides were synthesized from the omega and omega-1 hydroxy fatty acids derived from sophorolipids (SLs) prepared by fermentation from glucose:soybean oil and glucose:oleic acid, respectively. These estolides were utilized as additives in solution-cast poly(3-hydro...

SIMULATING RADIONUCLIDE FATE AND TRANSPORT IN THE UNSATURATED ZONE: EVALUATION AND SENSITIVITY ANALYSES OF SELECT COMPUTER MODELS

EPA Science Inventory

Numerical, mathematical models of water and chemical movement in soils are used as decision aids for determining soil screening levels (SSLs) of radionuclides in the unsaturated zone. Many models require extensive input parameters which include uncertainty due to soil variabil...

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

USDA-ARS?s Scientific Manuscript database

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

HYDROGENATION OF UNSATURATED CARBONYLS IN SCCO2 AS REACTION MEDIUM OVER NI-SUPPORTED CATALYSTS

EPA Science Inventory

Selective hydrogenation of a, a unsaturated carbonyls where molecules containing C=C and C=O double bonds has both practical importance for fine chemicals industry and theoretical significance. Various studies are reported to enhance the selective hydrogenation of C=O over group...

EXPOXIDATION OF OLEFINS AND α,β-UNSATURATED KEYTONES OVER SONOCHEMICALLY PREPARED HYDROXYAPATITES USING HYDROGEN PEROXIDE

EPA Science Inventory

An effective and environmentally friendly protocol for the epoxidation of olefins and α,β-unsaturated ketones in the presence of hydroxyapatite as catalyst using hydrogen peroxide is described. The catalyst is active and reusable for the selective epoxidation of a variety...

ULTRASOUND-ASSISTED EPOXIDATION OF OLEFINS AND A,B-UNSATURATED KETONES OVER HYDROTALCITES USING HYDROGEN PEROXIDE

EPA Science Inventory

An efficient ultrasound-assisted epoxidation of olefins and a,B-unsaturated ketones over hydrotacite catalysts in the presence of hydrogen peroxide and acetonitrile is described. This general and selective protocol is relatively fast and is applicable to a wide variety of substra...

Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

DOEpatents

Sugama, T.; Kukacka, L.E.; Horn, W.H.

1983-05-13

Quick setting polymer concrete compositions are described which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

Physically-based landslide assessment for railway infrastructure

NASA Astrophysics Data System (ADS)

Heyerdahl, Håkon; Høydal, Øyvind

2017-04-01

A new high-speed railway line in Eastern Norway passes through areas with Quaternary soil deposits where stability of natural slopes poses considerable challenges. The ground typically consist of thick layers of marine clay deposits, overlain by 8-10 m of silt and sand. Both shallow landslides in the top layers of silt and sand and deep-seated failures in clay must be accounted for. In one section of the railway, the potential for performing stabilizing measures is limited due to existing cultural heritage on top of the slope. Hence, the stability of a steep top section of the slope needs to be evaluated. Assessment of the slope stability for rainfall-triggered slides relies on many parameters. An approach based only on empirical relations will not comply with the design criteria, which only allows deterministic safety margins. From a classic geotechnical approach, the slope would also normally be considered unsafe. However, considerable suction is assumed to exist in the silty and sandy deposits above ground-water level, which will improve the stability. The stabilizing effect however is highly dependent on rainfall, infiltration and soil moisture, and thereby varies continuously. An unsaturated geomechanical approach was taken to assess the slope stability. Soil moisture sensors were installed to monitor changes of in situ water content in the vadose zone. Retention curves for silt/sand specimens samples were measured by pressure plate tests. Some triaxial tests soil strength were performed to check the effect of suction on soil shear strength (performed as drained constant water content tests on compacted specimens). Based on the performed laboratory tests, the unsaturated response of the slope will be modelled numerically and compared with measured soil moisture in situ. Work is still on-going. Initial conditions after respectively dry and wet periods need to be coupled with selected rainfall intensities and duration to see the effect on slope stability. The aim of the work is to reach a result informing the client about the probability of a landslide in the slope, based on expected critical rainfall. A strictly deterministic criterion for minimum safety margin may need to be replaced by scenarios for probability and geometry of potential failures for given return periods and rainfall events.

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

PubMed

Brewster, Robert; Safran, Samuel A

2010-03-17

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

Steady state method to determine unsaturated hydraulic conductivity at the ambient water potential

DOEpatents

HUbbell, Joel M.

2014-08-19

The present invention relates to a new laboratory apparatus for measuring the unsaturated hydraulic conductivity at a single water potential. One or more embodiments of the invented apparatus can be used over a wide range of water potential values within the tensiometric range, requires minimal laboratory preparation, and operates unattended for extended periods with minimal supervision. The present invention relates to a new laboratory apparatus for measuring the unsaturated hydraulic conductivity at a single water potential. One or more embodiments of the invented apparatus can be used over a wide range of water potential values within the tensiometric range, requires minimal laboratory preparation, and operates unattended for extended periods with minimal supervision.

Effect of cheese as a fat replacer in fermented sausage.

PubMed

Ercoşkun, Hüdayi

2014-08-01

The effects of beef fat substitution with kashar cheese were studied in traditional Turkish fermented sausage; sucuk. Six sucuk formulations were prepared by replacing 0, 10, 20, 30, 40 and 50% of beef fat was substituted with kashar cheese. The fat substitution of fat with kashar cheese decreased fat content and increased protein content of the product that affected the chemical, physical and sensorial characteristics of products. Saturated fatty acid content increased and unsaturated, mono-unsaturated and poly-unsaturated fatty acids amount were decreased as the cheese amount increased. The formulation with 10% substitution of beef fat with cheese took the best sensory overall acceptability scores followed by 20% and control groups.

Two-carbon homologation of aldehydes and ketones to α,β-unsaturated aldehydes.

PubMed

Petroski, Richard J; Vermillion, Karl; Cossé, Allard A

2011-06-17

Phosphonate reagents were developed for the two-carbon homologation of aldehydes or ketones to unbranched- or methyl-branched α,β-unsaturated aldehydes. The phosphonate reagents, diethyl methylformyl-2-phosphonate dimethylhydrazone and diethyl ethylformyl-2-phosphonate dimethylhydrazone, contained a protected aldehyde group instead of the usual ester group. A homologation cycle entailed condensation of the reagent with the starting aldehyde, followed by removal of the dimethylhydrazone protective group with a biphasic mixture of 1 M HCl and petroleum ether. This robust two-step process worked with a variety of aldehydes and ketones. Overall isolated yields of unsaturated aldehyde products ranged from 71% to 86% after the condensation and deprotection steps.

Filtrates and Residues: Saturated and Unsaturated Fats: An Organic Chemistry Demonstration.

ERIC Educational Resources Information Center

Broniec, Rick

1985-01-01

Background information and procedures are provided for an experiment in which an oxidation reaction is used to distinguish saturated from unsaturated fats. Results of the experiment lead to discussions and investigations of such areas as digestion chemistry, enzymes, hydrogenation, and the relationship between heart disease and fat consumption.…

Predicting Unsaturated Zone Nitrogen Mass Balances in Agricultural Settings of the United States

USDA-ARS?s Scientific Manuscript database

Unsaturated zone N fate and transport were evaluated at four sites to identify the predominant pathways of N cycling: an almond orchard and cornfield in the lower Merced River study basin, California (CA); and corn-soybean rotations in study basins at Maple Creek, Nebraska (NE) and at Morgan Creek, ...

RISK OF UNSATURATED/SATURATED TRANSPORT AND TRANSFORMATION OF CHEMICAL CONCENTRATIONS (RUSTIC): VOLUME 1. THEORY AND CODE VERIFICATION

EPA Science Inventory

The RUSTIC program links three subordinate models--PRZM, VADOFT, and SAFTMOD--in order to predict pesticide transport and transformation through the crop root zone, the unsaturated zone, and the saturated zone to drinking water wells. PRZM is a one-dimensional finite-difference m...

Preparation of .alpha., .beta.-unsaturated carboxylic acids and anhydrides

DOEpatents

Spivey, James Jerry; Gogate, Makarand Ratnakav; Zoeller, Joseph Robert; Tustin, Gerald Charles

1998-01-01

Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

Preparation of {alpha}, {beta}-unsaturated carboxylic acids and anhydrides

DOEpatents

Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Tustin, G.C.

1998-01-20

Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

Heuristical Strategies on the Study Theme "The Unsaturated Hydrocarbons -- Alkenes"

ERIC Educational Resources Information Center

Naumescu, Adrienne Kozan; Pasca, Roxana-Diana

2011-01-01

The influence of heuristical strategies upon the level of two experimental classes is studied in this paper. The didactic experiment took place at secondary school in Cluj-Napoca, in 2008-2009 school year. The study theme "The Unsaturated Hydrocarbons--Alkenes" has been efficiently learned by using the most active methods: laboratory…

Lipase catalyzed epoxidation of fatty acid methyl esters derived from unsaturated vegetable oils in absence of carboxylic acid.

PubMed

Sustaita-Rodríguez, Alejandro; Ramos-Sánchez, Víctor H; Camacho-Dávila, Alejandro A; Zaragoza-Galán, Gerardo; Espinoza-Hicks, José C; Chávez-Flores, David

2018-04-11

Nowadays the industrial chemistry reactions rely on green technologies. Enzymes as lipases are increasing its use in diverse chemical processes. Epoxidized fatty acid methyl esters obtained from transesterification of vegetable oils have recently found applications as polymer plasticizer, agrochemical, cosmetics, pharmaceuticals and food additives. In this research article, grapeseed, avocado and olive oils naturally containing high percents of mono and poly unsaturations were used as starting materials for the production of unsaturated fatty acid methyl esters. The effect of lauric acid as an active oxygen carrier was studied on epoxidation reactions where unsaturated fatty acid methyl esters were converted to epoxy fatty acid methyl esters using immobilized Candida antarctica Lipase type B as catalyst and hydrogen peroxide as oxygen donor at mild temperature and pressure conditions. After this study it was confirmed by 1 H NMR, 13 C NMR and GC-MS that the addition of lauric acid to the enzymatic reaction is unnecessary to transform the alkenes in to epoxides. It was found that quantitative conversions were possible in despite of a carboxylic acid absence.

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.

Porous Pt-Ni Nanowires within In Situ Generated Metal-Organic Frameworks for Highly Chemoselective Cinnamaldehyde Hydrogenation.

PubMed

Zhang, Nan; Shao, Qi; Wang, Pengtang; Zhu, Xing; Huang, Xiaoqing

2018-05-01

Although chemoselective hydrogenation of unsaturated aldehydes is the major route to highly valuable industrially demanded unsaturated alcohols, it is still challenging, as the production of saturated aldehydes is more favorable over unsaturated alcohols from the view of thermodynamics. By combining the structural features of porous nanowires (NWs) and metal-organic frameworks (MOFs), a unique class of porous Pt-Ni NWs in situ encapsuled by MOFs (Pt-Ni NWs@Ni/Fex-MOFs) is designed to enhance the unsaturated alcohols selectivity in the cinnamaldehyde (CAL) hydrogenation. A detailed catalytic study shows that the porous Pt-Ni NWs@Ni/Fe x -MOFs exhibit volcano-type activity and selectivity in CAL hydrogenation as a function of Fe content. The optimized porous PtNi 2.20 NWs@Ni/Fe 4 -MOF is highly active and selective with 99.5% CAL conversion and 83.3% cinnamyl alcohol selectivity due to the confinement effect, appropriate thickness of MOF and its optimized electronic structure, and excellent durability with negligible activity and selectivity loss after five runs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new lumped-parameter model for flow in unsaturated dual-porosity media

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

Zimmerman, Robert W.; Hadgu, Teklu; Bodvarsson, Gudmundur S.

A new lumped-parameter approach to simulating unsaturated flow processes in dual-porosity media such as fractured rocks or aggregated soils is presented. Fluid flow between the fracture network and the matrix blocks is described by a non-linear equation that relates the imbibition rate to the local difference in liquid-phase pressure between the fractures and the matrix blocks. Unlike a Warren-Root-type equation, this equation is accurate in both the early and late time regimes. The fracture/matrix interflow equation has been incorporated into an existing unsaturated flow simulator, to serve as a source/sink term for fracture gridblocks. Flow processes are then simulated usingmore » only fracture gridblocks in the computational grid. This new lumped-parameter approach has been tested on two problems involving transient flow in fractured/porous media, and compared with simulations performed using explicit discretization of the matrix blocks. The new procedure seems to accurately simulate flow processes in unsaturated fractured rocks, and typically requires an order of magnitude less computational time than do simulations using fully-discretized matrix blocks. [References: 37]« 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.

Preferential dealkylation reactions of s-triazine herbicides in the unsaturated zone

USGS Publications Warehouse

Mills, M.S.; Michael, Thurman E.

1994-01-01

The preferential dealkylation pathways of the s-triazine herbicides, atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine), propazine [2-chloro-4,6-bis(isopropylamino)-s-triazine], and simazine [2-chloro-4,6-bis(ethylamino)-s-triazine], and two monodealkylated triazine metabolites, deisopropylatrazine (DIA: 2-amino-4-chloro-6-ethylamino-s-triazine) and deethylatrazine (DEA: 2-amino-4-chloro-6-isopropylamino-s-triazine) were investigated on two adjacent Eudora silt-loam plots growing corn (Zea mays L.). Results from the shallow unsaturated zone and surface-water runoff showed preferential removal of an ethyl side chain from atrazine, simazine, and DIA relative to an isopropyl side chain from atrazine, propazine, and DEA. It is hypothesized that deethylation reactions may proceed at 2-3 times the rate of deisopropylation reactions. It is concluded that small concentrations of DIA reportedly associated with the degradation of atrazine may be due to a rapid turnover rate of the metabolite in the unsaturated zone, not to small production levels. Because of continued dealkylation of both monodealkylated metabolites, a strong argument is advanced for the presence of a didealkylated metabolite in the unsaturated zone.

Quantifying the Effects of Biofilm on the Hydraulic Properties of Unsaturated Soils

NASA Astrophysics Data System (ADS)

Volk, E.; Iden, S.; Furman, A.; Durner, W.; Rosenzweig, R.

2017-12-01

Quantifying the effects of biofilms on hydraulic properties of unsaturated soils is necessary for predicting water and solute flow in soil with extensive microbial presence. This can be relevant to bioremediation processes, soil aquifer treatment and effluent irrigation. Previous works showed a reduction in the hydraulic conductivity and an increase in water content due to the addition of biofilm analogue materials. The objective of this research is to quantify soil hydraulic properties of unsaturated soil (water retention and hydraulic conductivity) using real soil biofilm. In this work, Hamra soil was incubated with Luria Broth (LB) and biofilm-producing bacteria (Pseudomonas Putida F1). Hydraulic conductivity and water retention were measured by the evaporation method, Dewpoint method and a constant head permeameter. Biofilm was quantified using viable counts and the deficit of TOC. The results show that the presence of biofilms increases soil retention in the `dry' range of the curve and reduces the hydraulic conductivity (see figure). This research shows that biofilms may have a non-negligible effect on flow and transport in unsaturated soils. These findings contribute to modeling water flow in biofilm amended soil.

Identification of predominant odorants in thai desserts flavored by smoking with "Tian Op", a traditional Thai scented candle.

PubMed

Watcharananun, Wanwarang; Cadwallader, Keith R; Huangrak, Kittiphong; Kim, Hun; Lorjaroenphon, Yaowapa

2009-02-11

"Tian Op", a traditional Thai scented candle, is used for the smoking and flavoring of sweets, cakes, and other desserts for the purpose of adding a unique aroma to the final product. Gas chromatography-olfactometry, aroma extract dilution analysis, and GC-MS were applied to identify the potent odorants in two types of traditional Thai desserts ("num dok mai" and "gleep lum duan") prepared using a Tian Op smoking process. On the basis of the results of AEDA and calculated odor-activity values, the predominant odorants in the Tian Op flavored desserts were vinyl ketones (C(5)-C(9)), n-aldehydes (C(5)-C(11)), (E)-2-unsaturated aldehydes (C(8)-C(11)), and omega-1-unsaturated aldehydes (C(8) and C(9)). Sensory studies of model mixtures confirmed the importance of n-aldehydes, omega-1-unsaturated aldehydes, and guaiacol as predominant odorants; however, the results showed that vinyl ketones and (E)-2-unsaturated aldehydes, despite having high odor-activity values, may be of only minor importance in the typical aroma profiles of traditional Tian Op smoked desserts.

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.

Assessment of groundwater quality by unsaturated zone study due to migration of leachate from Abloradjei waste disposal site, Ghana

NASA Astrophysics Data System (ADS)

Egbi, Courage Davidson; Akiti, Tetteh Thomas; Osae, Shiloh; Dampare, Samuel Boakye; Abass, Gibrilla; Adomako, Dickson

2017-05-01

Leachate generated by open solid waste disposal sites contains substances likely to contaminate groundwater. The impact of potential contaminants migrating from leachate on groundwater can be quantified by monitoring their concentration and soil properties at specific points in the unsaturated zone. In this study, physical and chemical analyses were carried out on leachate, soil and water samples within the vicinity of the municipal solid waste disposal site at Abloradjei, a suburb of Accra, Ghana. The area has seen a massive increase in population and the residents depend on groundwater as the main source of water supply. Results obtained indicate alkaline pH for leachate and acidic conditions for unsaturated zone water. High EC values were recorded for leachate and unsaturated zone water. Major ions (Ca2+, Na+, Mg2+, K+, NO3 -, SO4 2-, Cl-, PO4 3- were analysed in leachate, unsaturated zone water, soil solution and groundwater while trace metals (Al, Fe, Cu, Zn, Pb) were analysed in both soil and extracted soil solution. Concentrations of major ions were high in all samples indicating possible anthropogenic origin. Mean % gravel, % sand, % clay, bulk density, volumetric water content and porosity were 28.8, 63.93, 6.6, 1 g cm-3, 35 and 62.7 %, respectively. Distribution of trace elements showed Kd variation of Al > Cu > Fe > Pb > Zn in the order of sequential increasing solubility. It was observed that the quality of groundwater is not suitable for drinking.

Virus transport during infiltration of a wetting front into initially unsaturated sand columns.

PubMed

Kenst, Andrew B; Perfect, Edmund; Wilhelm, Steven W; Zhuang, Jie; McCarthy, John F; McKay, Larry D

2008-02-15

We investigated the effect of different flow conditions on the transport of bacteriophage phiX174 in Memphis aquifer sand. Virus transport associated with a wetting front moving into an initially unsaturated horizontal sand column was experimentally compared with that observed under steady-state saturated vertical flow. Results obtained by sectioning the sand columns showthattotal (retained and free) resident virus concentrations decreased approximately exponentially with the travel distance. The rate of decline was similar under both transient unsaturated flow and steady-state saturated flow conditions. Total resident virus concentrations near the inlet were an order of magnitude greater than the virus concentration of the influent solution in both experiments, indicating continuous virus sorption during flow through this zone. Virus retardation was quantified using the ratio of the centroids of the relative saturation and virus concentration versus relative distance functions. The mean retardation factors were 6.43 (coefficient of variation, CV = 14.4%) and 8.22 (CV = 8.22%) for the transient unsaturated and steady-state saturated flow experiments, respectively. Attest indicated no significant difference between these values at P < 0.05. Air-water and air-water-solid interfaces are thought to enhance virus inactivation and sorption to solid particles. The similar retardation factors obtained may be attributable to the reduced presence of these interfaces in the two flow systems investigated as compared to steady-state unsaturated flow experiments in which these interfaces occur throughout the entire column.

Saturated and Unsaturated Dietary Fats Differentially Modulate Ethanol-Induced Changes in Gut Microbiome and Metabolome in a Mouse Model of Alcoholic Liver Disease.

PubMed

Kirpich, Irina A; Petrosino, Joseph; Ajami, Nadim; Feng, Wenke; Wang, Yuhua; Liu, Yanlong; Beier, Juliane I; Barve, Shirish S; Yin, Xinmin; Wei, Xiaoli; Zhang, Xiang; McClain, Craig J

2016-04-01

Alcoholic liver disease (ALD) ranks among major causes of morbidity and mortality. Diet and crosstalk between the gut and liver are important determinants of ALD. We evaluated the effects of different types of dietary fat and ethanol on the gut microbiota composition and metabolic activity and the effect of these changes on liver injury in ALD. Compared with ethanol and a saturated fat diet (medium chain triglycerides enriched), an unsaturated fat diet (corn oil enriched) exacerbated ethanol-induced endotoxemia, liver steatosis, and injury. Major alterations in gut microbiota, including a reduction in Bacteroidetes and an increase in Proteobacteria and Actinobacteria, were seen in animals fed an unsaturated fat diet and ethanol but not a saturated fat diet and ethanol. Compared with a saturated fat diet and ethanol, an unsaturated fat diet and ethanol caused major fecal metabolomic changes. Moreover, a decrease in certain fecal amino acids was noted in both alcohol-fed groups. These data support an important role of dietary lipids in ALD pathogenesis and provide insight into mechanisms of ALD development. A diet enriched in unsaturated fats enhanced alcohol-induced liver injury and caused major fecal metagenomic and metabolomic changes that may play an etiologic role in observed liver injury. Dietary lipids can potentially serve as inexpensive interventions for the prevention and treatment of ALD. Copyright © 2016 American Society for Investigative Pathology. Published by Elsevier Inc. All rights reserved.

Multimodel analysis of anisotropic diffusive tracer-gas transport in a deep arid unsaturated zone

USGS Publications Warehouse

Green, Christopher T.; Walvoord, Michelle Ann; Andraski, Brian J.; Striegl, Robert G.; Stonestrom, David A.

2015-01-01

Gas transport in the unsaturated zone affects contaminant flux and remediation, interpretation of groundwater travel times from atmospheric tracers, and mass budgets of environmentally important gases. Although unsaturated zone transport of gases is commonly treated as dominated by diffusion, the characteristics of transport in deep layered sediments remain uncertain. In this study, we use a multimodel approach to analyze results of a gas-tracer (SF6) test to clarify characteristics of gas transport in deep unsaturated alluvium. Thirty-five separate models with distinct diffusivity structures were calibrated to the tracer-test data and were compared on the basis of Akaike Information Criteria estimates of posterior model probability. Models included analytical and numerical solutions. Analytical models provided estimates of bulk-scale apparent diffusivities at the scale of tens of meters. Numerical models provided information on local-scale diffusivities and feasible lithological features producing the observed tracer breakthrough curves. The combined approaches indicate significant anisotropy of bulk-scale diffusivity, likely associated with high-diffusivity layers. Both approaches indicated that diffusivities in some intervals were greater than expected from standard models relating porosity to diffusivity. High apparent diffusivities and anisotropic diffusivity structures were consistent with previous observations at the study site of rapid lateral transport and limited vertical spreading of gas-phase contaminants. Additional processes such as advective oscillations may be involved. These results indicate that gases in deep, layered unsaturated zone sediments can spread laterally more quickly, and produce higher peak concentrations, than predicted by homogeneous, isotropic diffusion models.

Structural Analysis of Unsaturated Glycosphingolipids Using Shotgun Ozone-Induced Dissociation Mass Spectrometry

NASA Astrophysics Data System (ADS)

Barrientos, Rodell C.; Vu, Ngoc; Zhang, Qibin

2017-08-01

Glycosphingolipids are essential biomolecules widely distributed across biological kingdoms yet remain relatively underexplored owing to both compositional and structural complexity. While the glycan head group has been the subject of most studies, there is paucity of reports on the lipid moiety, particularly the location of unsaturation. In this paper, ozone-induced dissociation mass spectrometry (OzID-MS) implemented in a traveling wave-based quadrupole time-of-flight (Q-ToF) mass spectrometer was applied to study unsaturated glycosphingolipids using shotgun approach. Resulting high resolution mass spectra facilitated the unambiguous identification of diagnostic OzID product ions. Using [M+Na]+ adducts of authentic standards, we observed that the long chain base and fatty acyl unsaturation had distinct reactivity with ozone. The reactivity of unsaturation in the fatty acyl chain was about 8-fold higher than that in the long chain base, which enables their straightforward differentiation. Influence of the head group, fatty acyl hydroxylation, and length of fatty acyl chain on the oxidative cleavage of double bonds was also observed. Application of this technique to bovine brain galactocerebrosides revealed co-isolated isobaric and regioisomeric species, which otherwise would be incompletely identified using contemporary collision-induced dissociation (CID) alone. These results highlight the potential of OzID-MS in glycosphingolipids research, which not only provides complementary structural information to existing CID technique but also facilitates de novo structural determination of these complex biomolecules. [Figure not available: see fulltext.

Hydrochemical evolution of sodium-sulfate and sodium-chloride groundwater beneath the Northern Chihuahuan Desert, Trans-Pecos, Texas, USA

USGS Publications Warehouse

Fisher, R.S.; Mullican, W. F.

1997-01-01

Groundwater beneath the northern Chihuahuan Desert, Trans-Pecos, Texas, USA, occurs in both carbonate and siliciclastic aquifers beneath a thick unsaturated zone and in shallow Rio Grande alluvium. Groundwater hydrochemical evolution was investigated by analyzing soils, soil leachates, bolson-fill sediments, water from the unsaturated zone, and groundwater from three major aquifers. Ionic relations, mineral saturation states, and geochemical modeling show that groundwater compositions are controlled by reactions in the unsaturated zone, mineralogy of unsaturated sediments and aquifers, position in the groundwater flow system, and extensive irrigation. Recharge to aquifers unaffected by irrigation is initially a Ca-HCO3 type as a result of dissolving carbonate surficial salts. With continued flow and mineral-water interaction, saturation with calcite and dolomite is maintained, gypsum is dissolved, and aqueous Ca and Mg are exchanged for adsorbed Na to produce a Na-SO4 water. Groundwater in Rio Grande alluvium is a Na-Cl type, reflecting river-water composition and the effects of irrigation, evapotranspiration, and surficial salt recycling. These results document two hydrochemical evolution paths for groundwater in arid lands. If recharge is dilute precipitation, significant changes in water chemistry can occur in unsaturated media, ion exchange can be as important as dissolution-precipitation reactions in determining groundwater composition, and mineral-water reactions ultimately control groundwater composition. If recharge is return flow of irrigation water that already contains appreciable solutes, mineral-water reactions are less important than irrigation-water composition in determining groundwater chemistry.

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.

The Impact of Organo-Mineral Complexation on Mineral Weathering in the Soil Zone under Unsaturated Conditions

NASA Astrophysics Data System (ADS)

Michael, H. A.; Tan, F.; Yoo, K.; Imhoff, P. T.

2017-12-01

While organo-mineral complexes can protect organic matter (OM) from biodegradation, their impact on soil mineral weathering is not clear. Previous bench-scale experiments that focused on specific OM and minerals showed that the adsorption of OM to mineral surfaces accelerates the dissolution of some minerals. However, the impact of natural organo-mineral complexes on mineral dissolution under unsaturated conditions is not well known. In this study, soil samples prepared from an undisturbed forest site were used to determine mineral weathering rates under differing conditions of OM sorption to minerals. Two types of soil samples were generated: 1) soil with OM (C horizon soil from 84-100cm depth), and 2) soil without OM (the same soil as in 1) but with OM removed by heating to 350°for 24 h). Soil samples were column-packed and subjected to intermittent infiltration and drainage to mimic natural rainfall events. Each soil sample type was run in duplicate. The unsaturated condition was created by applying gas pressure to the column, and the unsaturated chemical weathering rates during each cycle were calculated from the effluent concentrations. During a single cycle, when applying the same gas pressure, soils with OM retained more moisture than OM-removed media, indicating increased water retention capacity under the impact of OM. This is consistent with the water retention data measured by evaporation experiments (HYPROP) and the dew point method (WP4C Potential Meter). Correspondingly, silicon (Si) denudation rates indicated that dissolution of silicate minerals was 2-4 times higher in OM soils, suggesting that organo-mineral complexes accelerate mineral dissolution under unsaturated conditions. When combining data from all cycles, the results showed that Si denudation rates were positively related to soil water content: denundation rate increased with increasing water content. Therefore, natural mineral chemical weathering under unsaturated conditions, while widely considered to be facilitated by biological and chemical activities, may also be affected by soil retention properties.

Cerebral microvascular changes induced by rich cholesterol and saturated fatty acid diet in Wistar rats.

PubMed

Stănescu, R; Stănescu, M R; Bold, Adriana; Mateescu, Garofiţa Olivia

2013-01-01

The impact of an excess of fatty acids in the diet on cardiovascular diseases has been studied and discussed both in human and animal studies. Generally, excessive saturated fats increase the risk, while unsaturated fats are considered less harmful. Our aim was to perform an experimental study in order to analyze how fatty diet quality (unsaturated vs. saturated fatty acids) influences atherogenesis. In our experimental study, 18 adult Wistar rats were randomly divided into two equal groups. One group was subjected to a rich unsaturated fatty acid diet (untar) and the other group to a rich saturated one (palm oil). Three animals from each group were sacrificed after 12, 18, and 48 weeks. The brain was removed and microscopically examined after Hematoxylin-Eosin, Orcein and Masson's trichrome classical staining, and after immunohistochemical marking using the anti-alpha smooth muscle actin antibody. Rats sacrificed after 12 weeks revealed modicum lesions, as intimal vacuoles or minute intraluminal thrombosis, and cerebral parenchymal edema. After 18 weeks, some of rats subjected to a rich saturated fatty acid diet presented vacuoles found in all arteriolar wall layers, and a tendency towards parietal thrombosis. In rats subjected to a rich unsaturated fatty acid diet, the subintimal arteriolar vacuolization was associated with an intramural and adventitial fibrosis. In rats sacrificed after 48 weeks, lesional polymorphism was pronounced, but in rats subjected to a rich unsaturated fatty acid diet complete luminal thrombosis was followed by a an organized thrombus with multiple capillary channels. Although in Wistar rats atherosclerosis appeared only after intensive changes in diet, different experimental studies showed that, in transgenic rats, rich saturated fatty acid diet induced progressive atherosclerotic lesions, resembling those observed by us, but also some aspects described in human pathology. Our experimental study reveals differences in atherogenesis under saturated vs. unsaturated fatty diet.

Consequences of varied soil hydraulic and meteorological complexity on unsaturated zone time lag estimates.

PubMed

Vero, S E; Ibrahim, T G; Creamer, R E; Grant, J; Healy, M G; Henry, T; Kramers, G; Richards, K G; Fenton, O

2014-12-01

The true efficacy of a programme of agricultural mitigation measures within a catchment to improve water quality can be determined only after a certain hydrologic time lag period (subsequent to implementation) has elapsed. As the biophysical response to policy is not synchronous, accurate estimates of total time lag (unsaturated and saturated) become critical to manage the expectations of policy makers. The estimation of the vertical unsaturated zone component of time lag is vital as it indicates early trends (initial breakthrough), bulk (centre of mass) and total (Exit) travel times. Typically, estimation of time lag through the unsaturated zone is poor, due to the lack of site specific soil physical data, or by assuming saturated conditions. Numerical models (e.g. Hydrus 1D) enable estimates of time lag with varied levels of input data. The current study examines the consequences of varied soil hydraulic and meteorological complexity on unsaturated zone time lag estimates using simulated and actual soil profiles. Results indicated that: greater temporal resolution (from daily to hourly) of meteorological data was more critical as the saturated hydraulic conductivity of the soil decreased; high clay content soils failed to converge reflecting prevalence of lateral component as a contaminant pathway; elucidation of soil hydraulic properties was influenced by the complexity of soil physical data employed (textural menu, ROSETTA, full and partial soil water characteristic curves), which consequently affected time lag ranges; as the importance of the unsaturated zone increases with respect to total travel times the requirements for high complexity/resolution input data become greater. The methodology presented herein demonstrates that decisions made regarding input data and landscape position will have consequences for the estimated range of vertical travel times. Insufficiencies or inaccuracies regarding such input data can therefore mislead policy makers regarding the achievability of water quality targets. Copyright © 2014 Elsevier B.V. All rights reserved.

Moditored unsaturated soil transport processes as a support for large scale soil and water management

NASA Astrophysics Data System (ADS)

Vanclooster, Marnik

2010-05-01

The current societal demand for sustainable soil and water management is very large. The drivers of global and climate change exert many pressures on the soil and water ecosystems, endangering appropriate ecosystem functioning. The unsaturated soil transport processes play a key role in soil-water system functioning as it controls the fluxes of water and nutrients from the soil to plants (the pedo-biosphere link), the infiltration flux of precipitated water to groundwater and the evaporative flux, and hence the feed back from the soil to the climate system. Yet, unsaturated soil transport processes are difficult to quantify since they are affected by huge variability of the governing properties at different space-time scales and the intrinsic non-linearity of the transport processes. The incompatibility of the scales between the scale at which processes reasonably can be characterized, the scale at which the theoretical process correctly can be described and the scale at which the soil and water system need to be managed, calls for further development of scaling procedures in unsaturated zone science. It also calls for a better integration of theoretical and modelling approaches to elucidate transport processes at the appropriate scales, compatible with the sustainable soil and water management objective. Moditoring science, i.e the interdisciplinary research domain where modelling and monitoring science are linked, is currently evolving significantly in the unsaturated zone hydrology area. In this presentation, a review of current moditoring strategies/techniques will be given and illustrated for solving large scale soil and water management problems. This will also allow identifying research needs in the interdisciplinary domain of modelling and monitoring and to improve the integration of unsaturated zone science in solving soil and water management issues. A focus will be given on examples of large scale soil and water management problems in Europe.

Transport and time lag of chlorofluorocarbon gases in the unsaturated zone, Rabis Creek, Denmark

USGS Publications Warehouse

Engesgaard, Peter; Højberg, Anker L.; Hinsby, Klaus; Jensen, Karsten H.; Laier, Troels; Larsen, Flemming; Busenberg, Eurybiades; Plummer, Niel

2004-01-01

Transport of chlorofluorocarbon (CFC) gases through the unsaturated zone to the water table is affected by gas diffusion, air–water exchange (solubility), sorption to the soil matrix, advective–dispersive transport in the water phase, and, in some cases, anaerobic degradation. In deep unsaturated zones, this may lead to a time lag between entry of gases at the land surface and recharge to groundwater. Data from a Danish field site were used to investigate how time lag is affected by variations in water content and to explore the use of simple analytical solutions to calculate time lag. Numerical simulations demonstrate that either degradation or sorption of CFC-11 takes place, whereas CFC-12 and CFC-113 are nonreactive. Water flow did not appreciably affect transport. An analytical solution for the period with a linear increase in atmospheric CFC concentrations (approximately early 1970s to early 1990s) was used to calculate CFC profiles and time lags. We compared the analytical results with numerical simulations. The time lags in the 15-m-deep unsaturated zone increase from 4.2 to between 5.2 and 6.1 yr and from 3.4 to 3.9 yr for CFC-11 and CFC-12, respectively, when simulations change from use of an exponential to a linear increase in atmospheric concentrations. The CFC concentrations at the water table before the early 1990s can be estimated by displacing the atmospheric input function by these fixed time lags. A sensitivity study demonstrates conditions under which a time lag in the unsaturated zone becomes important. The most critical parameter is the tortuosity coefficient. The analytical approach is valid for the low range of tortuosity coefficients (τ = 0.1–0.4) and unsaturated zones greater than approximately 20 m in thickness. In these cases the CFC distribution may still be from either the exponential or linear phase. In other cases, the use of numerical models, as described in our work and elsewhere, is an option.

An analytical model for flow induced by a constant-head pumping in a leaky unconfined aquifer system with considering unsaturated flow

NASA Astrophysics Data System (ADS)

Lin, Ye-Chen; Li, Ming-Hsu; Yeh, Hund-Der

2017-09-01

A new mathematical model is developed to describe the flow in response to a constant-head pumping (or constant-head test, CHT) in a leaky unconfined aquifer system of infinite lateral extent with considering unsaturated flow. The model consists of an unsaturated zone on the top, an unconfined aquifer in the middle, and a second aquifer (aquitard) at the bottom. The unsaturated flow is described by Richard's equation, and the flows in unconfined aquifer and second layer are governed by the groundwater flow equation. The well partially penetrates the unconfined aquifer with a constant head in the well due to CHT. The governing equations of the model are linearized by the perturbation method and Gardner's exponential model is adopted to describe the soil retention curves. The solution of the model for drawdown distribution is obtained by applying the methods of Laplace transform and Weber transform. Then the solution for the wellbore flowrate is derived from the drawdown solution with Darcy's law. The issue of the equivalence of normalized drawdown predicted by the present solution for constant-head pumping and Tartakovsky and Neuman's (2007) solution for constant-rate pumping is discussed. On the basis of the wellbore flowrate solution, the results of the sensitivity analysis indicate that the wellbore flowrate is very sensitive to the changes in the radial hydraulic conductivity and the thickness of the saturated zone. Moreover, the results predicted from the present wellbore flowrate solution indicate that this new solution can reduce to Chang's et al. (2010a) solution for homogenous aquifers when the dimensionless unsaturated exponent approaches 100. The unsaturated zone can be considered as infinite extent in the vertical direction if the thickness ratio of the unsaturated zone to the unconfined aquifer is equal to or greater than one. As for the leakage effect, it can be ignored when the vertical hydraulic conductivity ratio (i.e., the vertical hydraulic conductivity of the lower layer over that of the unconfined aquifer) is smaller than 0.1. The present solution is compared with the numerical solution from FEMWATER for validation and the results indicate good match between these two solutions. Finally, the present solution is applied to a set of field drawdown data obtained from a CHT for the estimation of hydrogeologic parameters.

The impact of dietary fat withdrawal on carcass iodine value, belly characteristics, and changes in body fat over time.

PubMed

Kellner, T A; Prusa, K J; Patience, J F

2015-01-01

The inclusion of unsaturated fats in pig diets has raised issues related to pork carcass fat quality. The objective of this experiment was to understand how withdrawal from the diet of unsaturated dietary fat before slaughter impacts the composition of jowl fat during the growth cycle and at market. Fifty individually housed pigs (PIC 337 × C22/29; initial BW = 59.3 ± 0.55 kg) were allotted based on sex and initial BW to 10 treatments for an 82-d experiment as follows: 3 dietary fat withdrawal times before slaughter (21, 42, or 63 d) by 3 dietary fat unsaturation loads (DFUL), which includea high intake of unsaturated fatty acids supplied through an inclusion of 5% corn oil (HIGH), a high intake of a mixture of saturated and unsaturated fatty acids supplied through an inclusion of 5% animal-vegetable blend (MED), and a moderate intake of unsaturated fatty acids supplied through an inclusion of 2.5% corn oil (LOW). Pigs were weighed and jowl adipose samples were collected on d 0, 21, 42, and 63 and at harvest on d 82. Data were analyzed using PROC MIXED with treatment and sex as fixed effects. At market (d 82), increasing the withdrawal of dietary fat further away from market increased 18:1 (P = 0.045) and tended to increase 14:0 concentrations (P = 0.054). It also significantly decreased 18:2 (P < 0.001) and tended to decrease 18:3 concentrations (P = 0.081). A HIGH DFUL resulted in the greatest 18:2 concentrations in jowl fat followed by LOW; MED resulted in the lowest 18:2 levels (P < 0.001). Dietary fat withdrawal before market significantly reduced carcass iodine value (IV) measured at d 82 (P = 0.006). In conclusion, elevated 18:2 intake makes lowering carcass IV in the depot fat very difficult and may take as long as 61 d. The withdrawal of unsaturated dietary fat apparently altered the fat depot to be more reflective of fat synthesized de novo, resulting in a more saturated depot fat. Importantly, this alteration of deposited fat composition did not translate into improved belly firmness, depth, weight, or fat color.

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.

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

77 FR 14717 - National Oil and Hazardous Substances Pollution Contingency Plan; National Priorities List...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-03-13

... preclude future actions under Superfund. This partial deletion pertains to the surface soil, unsaturated subsurface soil, surface water and sediments of Operable Unit (OU) 1, the Gateway Lake Ash Study Area, and.... Surface soil, unsaturated subsurface soil, surface water, and sediments at OU-2, OU-3, OU-4, OU-5, OU-6...

Numerical convergence improvements for porflow unsaturated flow simulations

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

Flach, Greg

2017-08-14

Section 3.6 of SRNL (2016) discusses various PORFLOW code improvements to increase modeling efficiency, in preparation for the next E-Area Performance Assessment (WSRC 2008) revision. This memorandum documents interaction with Analytic & Computational Research, Inc. (http://www.acricfd.com/default.htm) to improve numerical convergence efficiency using PORFLOW version 6.42 for unsaturated flow simulations.

Aedes aegypti (Diptera: culicidae) biting deterrence: structure-activity relationship of saturated and unsaturated fatty acids

USDA-ARS?s Scientific Manuscript database

In this study we systematically evaluated for the first time the biting deterrent effects of a series of saturated and unsaturated fatty acids against Aedes aegypti [yellow fever mosquito (Diptera: Culicidae)] using the K & D bioassay system (Klun et al 2005). The saturated fatty acids (C6:0 to C16...

Acrolein with an alpha, beta-unsaturated Carbonyl Group Inhibits LPS-induced Homodimerization of Toll-like Receptor 4

USDA-ARS?s Scientific Manuscript database

Acrolein is a highly electrophilic a,ß-unsaturated aldehyde present in a number of environmental sources, especially cigarette smoke. It reacts strongly with the thiol groups of cysteine residues by Michael addition and has been reported to inhibit nuclear factor-kB (NF-kB) activation by lipopolysac...

PRZM-2, A MODEL FOR PREDICTING PESTICIDE FATE IN THE CROP ROOT AND UNSATURATED SOIL ZONES: USERS MANUAL FOR RELEASE 2.0

EPA Science Inventory

PRZM-2 links two subordinate models--PRZM and VADOFT--in order to predict pesticide transport and transformation down through the crop root and unsaturated zones. RZM is a one-dimensional, finite difference model that accounts for pesticide fate in the crop root zone. his release...

MICHIGAN SOIL VAPOR EXTRACTION REMEDIATION (MISER) MODEL: A COMPUTER PROGRAM TO MODEL SOIL VAPOR EXTRACTION AND BIOVENTING OF ORGANIC CHEMICALS IN UNSATURATED GEOLOGICAL MATERIAL

EPA Science Inventory

Soil vapor extraction (SVE) and bioventing (BV) are proven strategies for remediation of unsaturated zone soils. Mathematical models are powerful tools that can be used to integrate and quantify the interaction of physical, chemical, and biological processes occurring in field sc...

The acyl desaturase CER17 is involved in producing wax unsaturated primary alcohols and cutin monomers

USDA-ARS?s Scientific Manuscript database

We report here n-6 mono-unsaturated primary alcohols (the C26:1, C28:1, and C30:1 homologues) in the cuticular waxes of Arabidopsis inflorescence stem, a class of wax compound not previously reported in Arabidopsis. Further, we used mutation and transgenic complementation analyses to demonstrate tha...

Tung oil-based unsaturated co-ester macromonomer for thermosetting polymers: Synergetic synthesis and copolymerization with styrene

USDA-ARS?s Scientific Manuscript database

A novel unsaturated co-ester (co-UE) macromonomer containing both maleates and acrylates was synthesized from tung oil (TO) and its chemical structure was characterized by FT-IR, 1H-NMR, 13C-NMR, and gel permeation chromatography (GPC). The monomer was synthesized via a new synergetic modification o...

Free-Field Ground Shock Pressures from Buried Detonations in Saturated and Unsaturated Soils

DTIC Science & Technology

1983-05-01

pressures are, therefore, which is shown in Figure 4 and compared to the higher at various standoff distances, unsaturated soil solution and test data on...IK-82 an4 ?g-84 bombs. As can be seen, the hydrodynamic Instead of using a soil solution , the propaga- solution works much better and predicts much

RHODIUM CATALYZED CONJUGATED ADDITION OF UNSATURATED CARBONYL COMPOUNDS BY TRIPHENYLBISMUTH IN AQUEOUS MEDIA AND UNDER AN AIR ATMOSPHERE. (R822668)

EPA Science Inventory

Abstract

In the presence of a rhodium catalyst, ,-unsaturated est...

Negative Electrode For An Alkaline Cell

DOEpatents

Coco, Isabelle; Cocciantelli, Jean-Michel; Villenave, Jean-Jacques

1998-07-14

The present invention concerns a negative electrode for an alkaline cell, comprising a current collector supporting a paste containing an electrochemically active material and a binder, characterized in that said binder is a polymer containing hydrophilic and hydrophobic groups, said polymer being selected from an acrylic homopolymer, copolymer and terpolymer, an unsaturated organic acid copolymer and an unsaturated acid anhydride copolymer.

Fractal Analysis of Permeability of Unsaturated Fractured Rocks

PubMed Central

Jiang, Guoping; Shi, Wei; Huang, Lili

2013-01-01

A physical conceptual model for water retention in fractured rocks is derived while taking into account the effect of pore size distribution and tortuosity of capillaries. The formula of calculating relative hydraulic conductivity of fractured rock is given based on fractal theory. It is an issue to choose an appropriate capillary pressure-saturation curve in the research of unsaturated fractured mass. The geometric pattern of the fracture bulk is described based on the fractal distribution of tortuosity. The resulting water content expression is then used to estimate the unsaturated hydraulic conductivity of the fractured medium based on the well-known model of Burdine. It is found that for large enough ranges of fracture apertures the new constitutive model converges to the empirical Brooks-Corey model. PMID:23690746

Fractal analysis of permeability of unsaturated fractured rocks.

PubMed

Jiang, Guoping; Shi, Wei; Huang, Lili

2013-01-01

A physical conceptual model for water retention in fractured rocks is derived while taking into account the effect of pore size distribution and tortuosity of capillaries. The formula of calculating relative hydraulic conductivity of fractured rock is given based on fractal theory. It is an issue to choose an appropriate capillary pressure-saturation curve in the research of unsaturated fractured mass. The geometric pattern of the fracture bulk is described based on the fractal distribution of tortuosity. The resulting water content expression is then used to estimate the unsaturated hydraulic conductivity of the fractured medium based on the well-known model of Burdine. It is found that for large enough ranges of fracture apertures the new constitutive model converges to the empirical Brooks-Corey model.

Asymmetric conjugate 1,4-addition of arylboronic acids to alpha, beta-unsaturated esters catalyzed by Rhodium(I)/(S)-binap

PubMed

Sakuma; Sakai; Itooka; Miyaura

2000-09-22

Arylboronic acids underwent the conjugate 1,4-addition to alpha, beta-unsaturated esters to give beta-aryl esters in high yields in the presence of a rhodium(I) catalyst. The addition of arylboronic acids to isopropyl crotonate resulted in high yields and high enantioselectivity exceeding 90% ee in the presence of 3 mol % of Rh(acac)(C(2)H(4))(2) and (S)-binap at 100 degrees C. The rhodium/(S)-binap complex provided (R)-3-phenylbutanoate in the addition of phenylboronic acid to benzyl crotonate. The effects on the enantioselectivity of chiral phosphine ligands, rhodium precursors, and substituents on alpha,beta-unsaturated esters are discussed, as well as the mechanistic aspect of the catalytic cycle.

On Unsaturated Soil Mechanics - Personal Views on Current Research

NASA Astrophysics Data System (ADS)

Pande, G. N.; Pietruszczak, S.

2015-09-01

This paper presents the authors' personal views on current research being conducted by various research groups around the world in the broad area of mechanics of unsaturated geomaterials in general and soils in particular. The topic is of interest to a wide spectrum of scientists and engineers working in diverse areas such as geology and geophysics, powder technology, agricultural, petroleum, chemical, geotechnical, civil, environmental and nuclear engineering. Even if we restrict ourselves to civil, geotechnical and environmental engineering, it is noted that a plethora of hypotheses as well as a number of empirical and semi-empirical relations have been introduced for describing the mechanics of unsaturated porous media. However, many of these proposed advances as well as methods of testing may lack sound theoretical basis.

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.

Widespread natural perchlorate in unsaturated zones of the southwest United States

USGS Publications Warehouse

Rao, Balaji; Anderson, Todd A.; Orris, Greta J.; Rainwater, Ken A.; Rajagopalan, Srinath; Sandvig, Renee M.; Scanlon, Bridget R.; Stonestrom, David A.; Walvoord, Michelle Ann; Jackson, W Andrew

2007-01-01

A substantial reservoir (up to 1 kg ha-1) of natural perchlorate is present in diverse unsaturated zones of the arid and semi-arid southwestern United States. The perchlorate co-occurs with meteoric chloride that has accumulated in these soils throughout the Holocene [0 to 10−15 ka (thousand years ago)] and possibly longer periods. Previously, natural perchlorate widely believed to be limited to the Atacama Desert, now appears widespread in steppe-to-desert ecoregions. The perchlorate reservoir becomes sufficiently large to affect groundwater when recharge from irrigation or climate change flushes accumulated salts from the unsaturated zone. This new source may help explain increasing reports of perchlorate in dry region agricultural products and should be considered when evaluating overall source contributions.

Review of potential subsurface permeable barrier emplacement and monitoring technologies

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

Riggsbee, W.H.; Treat, R.L.; Stansfield, H.J.

1994-02-01

This report focuses on subsurface permeable barrier technologies potentially applicable to existing waste disposal sites. This report describes candidate subsurface permeable barriers, methods for emplacing these barriers, and methods used to monitor the barrier performance. Two types of subsurface barrier systems are described: those that apply to contamination.in the unsaturated zone, and those that apply to groundwater and to mobile contamination near the groundwater table. These barriers may be emplaced either horizontally or vertically depending on waste and site characteristics. Materials for creating permeable subsurface barriers are emplaced using one of three basic methods: injection, in situ mechanical mixing, ormore » excavation-insertion. Injection is the emplacement of dissolved reagents or colloidal suspensions into the soil at elevated pressures. In situ mechanical mixing is the physical blending of the soil and the barrier material underground. Excavation-insertion is the removal of a soil volume and adding barrier materials to the space created. Major vertical barrier emplacement technologies include trenching-backfilling; slurry trenching; and vertical drilling and injection, including boring (earth augering), cable tool drilling, rotary drilling, sonic drilling, jetting methods, injection-mixing in drilled holes, and deep soil mixing. Major horizontal barrier emplacement technologies include horizontal drilling, microtunneling, compaction boring, horizontal emplacement, longwall mining, hydraulic fracturing, and jetting methods.« less

Predicted Infiltration for Sodic/Saline Soils from Reclaimed Coastal Areas: Sensitivity to Model Parameters

PubMed Central

She, Dongli; Yu, Shuang'en; Shao, Guangcheng

2014-01-01

This study was conducted to assess the influences of soil surface conditions and initial soil water content on water movement in unsaturated sodic soils of reclaimed coastal areas. Data was collected from column experiments in which two soils from a Chinese coastal area reclaimed in 2007 (Soil A, saline) and 1960 (Soil B, nonsaline) were used, with bulk densities of 1.4 or 1.5 g/cm3. A 1D-infiltration model was created using a finite difference method and its sensitivity to hydraulic related parameters was tested. The model well simulated the measured data. The results revealed that soil compaction notably affected the water retention of both soils. Model simulations showed that increasing the ponded water depth had little effect on the infiltration process, since the increases in cumulative infiltration and wetting front advancement rate were small. However, the wetting front advancement rate increased and the cumulative infiltration decreased to a greater extent when θ 0 was increased. Soil physical quality was described better by the S parameter than by the saturated hydraulic conductivity since the latter was also affected by the physical chemical effects on clay swelling occurring in the presence of different levels of electrolytes in the soil solutions of the two soils. PMID:25197699

Predicted infiltration for sodic/saline soils from reclaimed coastal areas: sensitivity to model parameters.

PubMed

Liu, Dongdong; She, Dongli; Yu, Shuang'en; Shao, Guangcheng; Chen, Dan

2014-01-01

This study was conducted to assess the influences of soil surface conditions and initial soil water content on water movement in unsaturated sodic soils of reclaimed coastal areas. Data was collected from column experiments in which two soils from a Chinese coastal area reclaimed in 2007 (Soil A, saline) and 1960 (Soil B, nonsaline) were used, with bulk densities of 1.4 or 1.5 g/cm(3). A 1D-infiltration model was created using a finite difference method and its sensitivity to hydraulic related parameters was tested. The model well simulated the measured data. The results revealed that soil compaction notably affected the water retention of both soils. Model simulations showed that increasing the ponded water depth had little effect on the infiltration process, since the increases in cumulative infiltration and wetting front advancement rate were small. However, the wetting front advancement rate increased and the cumulative infiltration decreased to a greater extent when θ₀ was increased. Soil physical quality was described better by the S parameter than by the saturated hydraulic conductivity since the latter was also affected by the physical chemical effects on clay swelling occurring in the presence of different levels of electrolytes in the soil solutions of the two soils.

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.

Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Compounds

NASA Astrophysics Data System (ADS)

George, C.; Passananti, M.; Kong, L.; Shang, J.; Perrier, S.; Jianmin, C.; Donaldson, D. J.

2016-12-01

The atmospheric formation of organosulfur derivatives through reaction with SO2 is generally mediated by oxidants such as O3, OH; recently we have proposed a direct reaction between SO2 and unsaturated compounds as another possible pathway for organosulfate formation in the troposphere. For the first time it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds on various unsaturated compounds, and may therefore have a general environmental impact. We used different experimental strategies i.e., a coated flow tube (CFT), an aerosol flow tube (AFT) and a DRIFT (diffuse reflectance infrared Fourier transform) cell. The reaction products were analyzed by means of liquid chromatography coupled to a high resolution mass spectrometer (LC-HR-MS). We report indeed that SO2 reacts with large variety of C=C unsaturations and that even in the presence of ozone, SO2 reacts with OA leading to organosulfur products. A strong enhancement in product formation is observed under actinic illumination, increases the atmospheric significance of this chemical pathway. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could be in excess of 5%. The detection in atmospheric aerosols of organosulfur compounds with the same chemical formulae as the products identified here seems to confirm the importance of this reaction in the atmosphere.

Volatile organic compounds in the unsaturated zone from radioactive wastes

USGS Publications Warehouse

Baker, Ronald J.; Andraski, Brian J.; Stonestrom, David A.; Luo, Wentai

2012-01-01

Volatile organic compounds (VOCs) are often comingled with low-level radioactive wastes (LLRW), but little is known about subsurface VOC emanations from LLRW landfills. The current study systematically quantified VOCs associated with LLRW over an 11-yr period at the USGS Amargosa Desert Research Site (ADRS) in southwestern Nevada. Unsaturated-zone gas samples of VOCs were collected by adsorption on resin cartridges and analyzed by thermal desorption and GC/MS. Sixty of 87 VOC method analytes were detected in the 110-m-thick unsaturated zone surrounding a LLRW disposal facility. Chlorofluorocarbons (CFCs) were detected in 100% of samples collected. Chlorofluorocarbons are powerful greenhouse gases, deplete stratospheric ozone, and are likely released from LLRW facilities worldwide. Soil-gas samples collected from a depth of 24 m and a horizontal distance 100 m south of the nearest waste-disposal trench contained >60,000 ppbv total VOCs, including >37,000 ppbv CFCs. Extensive sampling in the shallow unsaturated zone (0–2 m deep) identified areas where total VOC concentrations exceeded 5000 ppbv at the 1.5-m depth. Volatile organic compound concentrations exceeded background levels up to 300 m from the facility. Maximum vertical diffusive fluxes of total VOCs were estimated to be 1 g m-2 yr-1. Volatile organic compound distributions were similar but not identical to those previously determined for tritium and elemental mercury. To our knowledge, this study is the first to characterize the unsaturated zone distribution of VOCs emanating from a LLRW landfill. Our results may help explain anomalous transport of radionuclides at the ADRS and elsewhere.

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.

Mechanical properties of three layer glass fibre reinforced unsaturated polyester filled with P84 Polyimide

NASA Astrophysics Data System (ADS)

Ibrahim, Nik Noor Idayu Nik; Mamauod, Siti Nur Liyana; Romli, Ahmad Zafir

2017-12-01

The glass fibre reinforced orthophthalic unsaturated polyester composite was widely used in the pipeline industry as a replacement to the corroded steel pipes. A filler which possesses high mechanical performance at high temperature; P84 Polyimide used as the particulate reinforcement in the unsaturated polyester matrix system to increase the mechanical performance of the glass fibre reinforced unsaturated polyester. The glass fibre composite laminates were prepared through a hand lay-up technique and fabricated into three layer laminate. Prior to be used as the matrix system in the lamination process, the unsaturated polyester resin was mixed with masterbatch P84 Polyimide at three loadings amount of 1, 3, and 5 wt%. The addition of P84 Polyimide at 1, 3, and 5 wt% increased the tensile properties and flexural properties especially at 1 wt% filler loading. As the filler loading increased, the tensile properties and flexural properties showed decreasing pattern. In the dynamic mechanical analysis, the values of storage modulus were taken at two points; 50 °C and 150 °C which were the storage modulus before and after the glass transition temperature. All storage modulus showed fluctuation trend for both before and after Tg. However, the storage modulus of the filled composite laminates after Tg showed higher values than unfilled composite laminates at all filler loading. Since the P84 Polyimide possesses high thermal stability, the presence of P84 Polyimide inside the composite system had assisted in delaying the Tg. In terms of the filler dispersion, the Cole-Cole plot showed an imperfect semi-circular shape which indicated good filler dispersion.

Pathological hypertrophy and cardiac dysfunction are linked to aberrant endogenous unsaturated fatty acid metabolism

PubMed Central

Salomé Campos, Dijon Henrique; Grippa Sant’Ana, Paula; Okoshi, Katashi; Padovani, Carlos Roberto; Masahiro Murata, Gilson; Nguyen, Son; Kolwicz, Stephen C.; Cicogna, Antonio Carlos

2018-01-01

Pathological cardiac hypertrophy leads to derangements in lipid metabolism that may contribute to the development of cardiac dysfunction. Since previous studies, using high saturated fat diets, have yielded inconclusive results, we investigated whether provision of a high-unsaturated fatty acid (HUFA) diet was sufficient to restore impaired lipid metabolism and normalize diastolic dysfunction in the pathologically hypertrophied heart. Male, Wistar rats were subjected to supra-valvar aortic stenosis (SVAS) or sham surgery. After 6 weeks, diastolic dysfunction and pathological hypertrophy was confirmed and both sham and SVAS rats were treated with either normolipidic or HUFA diet. At 18 weeks post-surgery, the HUFA diet failed to normalize decreased E/A ratios or attenuate measures of cardiac hypertrophy in SVAS animals. Enzymatic activity assays and gene expression analysis showed that both normolipidic and HUFA-fed hypertrophied hearts had similar increases in glycolytic enzyme activity and down-regulation of fatty acid oxidation genes. Mass spectrometry analysis revealed depletion of unsaturated fatty acids, primarily linoleate and oleate, within the endogenous lipid pools of normolipidic SVAS hearts. The HUFA diet did not restore linoleate or oleate in the cardiac lipid pools, but did maintain body weight and adipose mass in SVAS animals. Overall, these results suggest that, in addition to decreased fatty acid oxidation, aberrant unsaturated fatty acid metabolism may be a maladaptive signature of the pathologically hypertrophied heart. The HUFA diet is insufficient to reverse metabolic remodeling, diastolic dysfunction, or pathologically hypertrophy, possibly do to preferentially partitioning of unsaturated fatty acids to adipose tissue. PMID:29494668

Artificial recharge through a thick, heterogeneous unsaturated zone

USGS Publications Warehouse

Izbicki, J.A.; Flint, A.L.; Stamos, C.L.

2008-01-01

Thick, heterogeneous unsaturated zones away from large streams in desert areas have not previously been considered suitable for artificial recharge from ponds. To test the potential for recharge in these settings, 1.3 ?? 10 6 m3 of water was infiltrated through a 0.36-ha pond along Oro Grande Wash near Victorville, California, between October 2002 and January 2006. The pond overlies a regional pumping depression 117 m below land surface and is located where thickness and permeability of unsaturated deposits allowed infiltration and saturated alluvial deposits were sufficiently permeable to allow recovery of water. Because large changes in water levels caused by nearby pumping would obscure arrival of water at the water table, downward movement of water was measured using sensors in the unsaturated zone. The downward rate of water movement was initially as high as 6 m/d and decreased with depth to 0.07 m/d; the initial time to reach the water table was 3 years. After the unsaturated zone was wetted, water reached the water table in 1 year. Soluble salts and nitrate moved readily with the infiltrated water, whereas arsenic and chromium were less mobile. Numerical simulations done using the computer program TOUGH2 duplicated the downward rate of water movement, accumulation of water on perched zones, and its arrival at the water table. Assuming 10 ?? 10 6 m3 of recharge annually for 20 years, a regional ground water flow model predicted water level rises of 30 m beneath the ponds, and rises exceeding 3 m in most wells serving the nearby urban area.

Effect of high fat diets on the NTPDase, 5'-nucleotidase and acetylcholinesterase activities in the central nervous system.

PubMed

Kaizer, Rosilene Rodrigues; Spanevello, Rosélia Maria; Costa, Eduarda; Morsch, Vera Maria; Schetinger, Maria Rosa Chitolina

2018-02-01

High fat diets are associated with the promotion of neurological diseases, such as Alzheimer disease (AD). This study aim investigate the high fat diets role to promotion of AD using as biochemistry parameter of status of central nervous system through the NTPDase, 5'-nucleotidase and acetylcholinesterase (AChE) activities in brain of young rats. The intake of high fat diets promotes an inhibition of purinergic and cholinergic functions, mainly in the long-term exposure to saturated and saturated/unsaturated diets. The AChE activity was decreased to supernatant and synaptosomes tissues preparations obtained from cerebral cortex in average of 20%, to both groups exposed to saturated and saturated/unsaturated diets, when compared to the control group. Very similar results were found in hippocampus and cerebellum brain areas. At same time, the adenine nucleotides hydrolysis in synaptosomes of cerebral cortex were decreased to ATP, ADP and AMP after the long-term exposure to high fat diets, as saturated and saturated/unsaturated. The inhibition of ATP hydrolysis was of 26% and 39% to saturated and saturated/unsaturated diets, respectively. ADP hydrolysis was decreased in 20% to saturated diet, and AMP hydrolysis was decreased in 25% and 33% to saturated and saturated/unsaturated diets, respectively, all in comparison to the control. Thus, we can suggest that the effects of high diets on the purinergic and cholinergic nervous system may contribute to accelerate the progressive memory loss, to decline in language and other cognitive disruptions, such as AD patients presents. Copyright © 2017 ISDN. Published by Elsevier Ltd. All rights reserved.

Unsaturated free fatty acids increase benzodiazepine receptor agonist binding depending on the subunit composition of the GABAA receptor complex.

PubMed

Witt, M R; Westh-Hansen, S E; Rasmussen, P B; Hastrup, S; Nielsen, M

1996-11-01

It has been shown previously that unsaturated free fatty acids (FFAs) strongly enhance the binding of agonist benzodiazepine receptor ligands and GABAA receptor ligands in the CNS in vitro. To investigate the selectivity of this effect, recombinant human GABAA/benzodiazepine receptor complexes formed by different subunit compositions (alpha x beta y gamma 2, x = 1, 2, 3, and 5; y = 1, 2, and 3) were expressed using the baculovirus-transfected Sf9 insect cell system. At 10(-4) M, unsaturated FFAs, particularly arachidonic (20:4) and docosahexaenoic (22:6) acids, strongly stimulated (> 200% of control values) the binding of [3H]flunitrazepam ([3H]FNM) to the alpha 3 beta 2 gamma 2 receptor combination in whole cell preparations. No effect or small increases in levels of unsaturated FFAs on [3H]FNM binding to alpha 1 beta x gamma 2 and alpha 2 beta x gamma 2 receptor combinations were observed, and weak effects (130% of control values) were detected using the alpha 5 beta 2 gamma 2 receptor combination. The saturated FFAs, stearic and palmitic acids, were without effect on [3H]FNM binding to any combination of receptor complexes. The hydroxylated unsaturated FFAs, ricinoleic and ricinelaidic acids, were shown to decrease the binding of [3H]FNM only if an alpha 1 beta 2 gamma 2 receptor combination was used. Given the heterogeneity of the GABAA/ benzodiazepine receptor subunit distribution in the CNS, the effects of FFAs on the benzodiazepine receptor can be assumed to vary at both cellular and regional levels.

PRZM-3, A MODEL FOR PREDICTING PESTICIDE AND NITROGEN FATE IN THE CROP ROOT AND UNSATURATED SOIL ZONES: USER'S MANUAL FOR RELEASE 3.12.2

EPA Science Inventory

This publication contains documentation for the PRZM-3 model. PRZM-3 is the most recent version of a modeling system that links two subordinate models, PRZM and VADOFT, in order to predict pesticide transport and transformation down through the crop root and unsaturated soil zone...

Characterization of polar organosulfates in secondary organic aerosol from the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal

EPA Science Inventory

We show in the present study that the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal are biogenic volatile organic compound (BVOC) precursors for polar organosulfates with molecular weights (MWs) 230 and 214, which are also present in ambient fine aerosol from a...

Polyestercarbonates which exhibit improved processibility

DOEpatents

Krabbenhoft, Herman Otto

1999-01-01

The invention relates to a polyestercarbonate polymer which comprises repeating units of a mono-unsaturated aliphatic dicarboxylic acid having about 12 to about 20 carbon atoms. Preferred dicarboxylic acids for incorporation into the polymer are cis-octadec-9-enedioic acid or trans-octadec-9-enedioic acid. The use of these mono-unsaturated acids results in polymers with lower glass transition temperatures, and enhances processibility.

MICHIGAN SOIL VAPOR EXTRACTION REMEDIATION (MISER) MODEL: A COMPUTER PROGRAM TO MODEL SOIL VAPORT EXTRACTION AND BIOVENTING OF ORGANIC MATERIALS IN UNSATURATED GEOLO-GICAL MATERIAL (EPA/600/SR-97/099)

EPA Science Inventory

Soil vapor extraction (SVE) and bioventing (BV) are proven strategies for remediation of unsaturated zone soils. Mathematical models are powerful tools that can be used to integrate and quantify the interaction of physical, chemical, and biological processes occurring in field sc...

Oxidizability of unsaturated fatty acids and of a non-phenolic lignin structure in the manganese peroxidase-dependent lipid peroxidation system

Treesearch

Alexander N. Kapich; Tatyana V. Korneichik; Annele Hatakka; Kenneth E. Hammel

2010-01-01

Unsaturated fatty acids have been proposed to mediate the oxidation of recalcitrant, non-phenolic lignin structures by fungal manganese peroxidases (MnP), but their precise role remains unknown. We investigated the oxidizability of three fatty acids with varying degrees of polyunsaturation (linoleic, linolenic, and arachidonic acids) by measuring conjugated dienes...

Organocatalytic sequential alpha-amination-Horner-Wadsworth-Emmons olefination of aldehydes: enantioselective synthesis of gamma-amino-alpha,beta-unsaturated esters.

PubMed

Kotkar, Shriram P; Chavan, Vilas B; Sudalai, Arumugam

2007-03-15

A novel and highly enantioselective method for the synthesis of gamma-amino-alpha,beta-unsaturated esters via tandem alpha-amination-Horner-Wadsworth-Emmons (HWE) olefination of aldehydes is described. The one-pot assembly has been demonstrated for the construction of functionalized chiral 2-pyrrolidones, subunits present in several alkaloids. [structure: see text

Base induced chemical conversion of 3-carbamoyl-2-isoxazolines.

PubMed

Nishiwaki, Nagatoshi; Maki, Asaka; Ariga, Masahiro

2009-01-01

3-Carbamoyl-2-isoxazolines, prepared by cycloaddition of functionalized nitrile oxide, serve as masked 3-unsubstituted isoxazolines to afford 2-isoxazoline-3-carboxylic acid, beta-cyanoalcohol, alpha,beta-unsaturated nitrile, and alpha,beta-unsaturated amide upon heating in the alkaline solution. The present reaction is also applicable to synthesis of 3,4-difunctionalized isoxazoles and beta-hydroxy-gamma-lactone.

Sorption Equilibria of Vapor Phase Organic Pollutants on Unsaturated Soils and Soil Minerals

DTIC Science & Technology

1990-04-01

Sorbent Characterization .. ........ .......... 6 a. Description of Inorganic Solids and Soils. .... ........ 6 b. Moisture Content...compounds (TCE and toluene) is compared for a cored depth profile obtained from an unsaturated soil and for simulated profiles using inorganic solids. The...Sorbent Characterization a. Description of Inorganic Solids and Soils Inorganic solids were used for initial sorption studies to develop experimental

Tandem isomerization-decarboxylation of unsaturated fatty acids to olefins via ruthenium metal-as-ligand catalysts

USDA-ARS?s Scientific Manuscript database

A new facile Ru-catalyzed route to bio-olefins3 from unsaturated fatty acids via readily accessible metal-as-ligand type catalyst precursors, [Ru(CO)2RCO2]n and Ru3(CO)12, will be described. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds i...

[Atherosclerosis and nutrition].

PubMed

Daubresse, J C

2000-09-01

Atherosclerosis is the main cause of mortality in industrialized countries and even in poorly developed ones. It is linked to age and gender and also to a number of well identified risk factors: lipids anomalies, arterial hypertension, diabetes, smoking and weight excess among others. Risk factors improvement significantly reduces cardiovascular events. It is evident that nutrition plays an important role as it can modulate the evolution of body weight and blood pressure. Nutrition is also able to reduce the prevalence and severity of hyperlipidemias and diabetes. Saturated fatty acids (excepted stearic acid), trans poly-unsaturated acids as well as cholesterol increase serum LDL-cholesterol. Mono- and poly-unsaturated and classical cis-mono-unsaturated acids do the opposite. N-3 poly-unsaturated acids reduce serum triglyceride levels and cardiovascular events. Carbohydrates with a low glycemic index are important determinants of serum HDL-cholesterol levels and reduce cardiovascular risk. Animal proteins bring essential amino-acids to the body but also saturated fats. It seems interesting to eat vegetal proteins among which those derived from soya look promising. Our diet will include enough fiber and phytosterols-containing margarines look interesting as well. Modest alcohol consumption improves cardiovascular mortality in the majority of the prospective studies.

Ecophysiology of syntrophic communities that degrade saturated and unsaturated long-chain fatty acids.

PubMed

Sousa, Diana Z; Smidt, Hauke; Alves, Maria M; Stams, Alfons J M

2009-06-01

Syntrophic relationships are the key for biodegradation in methanogenic environments. We review the ecological and physiological features of syntrophic communities involved in the degradation of saturated and unsaturated long-chain fatty acids (LCFA), as well as their potential application to convert lipids/fats containing waste to biogas. Presently, about 14 species have been described with the ability to grow on fatty acids in syntrophy with methanogens, all belonging to the families Syntrophomonadaceae and Syntrophaceae. The principle pathway of LCFA degradation is through beta-oxidation, but the initial steps in the conversion of unsaturated LCFA are unclear. Communities enriched on unsaturated LCFA also degrade saturated LCFA, but the opposite generally is not the case. For efficient methane formation, the physical and inhibitory effects of LCFA on methanogenesis need to be considered. LCFA adsorbs strongly to biomass, which causes encapsulation of active syntrophic communities and hampers diffusion of substrate and products in and out of the biomass. Quantification of archaea by real-time PCR analysis suggests that potential LCFA inhibitory effect towards methanogens might be reversible. Rather, the conversion of adsorbed LCFA in batch assays was shown to result in a significant increase of archaeal cell numbers in anaerobic sludge samples.

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

Biodegradation, sorption, and transport of 2,4-dichlorophenoxyacetic acid in saturated and unsaturated soils.

PubMed Central

Estrella, M R; Brusseau, M L; Maier, R S; Pepper, I L; Wierenga, P J; Miller, R M

1993-01-01

The fate of an organic contaminant in soil depends on many factors, including sorption, biodegradation, and transport. The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model compound to illustrate the impact of these interacting factors on the fate of an organic contaminant. Batch and column experiments performed with a sandy loam soil mixture under saturated and unsaturated conditions were used to determine the effects of sorption and biodegradation on the fate and transport of 2,4-D. Sorption of 2,4-D was found to have a slight but significant effect on transport of 2,4-D under saturated conditions (retardation factor, 1.8) and unsaturated conditions (retardation factor, 3.4). Biodegradation of 2,4-D was extensive under both batch and column conditions and was found to have a significant impact on 2,4-D transport in column experiments. In batch experiments, complete mineralization of 2,4-D (100 mg kg-1) occurred over a 4-day period following a 3-day lag phase under both saturated and unsaturated conditions. The biodegradation rate parameters calculated for batch experiments were found to be significantly different from those estimated for column experiments. PMID:8285717

Modulation of the Lactobacillus acidophilus La-5 lipidome by different growth conditions.

PubMed

Hansen, Marie-Louise R W; Clausen, Anders; Ejsing, Christer S; Risbo, Jens

2015-10-01

Probiotics are bacteria used in the food industry due to their potential health benefits. In this study, the plasma membrane of the probiotic Lactobacillus acidophilus La-5 was investigated using state-of-the-art high-resolution shotgun lipidomics. Comparisons of the lipidome of the plasma membrane were done after altering the fatty acid composition by supplementing L. acidophilus La-5 with saturated, mono-, di- and tri-unsaturated fatty acids during fermentation. The plasma membrane with the highest degree of saturation resulted in a lipid composition with the highest proportion of cardiolipin (CL) and lowest proportion of monolysocardiolipin (MLCL). No significant changes were found for other lipid classes. The bacteria grown with di- and tri-unsaturated fatty acids were expected to have more unsaturated plasma membranes than bacteria grown with mono-unsaturated fatty acids. This was also the case for MLCL, but the numbers of double bonds for CL were quite similar for these three samples. The results indicate that L. acidophilus La-5 possesses a molecular mechanism for remodelling and optimizing the fatty acid composition of CL and MLCL species and the molar ratio of CL and MLCL. This study contributes new knowledge on the previously uninvestigated lipidome of L. acidophilus La-5.

Differences in surfactant lipids collected from pleural and pulmonary lining fluids.

PubMed

Mills, Paul C; Chen, Yi; Hills, Yvette C; Hills, Brian A

2005-11-01

The type and relative importance of saturated and unsaturated phospholipid components of surfactant within the epithelial lining fluid (ELF) of the inner and outer surfaces of the lung is not known. Seven healthy dogs were anesthetized and a bronchoalveolar lavage (BAL) was performed, immediately followed by a pleural lavage (PL). Lipid was extracted from lavage fluid and then analyzed for saturated, primarily dipalmitoylphosphatidylcholine (DPPC), and unsaturated phosphatidylcholine (PC) species using high-performance liquid chromatography (HPLC) with combined fluorescence and ultraviolet detection. Dilution of ELF in lavage fluids was corrected for using the urea method. DPPC (494.7 +/- 213.9 microg/mL) was the predominant PC present in ELF collected from the alveolar surface. In contrast, significantly higher (p = 0.028) proportions of unsaturated PC species were measured in PL fluid (approximately 105 microg/mL), particularly stearoyl-linoleoyl-phosphatidylcholine (SLPC), which could not be measured in fluid collected from the alveoli, compared to DPPC (2.6 +/- 2.0 microg/mL). This study indicates that unsaturated PC species seem to be more important than saturated species, particularly DPPC, in the pleural cavity, which has implications for surfactant replenishment following pleural disease or thoracic surgery.

WTAQ version 2-A computer program for analysis of aquifer tests in confined and water-table aquifers with alternative representations of drainage from the unsaturated zone

USGS Publications Warehouse

Barlow, Paul M.; Moench, Allen F.

2011-01-01

The computer program WTAQ simulates axial-symmetric flow to a well pumping from a confined or unconfined (water-table) aquifer. WTAQ calculates dimensionless or dimensional drawdowns that can be used with measured drawdown data from aquifer tests to estimate aquifer hydraulic properties. Version 2 of the program, which is described in this report, provides an alternative analytical representation of drainage to water-table aquifers from the unsaturated zone than that which was available in the initial versions of the code. The revised drainage model explicitly accounts for hydraulic characteristics of the unsaturated zone, specifically, the moisture retention and relative hydraulic conductivity of the soil. The revised program also retains the original conceptualizations of drainage from the unsaturated zone that were available with version 1 of the program to provide alternative approaches to simulate the drainage process. Version 2 of the program includes all other simulation capabilities of the first versions, including partial penetration of the pumped well and of observation wells and piezometers, well-bore storage and skin effects at the pumped well, and delayed drawdown response of observation wells and piezometers.

Simulating Heterogeneous Infiltration and Contaminant leaching Processes at Chalk River, Ontario

NASA Astrophysics Data System (ADS)

Ali, M. A.; Ireson, A. M.; Keim, D.

2015-12-01

A study is conducted at a waste management area in Chalk River, Ontario to characterize flow and contaminant transport with the aim of contributing to improved hydrogeological risk assessment in the context of waste management. Field monitoring has been performed to gain insights into the unsaturated zone characteristics, moisture dynamics, and contaminant transport rates. The objective is to provide quantitative estimates of surface fluxes (quantification of infiltration and evaporation) and investigations of unsaturated zone processes controlling water infiltration and spatial variability in head distributions and flow rates. One particular issue is to examine the effectiveness of the clayey soil cap installed to prevent infiltration of water into the waste repository and the top sand soil cover above the clayey layer to divert the infiltrated water laterally. The spatial variability in the unsaturated zone properties and associated effects on water flow and contaminant transport observed at the site, have led to a concerted effort to develop improved model of flow and transport based on stochastic concepts. Results obtained through the unsaturated zone model investigations are combined with the hydrogeological and geochemical components and develop predictive tools to assess the long term fate of the contaminants at the waste management site.

Influence of cadmium and mycorrhizal fungi on the fatty acid profile of flax (Linum usitatissimum) seeds.

PubMed

Kaplan, Matthew E; Simmons, Ellen R; Hawkins, Jack C; Ruane, Lauren G; Carney, Jeffrey M

2015-09-01

The soil environment can affect not only the quantity of crops produced but also their nutritional quality. We examined the combined effects of below-ground cadmium (0, 5, and 15 ppm) and mycorrhizal fungi (presence and absence) on the concentration of five major fatty acids within flax seeds (Linum usitatissimum). Plants grown with mycorrhizal fungi produced seeds that contained higher concentrations of unsaturated (18:1, 18:2 and 18:3), but not saturated (16:0 and 18:0) fatty acids. The effects of mycorrhizal fungi on the concentration of unsaturated fatty acids in seeds were most pronounced when plant roots were exposed to 15 ppm Cd (i.e. the concentrations of 18:1, 18:2 and 18:3 increased by 169%, 370% and 150%, respectively). The pronounced effects of mycorrhizal fungi on the concentration of unsaturated fatty acids at 15 ppm Cd may have been due to the presence of elevated levels of Cd within seeds. Our results suggest that, once the concentration of cadmium within seeds reaches a certain threshold, this heavy metal may improve the efficiency of enzymes that convert saturated fatty acids to unsaturated fatty acids. © 2014 Society of Chemical Industry.

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.

Estimation of Unsaturated Zone Traveltimes for Rainier Mesa and Shoshone Mountain, Nevada Test Site, Nevada, Using a Source-Responsive Preferential-Flow Model

USGS Publications Warehouse

Ebel, Brian A.; Nimmo, John R.

2009-01-01

Traveltimes for contaminant transport by water from a point in the unsaturated zone to the saturated zone are a concern at Rainier Mesa and Shoshone Mountain in the Nevada Test Site, Nevada. Where nuclear tests were conducted in the unsaturated zone, contaminants must traverse hundreds of meters of variably saturated rock before they enter the saturated zone in the carbonate rock, where the regional groundwater system has the potential to carry them substantial distances to a location of concern. The unsaturated-zone portion of the contaminant transport path may cause a significant delay, in addition to the time required to travel within the saturated zone, and thus may be important in the overall evaluation of the potential hazard from contamination. Downward contaminant transport through the unsaturated zone occurs through various processes and pathways; this can lead to a broad distribution of contaminant traveltimes, including exceedingly slow and unexpectedly fast extremes. Though the bulk of mobile contaminant arrives between the time-scale end members, the fastest contaminant transport speed, in other words the speed determined by the combination of possible processes and pathways that would bring a measureable quantity of contaminant to the aquifer in the shortest time, carries particular regulatory significance because of its relevance in formulating the most conservative hazard-prevention scenarios. Unsaturated-zone flow is usually modeled as a diffusive process responding to gravity and pressure gradients as mediated by the unsaturated hydraulic properties of the materials traversed. The mathematical formulation of the diffuse-flow concept is known as Richards' equation, which when coupled to a solute transport equation, such as the advection-dispersion equation, provides a framework to simulate contaminant migration in the unsaturated zone. In recent decades awareness has increased that much fluid flow and contaminant transport within the unsaturated zone takes place as preferential flow, faster than would be predicted by the coupled Richards' and advection-dispersion equations with hydraulic properties estimated by traditional means. At present the hydrologic community has not achieved consensus as to whether a modification of Richards' equation, or a fundamentally different formulation, would best quantify preferential flow. Where the fastest contaminant transport speed is what needs to be estimated, there is the possibility of simplification of the evaluation process. One way of doing so is by a two-step process in which the first step is to evaluate whether significant preferential flow and solute transport is possible for the media and conditions of concern. The second step is to carry out (a) a basic Richards' and advection-dispersion equation analysis if it is concluded that preferential flow is not possible or (b) an analysis that considers only the fastest possible preferential-flow processes, if preferential flow is possible. For the preferential-flow situation, a recently published model describable as a Source-Responsive Preferential-Flow (SRPF) model is an easily applied option. This report documents the application of this two-step process to flow through the thick unsaturated zones of Rainier Mesa and Shoshone Mountain in the Nevada Test Site. Application of the SRPF model involves distinguishing between continuous and intermittent water supply to preferential flow paths. At Rainier Mesa and Shoshone Mountain this issue is complicated by the fact that contaminant travel begins at a location deep in the subsurface, where there may be perched water that may or may not act like a continuous supply, depending on such features as the connectedness of fractures and the nature of impeding layers. We have treated this situation by hypothesizing both continuous and intermittent scenarios for contaminant transport to the carbonate aquifer and reporting estimation of the fastest speed for both of th

Estimation of unsaturated zone traveltimes for Rainier Mesa and Shoshone Mountain, Nevada Test Site, Nevada, using a source-responsive preferential-flow model

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

Brian A. Ebel; John R. Nimmo

2009-09-11

Traveltimes for contaminant transport by water from a point in the unsaturated zone to the saturated zone are a concern at Rainier Mesa and Shoshone Mountain in the Nevada Test Site, Nevada. Where nuclear tests were conducted in the unsaturated zone, contaminants must traverse hundreds of meters of variably saturated rock before they enter the saturated zone in the carbonate rock, where the regional groundwater system has the potential to carry them substantial distances to a location of concern. The unsaturated-zone portion of the contaminant transport path may cause a significant delay, in addition to the time required to travelmore » within the saturated zone, and thus may be important in the overall evaluation of the potential hazard from contamination. Downward contaminant transport through the unsaturated zone occurs through various processes and pathways; this can lead to a broad distribution of contaminant traveltimes, including exceedingly slow and unexpectedly fast extremes. Though the bulk of mobile contaminant arrives between the time-scale end members, the fastest contaminant transport speed, in other words the speed determined by the combination of possible processes and pathways that would bring a measureable quantity of contaminant to the aquifer in the shortest time, carries particular regulatory significance because of its relevance in formulating the most conservative hazard-prevention scenarios. Unsaturated-zone flow is usually modeled as a diffusive process responding to gravity and pressure gradients as mediated by the unsaturated hydraulic properties of the materials traversed. The mathematical formulation of the diffuse-flow concept is known as Richards' equation, which when coupled to a solute transport equation, such as the advection-dispersion equation, provides a framework to simulate contaminant migration in the unsaturated zone. In recent decades awareness has increased that much fluid flow and contaminant transport within the unsaturated zone takes place as preferential flow, faster than would be predicted by the coupled Richards' and advection-dispersion equations with hydraulic properties estimated by traditional means. At present the hydrologic community has not achieved consensus as to whether a modification of Richards' equation, or a fundamentally different formulation, would best quantify preferential flow. Where the fastest contaminant transport speed is what needs to be estimated, there is the possibility of simplification of the evaluation process. One way of doing so is by a two-step process in which the first step is to evaluate whether significant preferential flow and solute transport is possible for the media and conditions of concern. The second step is to carry out (a) a basic Richards' and advection-dispersion equation analysis if it is concluded that preferential flow is not possible or (b) an analysis that considers only the fastest possible preferential-flow processes, if preferential flow is possible. For the preferential-flow situation, a recently published model describable as a Source-Responsive Preferential-Flow (SRPF) model is an easily applied option. This report documents the application of this two-step process to flow through the thick unsaturated zones of Rainier Mesa and Shoshone Mountain in the Nevada Test Site. Application of the SRPF model involves distinguishing between continuous and intermittent water supply to preferential flow paths. At Rainier Mesa and Shoshone Mountain this issue is complicated by the fact that contaminant travel begins at a location deep in the subsurface, where there may be perched water that may or may not act like a continuous supply, depending on such features as the connectedness of fractures and the nature of impeding layers. We have treated this situation by hypothesizing both continuous and intermittent scenarios for contaminant transport to the carbonate aquifer and reporting estimation of the fastest speed for both of these end members.« less

Evaluation of unsaturated zone water fluxes in heterogeneous alluvium at a Mojave Basin Site

USGS Publications Warehouse

Nimmo, John R.; Deason, Jeffrey A.; Izbicki, John A.; Martin, Peter

2002-01-01

Vertical and horizontal water fluxes in the unsaturated zone near intermittent streams critically affect ecosystems, water supply, and contaminant transport in arid and semiarid regions. The subsurface near the Oro Grande Wash is typical in having great textural diversity, pronounced layer contrasts, and extremely low hydraulic conductivities associated with nearly dry media. These features prevent a straightforward application of the Darcian method for recharge estimation, which has provided high‐quality flux estimates at simpler, wetter sites. We have augmented the basic Darcian method with theoretical developments such that a small number of core sample unsaturated hydraulic property measurements, combined with additional, easily obtained data (e.g., drillers' logs) can provide useful flux estimates and knowledge of two‐dimensional water behavior beneath the wash.

Gold-catalyzed heterogeneous aerobic dehydrogenative amination of α,β-unsaturated aldehydes to enaminals.

PubMed

Jin, Xiongjie; Yamaguchi, Kazuya; Mizuno, Noritaka

2014-01-07

Although enaminals (β-enaminals) are very important compounds and have been utilized as useful synthons for various important compounds, they have been synthesized through non-green and/or limited procedures until now. Herein, we have successfully developed a green synthetic procedure using a heterogeneous catalyst. In the presence of gold nanoparticles supported on manganese-oxide-based octahedral molecular sieves OMS-2 (Au/OMS-2), dehydrogenative amination of α,β-unsaturated aldehydes with amines proceeded efficiently, with the corresponding enaminals isolated in moderate to high yields (50-97 %). The catalysis was truly heterogeneous, and Au/OMS-2 could be reused. Furthermore, the formal Wacker-type oxidation of α,β-unsaturated aldehydes to enaminones has been realized. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative evaluation of manganese peroxidase- and Mn(III)-initiated peroxidation of C18 unsaturated fatty acids by different methods

Treesearch

Alexander N. Kapich; Tatyana V. Korneichik; Kenneth E. Hammel; Annele Hatakka

2011-01-01

The peroxidation of C18 unsaturated fatty acids by fungal manganese peroxidase (MnP)/Mn(II) and by chelated Mn(III) was studied with application of three different methods: by monitoring oxygen consumption, by measuring conjugated dienes and by thiobarbituric acid-reactive substances (TBARS) formation. All tested polyunsaturated fatty acids (PUFAs) were oxidized by MnP...

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

DOEpatents

Kung, H.H.; Chaar, M.A.

1988-10-11

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M[sub 3](VO[sub 4])[sub 2] and MV[sub 2]O[sub 6], M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

DOEpatents

Kung, Harold H.; Chaar, Mohamed A.

1988-01-01

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M.sub.3 (VO.sub.4).sub.2 and MV.sub.2 O.sub.6, M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

Alkaline battery containing a separator of a cross-linked copolymer of vinyl alcohol and unsaturated carboxylic acid

NASA Technical Reports Server (NTRS)

Hsu, L. C.; Philipp, W. H.; Sheibley, D. W.; Gonzalez-Sanabria, O. D. (Inventor)

1985-01-01

A battery separator for an alkaline battery is described. The separator comprises a cross linked copolymer of vinyl alcohol units and unsaturated carboxylic acid units. The cross linked copolymer is insoluble in water, has excellent zincate diffusion and oxygen gas barrier properties and a low electrical resistivity. Cross linking with a polyaldehyde cross linking agent is preferred.

C–H Functionalization of Cyclic Amines: Redox-Annulations with α,β-Unsaturated Carbonyl Compounds

PubMed Central

Kang, YoungKu; Richers, Matthew T.; Sawicki, Conrad H.; Seidel, Daniel

2015-01-01

Cyclic amines such as pyrrolidine and 1,2,3,4-tetrahydroisoquinoline undergo redox-annulations with α,β-unsaturated aldehydes and ketones. Carboxylic acid promoted generation of a conjugated azomethine ylide is followed by 6π-electrocylization, and, in some cases, tautomerization. The resulting ring-fused pyrrolines are readily oxidized to the corresponding pyrroles or reduced to pyrrolidines. PMID:26051897

Analysis of a mesoscale infiltration and water seepage test in unsaturated fractured rock: Spatial variabilities and discrete fracture patterns

USGS Publications Warehouse

Zhou, Q.; Salve, R.; Liu, H.-H.; Wang, J.S.Y.; Hudson, D.

2006-01-01

A mesoscale (21??m in flow distance) infiltration and seepage test was recently conducted in a deep, unsaturated fractured rock system at the crossover point of two underground tunnels. Water was released from a 3??m ?? 4??m infiltration plot on the floor of an alcove in the upper tunnel, and seepage was collected from the ceiling of a niche in the lower tunnel. Significant temporal and (particularly) spatial variabilities were observed in both measured infiltration and seepage rates. To analyze the test results, a three-dimensional unsaturated flow model was used. A column-based scheme was developed to capture heterogeneous hydraulic properties reflected by these spatial variabilities observed. Fracture permeability and van Genuchten ?? parameter [van Genuchten, M.T., 1980. A closed-form equation for predicting the hydraulic conductivity of unsaturated soils. Soil Sci. Soc. Am. J. 44, 892-898] were calibrated for each rock column in the upper and lower hydrogeologic units in the test bed. The calibrated fracture properties for the infiltration and seepage zone enabled a good match between simulated and measured (spatially varying) seepage rates. The numerical model was also able to capture the general trend of the highly transient seepage processes through a discrete fracture network. The calibrated properties and measured infiltration/seepage rates were further compared with mapped discrete fracture patterns at the top and bottom boundaries. The measured infiltration rates and calibrated fracture permeability of the upper unit were found to be partially controlled by the fracture patterns on the infiltration plot (as indicated by their positive correlations with fracture density). However, no correlation could be established between measured seepage rates and density of fractures mapped on the niche ceiling. This lack of correlation indicates the complexity of (preferential) unsaturated flow within the discrete fracture network. This also indicates that continuum-based modeling of unsaturated flow in fractured rock at mesoscale or a larger scale is not necessarily conditional explicitly on discrete fracture patterns. ?? 2006 Elsevier B.V. All rights reserved.

Kinetic study of the degradation of C5 and C6 unsaturated aldehydes and alcohols by ozone

NASA Astrophysics Data System (ADS)

Kalalian, Carmen; Roth, Estelle; Chakir, Abdelkhaleq

2017-04-01

Emissions of biogenic volatile organic compounds (VOCs) are higher than those from anthropogenic sources. They are therefore likely to have a great influence on atmospheric chemistry both locally and regionally, through their impact on the HOx balance (HOx = HO + HO2), ozone production and ability to form secondary organic aerosols (SOA). Among the volatile organic compounds of biogenic origin are the family of C5 and C6 unsaturated aldehydes and alcohols. Few information exist regarding the fate of these compounds in the atmosphere especially there reaction with ozone. In this work, we studied the kinetics of the reaction of three unsaturated aldehydes (trans-2-pentenal, trans-2-hexenal and 2-methyl-2-pentenal) and three unsaturated alcohols (1-penten-3-ol, cis-2-penten-1-ol and trans-3-hexen-1-ol) with ozone O3 in a rigid atmospheric simulation chamber coupled to an FTIR spectrometer at four different temperatures (273, 298, 333 and 353 K) and at atmospheric pressure. The rate constants of the ozonolysis reaction of the unsaturated aldehydes and the unsaturated alcohols studied were determined and the following Arrhenius expression was obtained (cm3 molecule -1 s -1): k (Trans -2-pentenal)= (3.83 ± 3.71) x 10-16 exp (- (1706 ± 295) / T) k (Trans-2-hexenal)= (1.43 ± 0.67) x 10-16 exp (- (1369 ± 141) / T) k(2-Methyl-2-pentenal)= (3.62± 0.22) x 10-18 exp (- (121 ± 20) / T) k(1-penten-3-ol) = (1.42 ± 1.24) x 10-16 exp (- (642 ± 250) / T) k(Cis-2-penten-1-ol)= (3.14 ± 0.45) x 10-15 exp (- (1045 ± 40) / T) k(Trans-3-hexen-1-ol)= (6.38 ± 1.75) x 10-16 exp (- (686 ± 89) / T) The obtained data will be discussed in terms of structure-reactivity relationship and compared with the reported reactivity with OH radicals. The atmospheric implications derived from this study are discussed as well.

Saturated and unsaturated salt transport in peat from a constructed fen

NASA Astrophysics Data System (ADS)

Simhayov, Reuven B.; Weber, Tobias K. D.; Price, Jonathan S.

2018-02-01

The underlying processes governing solute transport in peat from an experimentally constructed fen peatland were analyzed by performing saturated and unsaturated solute breakthrough experiments using Na+ and Cl- as reactive and non-reactive solutes, respectively. We tested the performance of three solute transport models, including the classical equilibrium convection-dispersion equation (CDE), a chemical non-equilibrium one-site adsorption model (OSA) and a model to account for physical non-equilibrium, the mobile-immobile (MIM) phases. The selection was motivated by the fact that the applicability of the MIM in peat soils finds a wide consensus. However, results from inverse modeling and a robust statistical evaluation of this peat provide evidence that the measured breakthrough of the conservative tracer, Cl-, could be simulated well using the CDE. Furthermore, the very high Damköhler number (which approaches infinity) suggests instantaneous equilibration between the mobile and immobile phases underscoring the redundancy of the MIM approach for this particular peat. Scanning electron microscope images of the peat show the typical multi-pore size distribution structures have been homogenized sufficiently by decomposition, such that physical non-equilibrium solute transport no longer governs the transport process. This result is corroborated by the fact the soil hydraulic properties were adequately described using a unimodal van Genuchten-Mualem model between saturation and a pressure head of ˜ -1000 cm of water. Hence, MIM was not the most suitable choice, and the long tailing of the Na+ breakthrough curve was caused by chemical non-equilibrium. Successful description was possible using the OSA model. To test our results for the unsaturated case, we conducted an unsaturated steady-state evaporation experiment to drive Na+ and Cl- transport. Using the parameterized transport models from the saturated experiments, we could numerically simulate the unsaturated transport using Hydrus-1-D. The simulation showed a good prediction of observed values, confirming the suitability of the parameters for use in a slightly unsaturated transport simulation. The findings improve the understanding of solute redistribution in the constructed fen and imply that MIM should not be automatically assumed for solute transport in peat but rather should be evidence based.

Production of 8,11-dihydroxy and 8-hydroxy unsaturated fatty acids from unsaturated fatty acids by recombinant Escherichia coli expressing 8,11-linoleate diol synthase from Penicillium chrysogenum.

PubMed

Kim, Min-Ji; Seo, Min-Ju; Shin, Kyung-Chul; Oh, Deok-Kun

2017-03-01

Hydroxy unsaturated fatty acids can be used as antimicrobial surfactants. 8,11-Linoleate diol synthase (8,11-LDS) catalyzes the conversion of unsaturated fatty acid to 8-hydroperoxy unsaturated fatty acid, and it is subsequently isomerized to 8,11-dihydroxy unsaturated fatty acid by the enzyme. The optimal reaction conditions of recombinant Escherichia coli expressing Penicillium chrysogenum 8,11-LDS for the production of 8,11-dihydroxy-9,12(Z,Z)-octadecadienoic acid (8,11-DiHODE), 8,11-dihydroxy-9,12,15(Z,Z,Z)-octadecatrienoic acid (8,11-DiHOTrE), 8-hydroxy-9(Z)-hexadecenoic acid (8-HHME), and 8-hydroxy-9(Z)-octadecenoic acid (8-HOME) were pH 7.0, 25°C, 10 g/L linoleic acid, and 20 g/L cells; pH 6.0, 25°C, 6 g/L α-linolenic acid, and 60 g/L cells; pH 7.0, 25°C, 8 g/L palmitoleic acid, and 25 g/L cells; and pH 8.5, 30°C, 6 g/L oleic acid, and 25 g/L cells, respectively. Under these optimized conditions, the recombinant cells produced 6.0 g/L 8,11-DiHODE for 60 min, with a conversion of 60% (w/w) and a productivity of 6.0 g/L/h; 4.3 g/L 8,11-DiHOTrE for 60 min, with a conversion of 72% (w/w) and a productivity of 4.3 g/L/h; 4.3 g/L 8-HHME acid for 60 min, with a conversion of 54% (w/w) and a productivity of 4.3 g/L/h; and 0.9 g/L 8-HOME for 30 min, with a conversion of 15% (w/w) and a productivity of 1.8 g/L/h. To best of our knowledge, this is the first report on the biotechnological production of 8,11-DiHODE, 8,11-DiHOTrE, 8-HHME, and 8-HOME. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:390-396, 2017. © 2017 American Institute of Chemical Engineers.

Reactive Secondary Sequence Oxidative Pathology Polymer Model and Antioxidant Tests

PubMed Central

Petersen, Richard C.

2014-01-01

Aims To provide common Organic Chemistry/Polymer Science thermoset free-radical crosslinking Sciences for Medical understanding and also present research findings for several common vitamins/antioxidants with a new class of drugs known as free-radical inhibitors. Study Design Peroxide/Fenton transition-metal redox couples that generate free radicals were combined with unsaturated lipid oils to demonstrate thermoset-polymer chain growth by crosslinking with the α-β-unsaturated aldehyde acrolein into rubbery/adhesive solids. Further, Vitamin A and beta carotene were similarly studied for crosslink pathological potential. Also, free-radical inhibitor hydroquinone was compared for antioxidant capability with Vitamin E. Place and Duration of Study Department of Materials Science and Engineering and Department of Biomaterials, University of Alabama at Birmingham, between June 2005 and August 2012. Methodology Observations were recorded for Fenton free-radical crosslinking of unsaturated lipids and vitamin A/beta carotene by photography further with weight measurements and percent-shrinkage testing directly related to covalent crosslinking of unsaturated lipids recorded over time with different concentrations of acrolein. Also, hydroquinone and vitamin E were compared at concentrations from 0.0–7.3wt% as antioxidants for reductions in percent-shrinkage measurements, n = 5. Results Unsaturated lipid oils responded to Fenton thermoset-polymer reactive secondary sequence reactions only by acrolein with crosslinking into rubbery-type solids and different non-solid gluey products. Further, molecular oxygen crosslinking was demonstrated with lipid peroxidation and acrolein at specially identified margins. By peroxide/Fenton free-radical testing, both vitamin A and beta-carotene demonstrated possible pathology chemistry for chain-growth crosslinking. During lipid/acrolein testing over a 50 hour time period at 7.3wt% antioxidants, hydroquinone significantly reduced percent shrinkage greatly compared to the standard antioxidant vitamin E, %shrinkage at 11.6 ±1.3 for hydroquinone and 27.8 ±2.2 for vitamin E, P = .001. Conclusion Free radicals crosslinked unsaturated lipid fatty acids into thermoset polymers through Fenton reactions when combined with acrolein. Further, hydroquinone was a superior antioxidant to vitamin E. PMID:25909053

Unsaturated Fatty Acids Improve Atherosclerosis Markers in Obese and Overweight Non-diabetic Elderly Patients.

PubMed

de Oliveira, Patrícia Amante; Kovacs, Cristiane; Moreira, Priscila; Magnoni, Daniel; Saleh, Mohamed Hassan; Faintuch, Joel

2017-10-01

Several studies have demonstrated the benefits of replacing trans and saturated fats with unsaturated fatty acids on cardiovascular diseases. We aimed to demonstrate the effect of polyunsaturated and monounsaturated fat supplementation on the biochemical and endothelial markers of atherosclerotic disease in obese or overweight non-diabetic elderly patients. Seventy-nine patients were randomly divided into three groups: flaxseed oil, olive oil, and sunflower oil; patients in each group received 30 mL of oil for 90 days. Patients were subjected to anthropometric and bioimpedance assessments; biochemical and endothelial evaluations were performed through ultrasonography of the brachial artery and carotid artery for endothelium-dependent dilation and intima-media thickness assessment, respectively, before and after the intervention. The participants' usual diet remained unchanged. The flaxseed oil group had improved ultra-sensitive C-reactive protein levels (p = 0.074) and reduced carotid intima-media thickness (CIMT) (p = 0.028); the olive oil group exhibited an improved apolipoprotein (Apo)B/ApoA ratio (p = 0.021), reduced CIMT (p = 0.028), and improved flow-mediated vasodilation (FMV) (p = 0.054); and similarly, the sunflower oil group showed an improved ApoB/ApoA ratio (p = 0.024), reduced CIMT (p = 0.048), and improved FMV (p = 0.001). Unsaturated fatty acid supplementation using the three vegetable oils attenuated pro-inflammatory properties and improved prothrombotic conditions. Therefore, introducing or replacing saturated and trans fat with unsaturated fatty acids is beneficial for cardiovascular risk reduction in obese or overweight non-diabetic elderly people. Further studies are needed to determine which unsaturated fat best prevents cardiovascular disease in elderly patients.

In situ crystallization and transformation kinetics of polymorphic forms of saturated-unsaturated-unsaturated triacylglycerols: 1-palmitoyl-2,3-dioleoyl glycerol, 1-stearoyl-2,3-dioleoyl glycerol, and 1-palmitoyl-2-oleoyl-3-linoleoyl glycerol.

PubMed

Bayés-García, L; Calvet, T; Cuevas-Diarte, M A; Ueno, S

2016-07-01

We examined the influence of dynamic thermal treatment (variation of cooling/heating rates) on the polymorphic crystallization and transformation pathways of 1-palmitoyl-2,3-dioleoyl glycerol (POO), 1-stearoyl-2,3-dioleoyl glycerol (SOO), and 1-palmitoyl-2-oleoyl-3-linoleoyl glycerol (POL), which are major saturated-unsaturated-unsaturated (SUU) triacylglycerols (TAGs) of vegetable oils and animal fats (e.g., palm oil, olive oil, and Iberian ham fat). Using mainly a combination of differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffraction (SR-XRD), we analyzed the polymorphic behavior of TAGs when high (15°Cmin -1 ), intermediate (2°Cmin -1 ), and low (0.5°Cmin -1 ) cooling and heating rates were applied. Multiple polymorphic forms were detected in POO, SOO, and POL (sub-α, α, β' 2 , and β' 1 ). Transient disordered phases, defined as kinetic liquid crystal (KLC) phases, were determined in POO and SOO for the first time. The results demonstrated that more stable forms were directly obtained from the melt by decreasing the cooling rates, whereas less stable forms predominated at high cooling rates, as confirmed in our previous work. Regarding heating rate variation, we confirmed that the nature of the polymorphic transformations observed (solid-state, transformation through KLC phase, or melt-mediation) depended largely on the heating rate. These results were discussed considering the activation energies involved in each process and compared with previous studies on TAGs with different saturated-unsaturated structures (1,3-dioleoyl-2-palmitoylglycerol, 1,3-dipalmitoyl-2-oleoyl-glycerol, trioleoyl glycerol, and 1,2-dioleoyl-3-linoleoyl glycerol). Copyright © 2016 Elsevier Ltd. All rights reserved.

Role of air-water interfaces on retention of viruses under unsaturated conditions

NASA Astrophysics Data System (ADS)

Torkzaban, S.; Hassanizadeh, S. M.; Schijven, J. F.; van den Berg, H. H. J. L.

2006-12-01

We investigated transport of viruses through saturated and unsaturated sand columns. Unsaturated experiments were conducted under conditions of uniform saturation and steady state water flow. The water saturation ranged from 1 to 0.5. Bacteriophages MS2 and ϕX174 were used as surrogates for pathogenic viruses in these studies. Phosphate-buffered solutions with different pH values (7.5, 6.2, 5.5, and 5) were utilized. Virus transport was modeled assuming first-order kinetic adsorption for interactions to the solid-water interface (SWI) and the air-water interface (AWI). Under saturated conditions, virus retention increased as pH decreased, and a one-site kinetic model produced a good fit to the breakthrough curves. Under unsaturated conditions a two-site kinetic model was needed to fit the breakthrough curves satisfactorily. The second site was attributed to the adsorption of phages to the AWI. According to our results, ϕX174 exhibits a high affinity to the AWI at pH values below 6.6 (the isoelectric point of ϕX174). Although it is believed that MS2 is more hydrophobic than ϕX174, MS2 had a lower affinity to the AWI than ϕX174, presumably because of the lower isoelectric point of MS2, which is equal to 3.9. Under unsaturated conditions, viruses captured within the column could be recovered in the column outflow by resaturating and immediately draining the column. Draining columns under saturated conditions, however, did not result in any recovery of viruses. Therefore the recovery can be attributed to the release of viruses adsorbed to the AWI. Our results suggest that electrostatic interactions of viruses with the AWI are much more important than hydrophobicity.

The mycotoxin patulin reacts with DNA bases with and without previous conjugation to GSH: implication for related α,β-unsaturated carbonyl compounds?

PubMed

Pfenning, Carolin; Esch, Harald L; Fliege, Ralph; Lehmann, Leane

2016-02-01

The α,β-unsaturated carbonyl group is recognized as alert for mutagenicity, attributed to (1) its direct reaction with DNA, counteractable by glutathione (GSH), and (2) oxidative stress caused indirectly by GSH depletion. Accordingly, the α,β,γ,δ-unsaturated lactone patulin (PAT), a mycotoxin detected in fruits and products derived thereof, is known to induce gene, chromosome, and genome mutations in vitro, its mutagenicity correlating inversely with intracellular GSH levels. Thus, the reactivity of PAT against DNA bases and nucleosides in the absence and presence of GSH and glutathione S-transferases (GSTs) was investigated under cell-free conditions using HPLC mass spectrometry techniques for identification of reaction products. Adduct formation with all four nucleobases as well as with purine base nucleosides occurred even in the presence of GSH, revealing several adducts of PAT, mono- and disubstituted with nucleobases/nucleosides as well as novel GSH-PAT adducts. In addition, novel mixed GSH-PAT-nucleobase adducts were observed. These adducts exhibited a ketohexanoic acid-type structure of the PAT molecule, C6 substituted with GSH and linking C1 of PAT with nitrogens of nucleobases/nucleosides via an amide bond. Formation of GSH-PAT-adenine adducts was not prevented by GSTs, and excess of GSH needed to reduce their formation was higher than for PAT-adenine adducts. The formation of mixed GSH-DNA base adducts has not been described for PAT or any other α,β-unsaturated carbonyl before, although the reaction mechanism seems to be applicable to a variety of α,β-unsaturated carbonyls occurring in food and in the environment.

Effect of Synthetic Dietary Triglycerides: A Novel Research Paradigm for Nutrigenomics

PubMed Central

Sanderson, Linda M.; de Groot, Philip J.; Hooiveld, Guido J. E. J.; Koppen, Arjen; Kalkhoven, Eric; Müller, Michael; Kersten, Sander

2008-01-01

Background The effect of dietary fats on human health and disease are likely mediated by changes in gene expression. Several transcription factors have been shown to respond to fatty acids, including SREBP-1c, NF-κB, RXRs, LXRs, FXR, HNF4α, and PPARs. However, it is unclear to what extent these transcription factors play a role in gene regulation by dietary fatty acids in vivo. Methodology/Principal Findings Here, we take advantage of a unique experimental design using synthetic triglycerides composed of one single fatty acid in combination with gene expression profiling to examine the effects of various individual dietary fatty acids on hepatic gene expression in mice. We observed that the number of significantly changed genes and the fold-induction of genes increased with increasing fatty acid chain length and degree of unsaturation. Importantly, almost every single gene regulated by dietary unsaturated fatty acids remained unaltered in mice lacking PPARα. In addition, the majority of genes regulated by unsaturated fatty acids, especially docosahexaenoic acid, were also regulated by the specific PPARα agonist WY14643. Excellent agreement was found between the effects of unsaturated fatty acids on mouse liver versus cultured rat hepatoma cells. Interestingly, using Nuclear Receptor PamChip® Arrays, fatty acid- and WY14643-induced interactions between PPARα and coregulators were found to be highly similar, although several PPARα-coactivator interactions specific for WY14643 were identified. Conclusions/Significance We conclude that the effects of dietary unsaturated fatty acids on hepatic gene expression are almost entirely mediated by PPARα and mimic those of synthetic PPARα agonists in terms of regulation of target genes and molecular mechanism. Use of synthetic dietary triglycerides may provide a novel paradigm for nutrigenomics research. PMID:18301758

Effect Of Air-Water Interface On Microorganism Transport Under Unsaturated Conditions

NASA Astrophysics Data System (ADS)

Torkzaban, S.; Hassanizadeh, S. M.; Schijven, J. F.

2005-12-01

Groundwater may become contaminated with pathogenic microorganisms from land application of treated wastewater, septic wells, and effluent from septic tanks, and leaking sewage pipes. The unsaturated zone is of special importance since it often represents the first line of natural defense against groundwater pollution. Moreover, many experimental studies have shown that contaminant removal is more significant under lower saturation levels. Interaction of microbial particles with the air-water interfaces (AWI) has been previously suggested to explain high removal of pathogenic microorganisms during transport through unsaturated soil. The objective of this research was to explore the effect of AWI on virus transport. The transport of bacteriophages MS2 and FiX174 in sand columns was studied under various conditions, such as different pH, and saturation levels. Fitting of a transport model to the breakthrough curves was performed to determine the adsorption parameters. FiX174 with isoelectric point of 6.7 exhibited high affinity to the air-water interface by decreasing pH from 7.5 to 6.2. MS2 with isoelectric point of 3.5 has lower affinity to air-water interfaces than FiX174, but has similar pH- dependence. These results show the importance of electrostatic interactions, instead of hydrophobic, between the AWI and viruses. Adsorption to AWI is strongly pH dependent, increasing as pH decreases. It was found that two-site kinetic model should be used for modeling of virus transport under unsaturated conditions Moreover, by draining the unsaturated column, we found out that the attached viruses to AWI are viable, which is in contrast with the literature where retained viruses to AWI are considered as inactivated.

An Approach Using Gas Monitoring to Find the Residual TCE Location in the Unsaturated Zone of Woosan Industrial Complex (WIC), Korea

NASA Astrophysics Data System (ADS)

Koh, Y.; Lee, S.; Yang, J.; Lee, K.

2012-12-01

An area accommodating various industrial facilities has fairly high probability of groundwater contamination with multiple chlorinated solvents such as trichloroethene (TCE), carbon tetrachloride (CT), and chloroform (CF). Source tracing of chlorinated solvents in the unsaturated zone is an essential procedure for the management and remediation of contaminated area. From the previous study on seasonal variations in hydrological stresses and spatial variations in geologic conditions on a TCE plume, the existence of residual DNAPLs at or above the water table has proved. Since TCE is one of the frequently detected VOCs (Volatile Organic Compounds) in groundwater, residual TCE can be detected by gas monitoring. Therefore, monitoring of temporal and spatial variations in the gas phase TCE contaminant at an industrial complex in Wonju, Korea, were used to find the residual TCE locations. As pilot tests, TCE gas samples collected in the unsaturated zone at 4 different wells were analyzed using SPME (Solid Phase MicroExtraction) fiber and Gas Chromatography (GC). The results indicated that detecting TCE in gas phase was successful from these wells and TCE analysis on gas samples, collected from the unsaturated zone, will be useful for source area characterization. However, some values were too high to doubt the accuracy of the current method, which needs a preliminary lab test with known concentrations. The modified experiment setups using packer at different depths are in process to find residual TCE locations in the unsaturated zone. Meanwhile, several PVD (polyethylene-membrane Passive Vapor Diffusion) samplers were placed under water table to detect VOCs by equilibrium between air in the vial and VOCs in pore water.

Acoustic waves in unsaturated soils

NASA Astrophysics Data System (ADS)

Lo, Wei-Cheng; Sposito, Garrison

2013-09-01

Seminal papers by Brutsaert (1964) and Brutsaert and Luthin (1964) provided the first rigorous theoretical framework for examining the poroelastic behavior of unsaturated soils, including an important application linking acoustic wave propagation to soil hydraulic properties. Theoretical developments during the 50 years that followed have led Lo et al., (2005) to a comprehensive model of these phenomena, but the relationship of its elasticity parameters to standard poroelasticity parameters measured in hydrogeology has not been established. In the present study, we develop this relationship for three key parameters, the Gassman modulus, Skempton coefficient, and Biot-Willis coefficient by generalizing them to an unsaturated porous medium. We demonstrate the remarkable result that well-known and widely applied relationships among these parameters for a porous medium saturated by a single fluid are also valid under very general conditions for unsaturated soils. We show further that measurement of the Biot-Willis coefficient along with three of the six elasticity coefficients in the model of Lo et al. (2005) is sufficient to characterize poroelastic behavior. The elasticity coefficients in the model of Lo et al. (2005) are sensitive to the dependence of capillary pressure on water saturation and its viscous-drag coefficients are functions of relative permeability, implying that hysteresis in the water retention curve and hydraulic conductivity function should affect acoustic wave behavior in unsaturated soils. To quantify these as-yet unknown effects, we performed numerical simulations for Dune sand at two representative wave excitation frequencies. Our results show that the acoustic wave investigated by Brutsaert and Luthin (1964) propagates at essentially the same speed during imbibition and drainage, but is attenuated more during drainage than imbibition. Overall, effects on acoustic wave behavior caused by hysteresis become more significant as the excitation frequency increases.

Temperature calibration and phylogenetically distinct distributions for freshwater alkenones: Evidence from northern Alaskan lakes

NASA Astrophysics Data System (ADS)

Longo, William M.; Theroux, Susanna; Giblin, Anne E.; Zheng, Yinsui; Dillon, James T.; Huang, Yongsong

2016-05-01

Alkenones are a class of unsaturated long-chain ketone biomarkers that have been used to reconstruct sea surface temperature and, more recently, continental temperature, by way of alkenone unsaturation indices (e.g. U37K and U37K‧). Alkenones are frequently found in brackish and saline lakes, however species effects confound temperature reconstructions when multiple alkenone-producing species with different temperature responses are present. Interestingly, available genetic data indicate that numerous freshwater lakes host a distinct phylotype of alkenone-producing haptophyte algae (the Group I or Greenland phylotype), providing evidence that species effects may be diminished in freshwater lakes. These findings encourage further investigation of alkenone paleotemperature proxies in freshwater systems. Here, we investigated lakes from northern Alaska (n = 35) and show that alkenones commonly occurred in freshwater lakes, where they featured distinct distributions, characterized by dominant C37:4 alkenones and a series of tri-unsaturated alkenone isomers. The distributions were characteristic of Group I-type alkenone distributions previously identified in Greenland and North America. Our analysis of suspended particulate matter from Toolik Lake (68° 38‧N, 149° 36‧W) yielded the first in situ freshwater U37K calibration (U37K = 0.021 * T - 0.68; r2 = 0.85; n = 52; RMSE = ±1.37 °C). We explored the environmental significance of the tri-unsaturated isomers using our northern Alaskan lakes dataset in conjunction with new data from haptophyte cultures and Canadian surface sediments. Our results show that these temperature-sensitive isomers are biomarkers for the Group I phylotype and indicators of multiple-species effects. Together, these findings highlight freshwater lakes as valuable targets for continental alkenone-based paleotemperature reconstructions and demonstrate the significance of the recently discovered tri-unsaturated isomers.

Imaging and Measurements of Flow Phenomena and Impact of Soil Associated Constituents Through Unsaturated Porous Media in a 2D System

NASA Astrophysics Data System (ADS)

Pales, A. R.; Li, B.; Clifford, H.; Edayilam, N.; Montgomery, D.; Dogan, M.; Tharayil, N.; Martinez, N. E.; Moysey, S. M.; Darnault, C. J. G.

2016-12-01

This research aims to build upon past two-dimension (2D) tank light transmission methods to quantify real-time flow in unsaturated porous media (ASTM silica sand; US Silica, Ottawa, IL, USA) and how exudates effect unstable flow patterns. A 2D tank light transmission method was created using a transparent flow through tank coupled with a random rainfall simulator; a commercial LED light and a complementary metal oxide semiconductor digital single lens reflex (CMOS DSLR) Nikon D5500 camera were used to capture the real-time flow images. The images were broken down from red-green-blue (RGB) into hue-saturation-intensity (HVI) and analyzed in Matlab to produce quantifiable data about finger formation and water saturation distribution. Contact angle and surface tension of the chemical plant exudate solutions was measured using a Kruss EasyDrop FM40Mk2 (Kruss GmbH Germany). The exudates (oxalate, citrate, tannic acid, and Suwannee River Natural Organic Matter) had an increased wettability effect compared to control rain water (0.01M NaCl). This resulted in variable finger formation and speed of finger propagation; dependent on exudate type and concentration. Water saturation along the vertical and horizontal profile (Matlab) was used to quantify the finger more objectively than by eye assessment alone. The changes in finger formation and speed of propagation between the control rain water (0.01M NaCl) and the solutions containing plant exudates illustrates that the plant exudates increased the wettability (mobility) of water moving through unsaturated porous media. This understanding of plant exudates effect on unsaturated flow is important for future works in this study to analyze how plants, their roots and exudates, may affect the mobility of radionuclides in unsaturated porous media.

Metal-organic frameworks as selectivity regulators for hydrogenation reactions

NASA Astrophysics Data System (ADS)

Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong

2016-11-01

Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe3+, Cr3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design strategy will allow the development of other selective heterogeneous catalysts for important yet challenging transformations.

Effect of grain-coating mineralogy on nitrate and sulfate storage in the unsaturated zone

USGS Publications Warehouse

Reilly, T.J.; Fishman, N.S.; Baehr, A.L.

2009-01-01

Unsaturated-zone sediments and the chemistry of shallow groundwater underlying a small (???8-km2) watershed were studied to identify the mechanisms responsible for anion storage within the Miocene Bridgeton Formation and weathered Coastal Plain deposits in southern New Jersey. Lower unsaturated-zone sediments and shallow groundwater samples were collected and concentrations of selected ions (including NO3- and SO42-) from 11 locations were determined. Grain size, sorting, and color of the lower unsaturated-zone sediments were determined and the mineralogy of these grains and the composition of coatings were analyzed by petrographic examination, scanning electron microscopy and energy dispersive analysis of x-rays, and quantitative whole-rock x-ray diffraction. The sediment grains, largely quartz and chert (80-94% w/w), are coated with a very fine-grained (<20 ??m), complex mixture of kaolinite, halloysite, goethite, and possibly gibbsite and lepidocrocite. The mineral coatings are present as an open fabric, resulting in a large surface area in contact with pore water. Significant correlations between the amount of goethite in the grain coatings and the concentration of sediment-bound SO42- were observed, indicative of anion sorption. Other mineral-chemical relations indicate that negatively charged surfaces and competition with SO 42- results in exclusion of NO3- from inner sphere exchange sites. The observed NO3- storage may be a result of matrix forces within the grain coatings and outer sphere complexation. The results of this study indicate that the mineralogy of grain coatings can have demonstrable effects on the storage of NO 3- and SO42- in the unsaturated zone. ?? Soil Science Society of America. All rights reserved.

Modeling variably saturated subsurface solute transport with MODFLOW-UZF and MT3DMS

USGS Publications Warehouse

Morway, Eric D.; Niswonger, Richard G.; Langevin, Christian D.; Bailey, Ryan T.; Healy, Richard W.

2013-01-01

The MT3DMS groundwater solute transport model was modified to simulate solute transport in the unsaturated zone by incorporating the unsaturated-zone flow (UZF1) package developed for MODFLOW. The modified MT3DMS code uses a volume-averaged approach in which Lagrangian-based UZF1 fluid fluxes and storage changes are mapped onto a fixed grid. Referred to as UZF-MT3DMS, the linked model was tested against published benchmarks solved analytically as well as against other published codes, most frequently the U.S. Geological Survey's Variably-Saturated Two-Dimensional Flow and Transport Model. Results from a suite of test cases demonstrate that the modified code accurately simulates solute advection, dispersion, and reaction in the unsaturated zone. Two- and three-dimensional simulations also were investigated to ensure unsaturated-saturated zone interaction was simulated correctly. Because the UZF1 solution is analytical, large-scale flow and transport investigations can be performed free from the computational and data burdens required by numerical solutions to Richards' equation. Results demonstrate that significant simulation runtime savings can be achieved with UZF-MT3DMS, an important development when hundreds or thousands of model runs are required during parameter estimation and uncertainty analysis. Three-dimensional variably saturated flow and transport simulations revealed UZF-MT3DMS to have runtimes that are less than one tenth of the time required by models that rely on Richards' equation. Given its accuracy and efficiency, and the wide-spread use of both MODFLOW and MT3DMS, the added capability of unsaturated-zone transport in this familiar modeling framework stands to benefit a broad user-ship.

Modeling variably saturated subsurface solute transport with MODFLOW-UZF and MT3DMS.

PubMed

Morway, Eric D; Niswonger, Richard G; Langevin, Christian D; Bailey, Ryan T; Healy, Richard W

2013-03-01

The MT3DMS groundwater solute transport model was modified to simulate solute transport in the unsaturated zone by incorporating the unsaturated-zone flow (UZF1) package developed for MODFLOW. The modified MT3DMS code uses a volume-averaged approach in which Lagrangian-based UZF1 fluid fluxes and storage changes are mapped onto a fixed grid. Referred to as UZF-MT3DMS, the linked model was tested against published benchmarks solved analytically as well as against other published codes, most frequently the U.S. Geological Survey's Variably-Saturated Two-Dimensional Flow and Transport Model. Results from a suite of test cases demonstrate that the modified code accurately simulates solute advection, dispersion, and reaction in the unsaturated zone. Two- and three-dimensional simulations also were investigated to ensure unsaturated-saturated zone interaction was simulated correctly. Because the UZF1 solution is analytical, large-scale flow and transport investigations can be performed free from the computational and data burdens required by numerical solutions to Richards' equation. Results demonstrate that significant simulation runtime savings can be achieved with UZF-MT3DMS, an important development when hundreds or thousands of model runs are required during parameter estimation and uncertainty analysis. Three-dimensional variably saturated flow and transport simulations revealed UZF-MT3DMS to have runtimes that are less than one tenth of the time required by models that rely on Richards' equation. Given its accuracy and efficiency, and the wide-spread use of both MODFLOW and MT3DMS, the added capability of unsaturated-zone transport in this familiar modeling framework stands to benefit a broad user-ship. Published 2012. This article is a U.S. Government work and is in the public domain in the USA.

New Hydrologic Insights to Advance Geophysical Investigation of the Unsaturated Zone

NASA Astrophysics Data System (ADS)

Nimmo, J. R.; Perkins, K. S.

2015-12-01

Advances in hydrology require information from the unsaturated zone, especially for problems related to groundwater contamination, water-supply sustainability, and ecohydrology. Unsaturated-zone processes are notoriously difficult to quantify; soils and rocks are visually opaque, spatially variable in the extreme, and easily disturbed by instrument installation. Thus there is great value in noninvasive techniques that produce water-related data of high density in space and time. Methods based on resistivity and electromagnetic waves have already produced significant new understanding of percolation processes, root-zone water retention, influences of evapotranspiration on soil-water, and effects of preferential flow. Further developments are underway for such purposes as noninvasive application to greater depths, increased resolution, adaptation for lab-scale experiments, and calibration in heterogeneous media. Beyond these, however, there is need for a stronger marriage of hydrologic and geophysical knowledge and perspective. Possible means to greater and faster progress include: Apply the latest hydrologic understanding, both pore-scale and macroscopic, to the detection of preferential flow paths and their degree of activation. In the continuing advancement of hardware and techniques, draw creatively from developments in such fields as high-energy physics, medical imaging, astrogeology, high-tech semiconductors, and bioinstrumentation. Sidestep the imaging process where possible to measure essential properties and fluxes more directly. Pose questions that have a strong end-use character, like "how does storm intensity relate to aquifer recharge rate" rather than "what is the shape of the wetting front". The greatest advances in geophysical investigation of the unsaturated zone will come from methods informed by the latest understanding of unsaturated systems and processes, and aimed as directly as possible at the answers to important hydrologic questions.

Metal-organic frameworks as selectivity regulators for hydrogenation reactions.

PubMed

Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong

2016-11-03

Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe 3+ , Cr 3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design strategy will allow the development of other selective heterogeneous catalysts for important yet challenging transformations.

Unsaturation of Very-Long-Chain Ceramides Protects Plant from Hypoxia-Induced Damages by Modulating Ethylene Signaling in Arabidopsis

PubMed Central

Yu, Lu-Jun; Huang, Li; Chen, Liang; Wang, Feng-Zhu; Xia, Fan-Nv; Zhu, Tian-Ren; Wu, Jian-Xin; Yin, Jian; Liao, Bin; Shi, Jianxin; Zhang, Jian-Hua; Aharoni, Asaph; Yao, Nan; Shu, Wensheng; Xiao, Shi

2015-01-01

Lipid remodeling is crucial for hypoxic tolerance in animals, whilst little is known about the hypoxia-induced lipid dynamics in plants. Here we performed a mass spectrometry-based analysis to survey the lipid profiles of Arabidopsis rosettes under various hypoxic conditions. We observed that hypoxia caused a significant increase in total amounts of phosphatidylserine, phosphatidic acid and oxidized lipids, but a decrease in phosphatidylcholine (PC) and phosphatidylethanolamine (PE). Particularly, significant gains in the polyunsaturated species of PC, PE and phosphatidylinositol, and losses in their saturated and mono-unsaturated species were evident during hypoxia. Moreover, hypoxia led to a remarkable elevation of ceramides and hydroxyceramides. Disruption of ceramide synthases LOH1, LOH2 and LOH3 enhanced plant sensitivity to dark submergence, but displayed more resistance to submergence under light than wild type. Consistently, levels of unsaturated very-long-chain (VLC) ceramide species (22:1, 24:1 and 26:1) predominantly declined in the loh1, loh2 and loh3 mutants under dark submergence. In contrast, significant reduction of VLC ceramides in the loh1-1 loh3-1 knockdown double mutant and lacking of VLC unsaturated ceramides in the ads2 mutants impaired plant tolerance to both dark and light submergences. Evidence that C24:1-ceramide interacted with recombinant CTR1 protein and inhibited its kinase activity in vitro, enhanced ER-to-nucleus translocation of EIN2-GFP and stabilization of EIN3-GFP in vivo, suggests a role of ceramides in modulating CTR1-mediated ethylene signaling. The dark submergence-sensitive phenotypes of loh mutants were rescued by a ctr1-1 mutation. Thus, our findings demonstrate that unsaturation of VLC ceramides is a protective strategy for hypoxic tolerance in Arabidopsis. PMID:25822663

Triaxial- and uniaxial-compression testing methods developed for extraction of pore water from unsaturated tuff, Yucca Mountain, Nevada

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

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

1989-12-31

To support the study of hydrologic system in the unsaturated zone at Yucca Mountain, Nevada, two extraction methods were examined to obtain representative, uncontaminated pore-water samples from unsaturated tuff. Results indicate that triaxial compression, which uses a standard cell, can remove pore water from nonwelded tuff that has an initial moisture content greater than 11% by weight; uniaxial compression, which uses a specifically fabricated cell, can extract pore water from nonwelded tuff that has an initial moisture content greater than 8% and from welded tuff that has an initial moisture content greater than 6.5%. For the ambient moisture conditions ofmore » Yucca Mountain tuffs, uniaxial compression is the most efficient method of pore-water extraction. 12 refs., 7 figs., 2 tabs.« less

A Similarity Theory for Unsaturated Downdrafts within Clouds.

NASA Astrophysics Data System (ADS)

Emanuel, Kerry A.

1981-08-01

Recent observations of cumulus clouds strongly support the hypothesis of Squires (1958) that much of the mixing within such clouds is associated with downward propagating currents initiated near their tops. A similarity theory is here proposed to describe the properties of such currents; the use of similarity is defended on the basis of the observed and predicted scale of the downdrafts. The theory suggests that downward-propagating unsaturated thermals are pervasive throughout all but the largest convective clouds and that quasi-steady unsaturated downdraft plumes may exist in the lower portions of cumulonimbi. In addition to providing a reasonable explanation for the microstructure of and liquid water distribution within cumulus clouds, the theory appears to account for certain severe convective phenomena, including down-bursts. A new but related cloud instability is proposed to account for the occurrence of mamma.

Solution of AntiSeepage for Mengxi River Based on Numerical Simulation of Unsaturated Seepage

PubMed Central

Ji, Youjun; Zhang, Linzhi; Yue, Jiannan

2014-01-01

Lessening the leakage of surface water can reduce the waste of water resources and ground water pollution. To solve the problem that Mengxi River could not store water enduringly, geology investigation, theoretical analysis, experiment research, and numerical simulation analysis were carried out. Firstly, the seepage mathematical model was established based on unsaturated seepage theory; secondly, the experimental equipment for testing hydraulic conductivity of unsaturated soil was developed to obtain the curve of two-phase flow. The numerical simulation of leakage in natural conditions proves the previous inference and leakage mechanism of river. At last, the seepage control capacities of different impervious materials were compared by numerical simulations. According to the engineering actuality, the impervious material was selected. The impervious measure in this paper has been proved to be effectible by hydrogeological research today. PMID:24707199

Unsaturated C3,5,7,9-Monocarboxylic Acids by Aqueous, One-Pot Carbon Fixation: Possible Relevance for the Origin of Life

PubMed Central

Scheidler, Christopher; Sobotta, Jessica; Eisenreich, Wolfgang; Wächtershäuser, Günter; Huber, Claudia

2016-01-01

All scientific approaches to the origin of life share a common problem: a chemical path to lipids as main constituents of extant cellular enclosures. Here we show by isotope-controlled experiments that unsaturated C3,5,7,9-monocarboxylic acids form by one-pot reaction of acetylene (C2H2) and carbon monoxide (CO) in contact with nickel sulfide (NiS) in hot aqueous medium. The primary products are toto-olefinic monocarboxylic acids with CO-derived COOH groups undergoing subsequent stepwise hydrogenation with CO as reductant. In the resulting unsaturated monocarboxylic acids the double bonds are mainly centrally located with mainly trans-configuration. The reaction conditions are compatible with an origin of life in volcanic-hydrothermal sub-seafloor flow ducts. PMID:27283227

[Role of Mediterranean diet on the prevention of Alzheimer disease].

PubMed

Miranda, Arnoldo; Gómez-Gaete, Carolina; Mennickent, Sigrid

2017-04-01

Type 2 diabetes and obesity are possible risk factors for Alzheimer’s disease and these can be modified by physical activity and changes in dietary patterns, such as switching to a Mediterranean diet. This diet includes fruits, vegetables, olive oil, fish and moderate wine intake. These foods provide vitamins, polyphenols and unsaturated fatty acids. This diet should be able to reduce oxidative stress. The inflammatory response is also reduced by unsaturated fatty acids, resulting in a lower expression and a lower production of pro-inflammatory cytokines. The Cardiovascular protection is related to the actions of polyphenols and unsaturated fatty acids on the vascular endothelium. The Mediterranean diet also can improve cardiovascular risk factors such as dyslipidemia, hypertension and metabolic syndrome. These beneficial effects of the Mediterranean diet should have a role in Alzheimer’s disease prevention.

From Solvolysis to Self-Assembly*

PubMed Central

Stang, Peter J.

2009-01-01

My sojourn from classical physical-organic chemistry and solvolysis to self-assembly and supramolecular chemistry, over the last forty years, is described. My contributions to unsaturated reactive intermediates, namely vinyl cations and unsaturated carbenes, along with my decade long involvement with polyvalent iodine chemistry, especially alkynyliodonium salts, as well as my more recent research with metal-ligand, coordination driven and directed self-assembly of finite supramolecular ensembles are discussed. PMID:19111062

Organocatalytic Enantioselective Michael/Cyclization Domino Reaction between 3-Amideoxindoles and α,β-Unsaturated Aldehydes: One-Pot Preparation of Chiral Spirocyclic Oxindole-γ-lactams.

PubMed

Yang, Peng; Wang, Xiao; Chen, Feng; Zhang, Zheng-Bing; Chen, Chao; Peng, Lin; Wang, Li-Xin

2017-04-07

The first organocatalytic enantioselective Michael/cyclization domino reaction between 3-amideoxindoles and α,β-unsaturated aldehydes is described. After sequential oxidation with pyridinium chlorochromate, a direct and one-pot preparation of highly sterically hindered spirocyclic oxindole-γ-lactams was achieved in 51-81% yields with 75-97% ee and ≤80/20 dr.

Lateral water flux in the unsaturated zone: A mechanism for the formation of spatial soil heterogeneity in a headwater catchment

Treesearch

John P. Gannon; Kevin J. McGuire; Scott W. Bailey; Rebecca R. Bourgault; Donald S. Ross

2017-01-01

Measurements of soil water potential and water table fluctuations suggest that morphologically distinct soils in a headwater catchment at the Hubbard Brook Experimental Forest in New Hampshire formed as a result of variations in saturated and unsaturated hydrologic fluxes in the mineral soil. Previous work showed that each group of these soils had distinct water table...

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.

Unsaturated Lipids Change in Olive Tree Drupe and Seed during Fruit Development and in Response to Cold-Stress and Acclimation

PubMed Central

D’Angeli, Simone; Altamura, Maria Maddalena

2016-01-01

The olive tree is a plant of economic value for the oil of its drupe. It is a cultigen complex composed of genotypes with differences in cold-hardiness. About 90% of the oil is stored in oil bodies (OBs) in the drupe during the oleogenic phase. Phenols and lipids contribute to oil quality, but the unsaturated fatty acid (FA) fraction is emerging as the most important for quality, because of the very high content in oleic acid, the presence of ω6-linoleic acid and ω3-linolenic acid, and the very low saturated FA content. Another 10% of oil is produced by the seed. Differences in unsaturated FA-enriched lipids exist among seed coat, endosperm, and embryo. Olive oil quality is also affected by the environmental conditions during fruit growth and genotype peculiarities. Production of linoleic and α-linolenic acids, fruit growth, fruit and leaf responses to low temperatures, including cuticle formation, and cold-acclimation are related processes. The levels of unsaturated FAs are changed by FA-desaturase (FAD) activities, involving the functioning of chloroplasts and endoplasmic reticulum. Cold induces lipid changes during drupe and seed development, affecting FADs, but its effect is related to the genotype capability to acclimate to the cold. PMID:27845749

Does water content or flow rate control colloid transport in unsaturated porous media?

PubMed

Knappenberger, Thorsten; Flury, Markus; Mattson, Earl D; Harsh, James B

2014-04-01

Mobile colloids can play an important role in contaminant transport in soils: many contaminants exist in colloidal form, and colloids can facilitate transport of otherwise immobile contaminants. In unsaturated soils, colloid transport is, among other factors, affected by water content and flow rate. Our objective was to determine whether water content or flow rate is more important for colloid transport. We passed negatively charged polystyrene colloids (220 nm diameter) through unsaturated sand-filled columns under steady-state flow at different water contents (effective water saturations Se ranging from 0.1 to 1.0, with Se = (θ - θr)/(θs - θr)) and flow rates (pore water velocities v of 5 and 10 cm/min). Water content was the dominant factor in our experiments. Colloid transport decreased with decreasing water content, and below a critical water content (Se < 0.1), colloid transport was inhibited, and colloids were strained in water films. Pendular ring and water film thickness calculations indicated that colloids can move only when pendular rings are interconnected. The flow rate affected retention of colloids in the secondary energy minimum, with less colloids being trapped when the flow rate increased. These results confirm the importance of both water content and flow rate for colloid transport in unsaturated porous media and highlight the dominant role of water content.

Cuticular lipids and odors induce sex-specific behaviors in the male cricket Gryllus bimaculatus.

PubMed

Iwasaki, Masazumi; Katagiri, Chihiro

2008-03-01

Male crickets display sex-specific (e.g., mating and agonistic) behaviors towards conspecific individuals. One of the key signals for these behaviors is the chemical substance on the cricket body surface. In the present study, we analyzed female and male cuticular substances in behavioral assays. Antennal contact stimulation using female forewings elicited a mating behavior in males, while that using male forewings elicited an agonistic behavior in males. Thin-layer-chromatographic and other techniques analysis showed that saturated cuticular lipids were present in both female and male cuticles and that unsaturated lipids were present only in the male cuticle. Filter papers soaked with saturated or unsaturated cuticular lipids were applied to antennae of male crickets. Males showed mating behavior in response to stimulation with saturated lipids from both females and males but showed avoidance behavior in response to stimulation with male unsaturated lipids. Because cuticular lipids did not induce agonistic behavior in males, we collected odors from male crickets and found that these odors induced agonistic behavior in males. Therefore, we concluded that the key signals for mating, avoidance and agonistic behaviors of male crickets are comprised of at least three different components, saturated and unsaturated cuticular lipids and male odors, respectively.

Unsaturated Fatty Acids Supplementation Reduces Blood Lead Level in Rats

PubMed Central

Skoczyńska, Anna; Wojakowska, Anna; Nowacki, Dorian; Bobak, Łukasz; Turczyn, Barbara; Smyk, Beata; Szuba, Andrzej; Trziszka, Tadeusz

2015-01-01

Some dietary factors could inhibit lead toxicity. The aim of this study was to evaluate the effect of dietary compounds rich in unsaturated fatty acids (FA) on blood lead level, lipid metabolism, and vascular reactivity in rats. Serum metallothionein and organs' lead level were evaluated with the aim of assessing the possible mechanism of unsaturated FA impact on blood lead level. For three months, male Wistar rats that were receiving drinking water with (100 ppm Pb) or without lead acetate were supplemented per os daily with virgin olive oil or linseed oil (0.2 mL/kg b.w.) or egg derived lecithin fraction: “super lecithin” (50 g/kg b.w.). Mesenteric artery was stimulated ex vivo by norepinephrine (NE) administered at six different doses. Lecithin supplementation slightly reduced pressor responses of artery to NE. Lead administered to rats attenuated the beneficial effect of unsaturated FA on lipid metabolism and vascular reactivity to adrenergic stimulation. On the other hand, the super lecithin and linseed oil that were characterized by low omega-6 to omega-3 ratio (about 1) reduced the blood lead concentration. This effect was observed in lead poisoned rats (p < 0.0001) and also in rats nonpoisoned with lead (p < 0.05). PMID:26075218

Performance of the Fluidized Bed Steam Reforming Product Under Hydraulically Unsaturated Conditions

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

Neeway, James J.; Qafoku, Nikolla; Williams, Benjamin D.

2014-05-01

Currently, several candidates for secondary waste immobilization at the Hanford site in the State of Washington, USA are being considered. To demonstrate the durability of the product in the unsaturated Integrated Disposal Facility (IDF) at the site, a series of tests have been performed one of the candidate materials using the Pressurized Unsaturated Flow (PUF) system. The material that was tested was the Fluidized Bed Steam Reformer (FBSR) granular product and the granular product encapsulated in a geopolymer matrix. The FBSR product is composed primarily of an insoluble sodium aluminosilicate matrix with the dominant phases being feldspathoid minerals mostly nepheline,more » sodalite, and nosean. The PUF test method allows for the accelerated weathering of materials, including radioactive waste forms, under hydraulically unsaturated conditions, thus mimicking the open-flow and transport properties that most likely will be present at the IDF. The experiments show a trend of decreasing tracer release as a function of time for several of the elements released from the material including Na, Si, Al, and Cs. However, some of the elements, notably I and Re, show a steady release throughout the yearlong test. This result suggests that the release of these minerals from the sodalite cage occurs at a different rate compared with the dissolution of the predominant nepheline phase.« less

Limited denitrification in glacial deposit aquifers having thick unsaturated zones (Long Island, USA)

NASA Astrophysics Data System (ADS)

Young, Caitlin; Kroeger, Kevin D.; Hanson, Gilbert

2013-12-01

The goal of this study was to demonstrate how the extent of denitrification, which is indirectly related to dissolved organ carbon and directly related to oxygen concentrations, can also be linked to unsaturated-zone thickness, a mappable aquifer property. Groundwater from public supply and monitoring wells in Northport on Long Island, New York state (USA), were analyzed for denitrification reaction progress using dissolved N2/Ar concentrations by membrane inlet mass spectrometry. This technique allows for discernment of small amounts of excess N2, attributable to denitrification. Results show an average 15 % of total nitrogen in the system was denitrified, significantly lower than model predictions of 35 % denitrification. The minimal denitrification is due to low dissolved organic carbon (29.3-41.1 μmol L-1) and high dissolved oxygen concentrations (58-100 % oxygen saturation) in glacial sediments with minimal solid-phase electron donors to drive denitrification. A mechanism is proposed that combines two known processes for aquifer re-aeration in unconsolidated sands with thick (>10 m) unsaturated zones. First, advective flux provides 50 % freshening of pore space oxygen in the upper 2 m due to barometric pressure changes. Then, oxygen diffusion across the water-table boundary occurs due to high volumetric air content in the unsaturated-zone catchment area.

Using ambient ozone for assignment of double bond position in unsaturated lipids.

PubMed

Ellis, Shane R; Hughes, Jessica R; Mitchell, Todd W; in het Panhuis, Marc; Blanksby, Stephen J

2012-03-07

Unsaturated lipids deposited onto a range of materials are observed to react with the low concentrations of ozone present in normal laboratory air. Parent lipids and ozonolysis cleavage products are both detected directly from surfaces by desorption electrospray ionisation mass spectrometry (DESI-MS) with the resulting mass spectra providing clear evidence of the double bond position within these molecules. This serendipitous process has been coupled with thin-layer chromatography (TLC) to provide a simple but powerful approach for the detailed structural elucidation of lipids present in complex biological extracts. Lipid extracts from human lens were deposited onto normal phase TLC plates and then developed to separate components according to lipid class. Exposure of the developed plates to laboratory air for ca. 1 h prior to DESI-MS analysis gave rise to ozonolysis products allowing for the unambiguous identification of double bond positions in even low abundant, unsaturated lipids. In particular, the co-localization of intact unsaturated lactosylceramides (LacCer) with products from their oxidative cleavage provide the first evidence for the presence of three isomeric LacCer (d18:0/24:1) species in the ocular lens lipidome, i.e., variants with double bonds at the n-9, n-7 and n-5 positions.

Onsite wastewater nitrogen reduction with expanded media and elemental sulfur biofiltration.

PubMed

Smith, D P

2012-01-01

A passive biofiltration process has been developed to enhance nitrogen removal from onsite sanitation water. The system employs an initial unsaturated vertical flow biofilter with expanded clay media (nitrification), followed in series by a horizontal saturated biofilter for denitrification containing elemental sulfur media as electron donor. A small-scale prototype was operated continuously over eight months on primary wastewater effluent with total nitrogen (TN) of 72.2 mg/L. The average hydraulic loading to the unsaturated biofilter surface was 11.9 cm/day, applied at a 30 min dosing cycle. Average effluent TN was 2.6 mg/L and average TN reduction efficiency was 96.2%. Effluent nitrogen was 1.7 mg/L as organic N, 0.93 mg/L as ammonium (NH(4)-N), and 0.03 as oxidized (NO(3) + NO(2)) N. There was no surface clogging of unsaturated media, nitrate breakthrough, or replenishment of sulfur media over eight months. Visual and microscopic examinations revealed substantially open pores with limited material accumulation on the upper surface of the unsaturated media. Material accumulation was observed at the inlet zone of the denitrification biofilter, and sulfur media exhibited surface cavities consistent with oxidative dissolution. Two-stage biofiltration is a simple and resilient system for achieving high nitrogen reductions in onsite wastewater.

Simulated fate and transport of metolachlor in the unsaturated zone, Maryland, USA

USGS Publications Warehouse

Bayless, E.R.; Capel, P.D.; Barbash, J.E.; Webb, R.M.T.; Hancock, T.L.C.; Lampe, D.C.

2008-01-01

An unsaturated-zone transport model was used to examine the transport and fate of metolachlor applied to an agricultural site in Maryland, USA. The study site was instrumented to collect data on soil-water content, soil-water potential, ground water levels, major ions, pesticides, and nutrients from the unsaturated zone during 2002-2004. The data set was enhanced with site-specific information describing weather, soils, and agricultural practices. The Root Zone Water Quality Model was used to simulate physical, chemical, and biological processes occurring in the unsaturated zone. Model calibration to bromide tracer concentrations indicated flow occurred through the soil matix. Simulated recharge rates were within the measured range of values. The pesticide transport model was calibrated to the intensive data collection period (2002-2004), and the calibrated model was then used to simulate the period 1984 through 2004 to examine the impact of sustained agricultural management practices on the concentrations of metolachlor and its degradates at the study site. Simulation results indicated that metolachlor degrades rapidly in the root zone but that the degradates are transported to depth in measurable quantities. Simulations indicated that degradate transport is strongly related to the duration of sustained use of metolachlor and the extent of biodegradation. 

Graphene oxide-facilitated transport of levofloxacin and ciprofloxacin in saturated and unsaturated porous media.

PubMed

Sun, Kaixuan; Dong, Shunan; Sun, Yuanyuan; Gao, Bin; Du, Wenchao; Xu, Hongxia; Wu, Jichun

2018-04-15

In this work, effects of graphene oxide (GO) on the co-transport of the two typical Fluoroquinolones (FQs) - levofloxacin (LEV) and ciprofloxacin (CIP) in saturated and unsaturated quartz sand media were studied. The adsorption isotherms showed that GO had much larger sorption capacities to LEV and CIP than sand with the largest Langmuir adsorption capacity of 409 mg g -1 (CIP-GO); while the sorption affinity of the two FQs onto the two adsorbents might follow the order of CIP-sand > LEV-sand > LEV-GO > CIP-GO. GO promoted the mobility of the two FQs in both saturated and unsaturated porous media due to its strong mobility and sorption capacity. The GO-bound LEV/CIP was responsible for the LEV/CIP transport in the porous media, and transport of GO-bound FQs increased with the increasing of initial GO concentration. Under unsaturated conditions, moisture showed little effect on the transport of GO-bound CIP; however, the mobility of GO-bound LEV reduced with the decreasing of moisture content, suggesting the transport of adsorbed LEV from GO to air-water interface. GO sorption reduced the antibacterial ability of the two FQs, but they were still effective in inhibiting E. coli growth. Copyright © 2018 Elsevier B.V. All rights reserved.

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

Development of sugar palm yarn/glass fibre reinforced unsaturated polyester hybrid composites

NASA Astrophysics Data System (ADS)

Nurazzi, N. Mohd; Khalina, A.; Sapuan, S. Mohd; Rahmah, M.

2018-04-01

This study investigates the effect of fibre hybridization for sugar palm yarn fibre with glass fibre reinforced with unsaturated polyester composites. In this work, unsaturated polyester resin are reinforced with fibre at a ratio of 70:30 wt% and 60:40 wt%. The hybrid composites were characterized in terms of physical (density and water absorption), mechanical (tensile, flexural and compression) and thermal properties through thermal gravimetry analysis (TGA). Density determination showed that density increased with higher wt% of glass fibre. The inherently higher density of glass fibre increased the density of hybrid composite. Resistance to water absorption is improved upon the incorporation of glass fibre and the hybrid composites were found to reach equilibrium absorption at days 4 and 5. As for mechanical performance, the highest tensile strength, tensile modulus, flexural strength, flexural modulus and compression strength were obtained from 40 wt% of fibres reinforcement with ratio of 50:50 wt% of sugar palm yarn fibre and glass fibre reinforced unsaturated polyester composites. The increase of glass fibre loading had a synergistic effect on the mechanical properties to the composites structure due to its superior strength and modulus. The thermal stability of hybrid composites was improved by the increase of onset temperature and the reduction of residues upon increase in temperature.

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.

Enantioselective Diels-Alder reactions of unsaturated beta-ketoesters catalyzed by chiral ruthenium PNNP complexes.

PubMed

Schotes, Christoph; Mezzetti, Antonio

2011-01-01

We report here dicationic ruthenium PNNP complexes that promote the enantioselective Diels-Alder reaction of alpha-methylene beta-ketoesters with various dienes. Complex [Ru(OEt2)2(PNNP)](PF6)2, formed in situ from [RuCl2,(PNNP)] and (Et3O)PF6 (2 equiv.), catalyzes the Diels-Alder reaction of such unsaturated beta-ketoesters to give novel alkoxycarbonyltetrahydro-1-indanone derivatives (nine examples) with up to 93% ee. The crystal structure of the substrate-catalyst adduct shows that the lower face of the substrate is shielded by a phenyl ring of the PNNP ligand, which accounts for the high enantioselectivity. The attack of the diene from the open re enantioface of the unsaturated beta-ketoester is consistent with the absolute configuration of the product. A useful application of this method is the reaction with Dane's diene to give estrone derivatives with up to 99% ee and an ester-exo:endo ratio of up to 145:1 (after recrystallization). Besides the enantioselective formation of all-carbon quaternary centers, this methodology is notable because unsaturated beta-ketoesters have been rarely used in Diels-Alder reactions. Furthermore, enantiomerically pure estrone derivatives are interesting in view of their potential applications, including the treatment of breast cancer.

Unsaturated fatty acids supplementation reduces blood lead level in rats.

PubMed

Skoczyńska, Anna; Wojakowska, Anna; Nowacki, Dorian; Bobak, Łukasz; Turczyn, Barbara; Smyk, Beata; Szuba, Andrzej; Trziszka, Tadeusz

2015-01-01

Some dietary factors could inhibit lead toxicity. The aim of this study was to evaluate the effect of dietary compounds rich in unsaturated fatty acids (FA) on blood lead level, lipid metabolism, and vascular reactivity in rats. Serum metallothionein and organs' lead level were evaluated with the aim of assessing the possible mechanism of unsaturated FA impact on blood lead level. For three months, male Wistar rats that were receiving drinking water with (100 ppm Pb) or without lead acetate were supplemented per os daily with virgin olive oil or linseed oil (0.2 mL/kg b.w.) or egg derived lecithin fraction: "super lecithin" (50 g/kg b.w.). Mesenteric artery was stimulated ex vivo by norepinephrine (NE) administered at six different doses. Lecithin supplementation slightly reduced pressor responses of artery to NE. Lead administered to rats attenuated the beneficial effect of unsaturated FA on lipid metabolism and vascular reactivity to adrenergic stimulation. On the other hand, the super lecithin and linseed oil that were characterized by low omega-6 to omega-3 ratio (about 1) reduced the blood lead concentration. This effect was observed in lead poisoned rats (p < 0.0001) and also in rats nonpoisoned with lead (p < 0.05).

DASH-like diets high in protein or monounsaturated fats improve metabolic syndrome and calculated vascular risk.

PubMed

Root, Martin M; Dawson, Hannah R

2013-01-01

Weight-loss diets with varying proportions of macronutrients have had varying effects on weight loss, and components of metabolic syndrome and risk factors for vascular diseases. However, little work has examined the effect of weight-neutral dietary changes in macronutrients on these factors. This is an investigation using the OMNI Heart datasets available from the NHLBI BioLINCC program. This study compared a DASH-like diet high in carbohydrates with similar diets high in protein and high in unsaturated fats. Measures of metabolic syndrome, except waist, and measures of risk factors for vascular diseases were taken at the end of each dietary period. All 3 diets significantly lowered the number of metabolic syndrome components (p ≤ 0.002) with a standardized measure of changes in metabolic syndrome components, suggesting that the high-protein, high-fat diet was most efficacious overall (p = 0.035). All 3 diets lowered a calculated 10-year risk of cardiovascular disease, with the high-protein and unsaturated fat diet being the most efficacious (p < 0.001). Only the unsaturated fat diet showed a slightly decreased calculated 9-year risk of diabetes (p = 0.11). Of the 3 weight-neutral diets, those high in protein and unsaturated fats appeared partially or wholly most beneficial.

Synopsis of hydrologic data collected by waste management for characterization of unsaturated transport at Area G

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

Vold, E.

1998-03-01

Data which have been collected by Los Alamos National Laboratory waste management for the hydrologic characterization of the subsurface at the low level radioactive waste disposal facility, Area G, are reported and discussed briefly. The data includes Unsaturated Flow Apparatus measurements of the unsaturated conductivity in samples from borehole G-5. Analysis compares these values to the predictions from van Genuchten estimates, and the implications for transport and data matching are discussed, especially at the location of the Vapor Phase Notch (VPN). There, evaporation drives a significant vapor flux and the liquid flux cannot be measured accurately by the UFA device.more » Data also include hydrologic characterization of samples from borehole G-5, Area G surface soils, Los Alamos (Cerros de Rio) basalt, Tsankawi and Cerro-Toledo layers, the Vapor Phase Notch (VPN), and additional new samples from the uppermost tuff layer at Area G. Hydraulic properties from these sample groups can be used to supplement the existing data base. The data in this report can be used to improve the accuracy and reduce the uncertainty in future computational modeling of the unsaturated transport at Area G. This report supports the maintenance plan for the Area G Performance Assessment.« less

Barometric fluctuations in wells tapping deep unconfined aquifers

USGS Publications Warehouse

Weeks, Edwin P.

1979-01-01

Water levels in wells screened only below the water table in unconfined aquifers fluctuate in response to atmospheric pressure changes. These fluctuations occur because the materials composing the unsaturated zone resist air movement and have capacity to store air with a change in pressure. Consequently, the translation of any pressure change at land surface is slowed as it moves through the unsaturated zone to the water table, but it reaches the water surface in the well instantaneously. Thus a pressure imbalance is created that results in a water level fluctuation. Barometric effects on water levels in unconfined aquifers can be computed by solution of the differential equation governing the flow of gas in the unsaturated zone subject to the appropriate boundary conditions. Solutions to this equation for two sets of boundary conditions were applied to compute water level response in a well tapping the Ogallala Formation near Lubbock, Texas from simultaneous microbarograph records. One set of computations, based on the step function unit response solution and convolution, resulted in a very good match between computed and measured water levels. A second set of computations, based on analysis of the amplitude ratios of simultaneous cyclic microbarograph and water level fluctuations, gave inconsistent results in terms of the unsaturated zone pneumatic properties but provided useful insights on the nature of unconfined-aquifer water level fluctuations.

Synthesis of α,β-unsaturated aldehydes as potential substrates for bacterial luciferases.

PubMed

Brodl, Eveline; Ivkovic, Jakov; Tabib, Chaitanya R; Breinbauer, Rolf; Macheroux, Peter

2017-02-15

Bacterial luciferase catalyzes the monooxygenation of long-chain aldehydes such as tetradecanal to the corresponding acid accompanied by light emission with a maximum at 490nm. In this study even numbered aldehydes with eight, ten, twelve and fourteen carbon atoms were compared with analogs having a double bond at the α,β-position. These α,β-unsaturated aldehydes were synthesized in three steps and were examined as potential substrates in vitro. The luciferase of Photobacterium leiognathi was found to convert these analogs and showed a reduced but significant bioluminescence activity compared to tetradecanal. This study showed the trend that aldehydes, both saturated and unsaturated, with longer chain lengths had higher activity in terms of bioluminescence than shorter chain lengths. The maximal light intensity of (E)-tetradec-2-enal was approximately half with luciferase of P. leiognathi, compared to tetradecanal. Luciferases of Vibrio harveyi and Aliivibrio fisheri accepted these newly synthesized substrates but light emission dropped drastically compared to saturated aldehydes. The onset and the decay rate of bioluminescence were much slower, when using unsaturated substrates, indicating a kinetic effect. As a result the duration of the light emission is doubled. These results suggest that the substrate scope of bacterial luciferases is broader than previously reported. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Diastereoselective synthesis of chiral 1,3-cyclohexadienals

PubMed Central

de la Granja, Ángela P.; Capitán, M. Carmen; Moro, R. F.; Marcos, Isidro S.; Garrido, Narciso M.; Sanz, Francisca; Calle, Emilio

2018-01-01

A novel approach to the production of chiral 1,3-cyclohexadienals has been developed. The organocatalysed asymmetric reaction of different β-disubstituted-α,β-unsaturated aldehydes with a chiral α,β-unsaturated aldehyde in the presence of a Jørgensen-Hayashi organocatalyst provides easy and stereocontrolled access to the cyclohexadienal backbone. This method allows for the synthesis of potential photoprotective chiral 1,3-cyclohexadienals and extra extended conjugation compounds in a simple manner. PMID:29438416

Asymmetric hydrogenation of α,β-unsaturated phosphonates with Rh-BisP* and Rh-MiniPHOS catalysts: Scope and mechanism of the reaction

PubMed Central

Gridnev, Ilya D.; Yasutake, Masaya; Imamoto, Tsuneo; Beletskaya, Irina P.

2004-01-01

Optically active 1,2-bis(alkylmethylphosphino)ethanes and bis(alkylmethylphosphino)methanes are unique diphosphine ligands combining the simple molecular structure and P-stereogenic asymmetric environment. This work shows that these ligands exhibit excellent enantioselectivity in rhodium-catalyzed asymmetric hydrogenation of α,β-unsaturated phosphonic acid derivatives. The enantioselective hydrogenation mechanism elucidated by NMR study is also described. PMID:15024119

Asymmetric synthesis of α-alkenyl homoallylic primary amines via 1,2-addition of Grignard reagent to α,β-unsaturated phosphonyl imines.

PubMed

Xiong, Yiwen; Mei, Haibo; Xie, Chen; Han, Jianlin; Li, Guigen; Pan, Yi

2013-01-01

A series of chiral N -phosphonyl protected α-alkenyl homoallylic primary amines were synthesized by asymmetric addition of allylmagnesium bromide Grignard reagent towards chiral α,β-unsaturated imines. Only 1,2-adduct was obtained for all the imines with good yields and excellent diastereoselectivities. The chiral auxiliary could be easily removed under simple conditions, giving free multiple functionalized primary amines.

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.

Diastereoselective synthesis of chiral 1,3-cyclohexadienals.

PubMed

Urosa, Aitor; Tobal, Ignacio E; de la Granja, Ángela P; Capitán, M Carmen; Moro, R F; Marcos, Isidro S; Garrido, Narciso M; Sanz, Francisca; Calle, Emilio; Díez, David

2018-01-01

A novel approach to the production of chiral 1,3-cyclohexadienals has been developed. The organocatalysed asymmetric reaction of different β-disubstituted-α,β-unsaturated aldehydes with a chiral α,β-unsaturated aldehyde in the presence of a Jørgensen-Hayashi organocatalyst provides easy and stereocontrolled access to the cyclohexadienal backbone. This method allows for the synthesis of potential photoprotective chiral 1,3-cyclohexadienals and extra extended conjugation compounds in a simple manner.

The Effect of Dynamic Evaporation Rates on the Mobility of Pharmaceuticals in Unsaturated Environments

NASA Astrophysics Data System (ADS)

Normile, H.; Papelis, C.; Kibbey, T. C. G.

2015-12-01

The focus of this work was on investigating how dynamic rates of evaporation affect the fate and transport of pharmaceutical compounds in unsaturated porous media. The environmental processes of saturation and evaporation control local concentrations of contaminants in pore water of porous media. Specifically, the rate of evaporation can affect the identity and extent of solid formation of a pharmaceutical compound. A range of experiments with different evaporation rates were conducted on sand columns saturated with a solution of ciprofloxacin, a fluoroquinolone antibiotic. Experiments were designed to simulate increased and decreased pore-water concentrations of a compound due to evaporation and resaturation, respectively. Results suggest that varied rates of evaporation cause differences in compound adsorption behavior. This result has significant implications for understanding fate and transport within the unsaturated zone. Preliminary models exploring the impact on contaminant mobility are discussed.

Effect of Manufacturing Method to Tensile Properties of Hybrid Composite Reinforced by Natural (Agel Leaf Fiber) and Glass Fibers

NASA Astrophysics Data System (ADS)

Nugroho, A.; Abdurohman, K.; Kusmono; Hestiawan, H.; Jamasri

2018-04-01

This paper described the effect of different type of manufacturing method to tensile properties of hybrid composite woven agel leaf fiber and glass fiber as an alternative of LSU structure material. The research was done by using 3 ply of woven agel leaf fiber (ALF) and 3 ply of glass fiber (wr200) while the matrix was using unsaturated polyester. Composite manufacturing method used hand lay-up and vacuum bagging. Tensile test conducted with Tensilon universal testing machine, specimen shape and size according to standard size ASTM D 638. Based on tensile test result showed that the tensile strength of agel leaf fiber composite with unsaturated polyester matrix is 54.5 MPa by hand lay-up and 84.6 MPa with vacuum bagging method. From result of tensile test, hybrid fiber agel composite and glass fiber with unsaturated polyester matrix have potential as LSU structure.

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.

Rhodium-catalyzed 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds: large accelerating effects of bases and ligands.

PubMed

Itooka, Ryoh; Iguchi, Yuki; Miyaura, Norio

2003-07-25

The effects of ligands and bases in the rhodium(I)-catalyzed 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds were reinvestigated to carry out the reaction under mild conditions. Rhodium(I) complexes possessing a 1,5-cyclooctadiene (cod) and a hydroxo ligand such as [RhOH(cod)](2) exhibited excellent catalyst activities compared to those of the corresponding rhodium-acac or -chloro complexes and their phosphine derivatives. The reaction was further accelerated in the presence of KOH, thus allowing the 1,4-addition even at 0 degrees C. A cationic rhodium(I)-(R)-binap complex, [Rh(R-binap)(nbd)]BF(4), catalyzed the reaction at 25-50 degrees C in the presence of Et(3)N with high enantioselectivities of up to 99% ee for alpha,beta-unsaturated ketones, 92% for aldehydes, 94% for esters, and 92% for amides.

Binary Phase Behavior of Saturated-Unsaturated Mixed-Acid Triacylglycerols-A Review.

PubMed

Zhang, Lu; Ueno, Satoru; Sato, Kiyotaka

2018-06-01

Most natural lipids contain a complex mixture of individual triacylglycerols (TAGs). An in-depth knowledge of the mixing behavior of TAGs is necessary for the rational design and engineering of food materials. The binary phase diagram of TAGs is a simplified model that can be explored to help foster an understanding of the phase behavior of complex fats and oils. This article reviews recent research on the binary phase behavior of saturated-unsaturated mixed-acid TAGs, with special emphasis on the stearicunsaturated and palmitic-unsaturated diacid TAGs. The occurrence of polymorphic forms and mutual solubility of TAG mixtures are strongly related to the glycerol conformation of the saturated-oleic diacid TAGs; it appears to be most influenced by the chain-length mismatch in saturated-elaidic diacid TAGs. In addition, the polymorphism of pure enantiomers and racemic mixture of chiral TAGs was also reviewed, while the effect of chirality on mixing behavior was discussed.

Transport of viruses through saturated and unsaturated columns packed with sand

USGS Publications Warehouse

Anders, R.; Chrysikopoulos, C.V.

2009-01-01

Laboratory-scale virus transport experiments were conducted in columns packed with sand under saturated and unsaturated conditions. The viruses employed were the male-specific RNA coliphage, MS2, and the Salmonella typhimurium phage, PRD1. The mathematical model developed by Sim and Chrysikopoulos (Water Resour Res 36:173-179, 2000) that accounts for processes responsible for removal of viruses during vertical transport in one-dimensional, unsaturated porous media was used to fit the data collected from the laboratory experiments. The liquid to liquid-solid and liquid to air-liquid interface mass transfer rate coefficients were shown to increase for both bacteriophage as saturation levels were reduced. The experimental results indicate that even for unfavorable attachment conditions within a sand column (e.g., phosphate-buffered saline solution; pH = 7.5; ionic strength = 2 mM), saturation levels can affect virus transport through porous media. ?? Springer Science+Business Media B.V. 2008.

Non-methylene-interrupted fatty acids with Δ5 unsaturation in Sargassum species.

PubMed

Kim, Gwang-Woo; Itabashi, Yutaka

2012-01-01

Detailed fatty acid compositions of five species of the brown algae Sargassum (S. fulvellum, S. horneri, S. boreale, S. thunbergii, and S. yezoense) were determined using silver ion solid phase extraction, gas chromatography (GC), and GC-mass spectrometry (GC-MS) techniques. In addition to a high number of typical saturated and unsaturated fatty acids, the GC-MS spectra of the 4,4-dimethyloxazoline derivatives of fatty acids revealed the occurrence of small amounts of unusual non-methylene-interrupted (NMI) fatty acids with Δ5 unsaturation, namely, 5,9-eicosadienoic (5,9-20:2), 5,11,14-eicosatrienoic (5,11,14-20:3), and 5,11,14,17-eicosatetraenoic (5,11,14,17-20:4) acids. Of these three NMI acids, the 5,9-20:2 acid was found to be the most abundant (0.4%-2.3% of the total fatty acids) and was detected for the first time in algae.

UZIG USGS research: Advances through interdisciplinary interaction

USGS Publications Warehouse

Nimmo, J.R.; Andraski, Brian J.; Rafael, M.-C.

2009-01-01

BBecause vadose zone research relates to diverse disciplines, applications, and modes of research, collaboration across traditional operational and topical divisions is especially likely to yield major advances in understanding. The Unsaturated Zone Interest Group (UZIG) is an informal organization sponsored by the USGS to encourage and support interdisciplinary collaboration in vadose or unsaturated zone hydrologic research across organizational boundaries. It includes both USGS and non-USGS scientists. Formed in 1987, the UZIG operates to promote communication, especially through periodic meetings with presentations, discussions, and field trips. The 10th meeting of the UZIG at Los Alamos, NM, in August 2007 was jointly sponsored by the USGS and Los Alamos National Laboratory. Presentations at this meeting served as the initial basis for selecting papers for this special section of Vadose Zone Journal, the purpose of which is to present noteworthy cutting-edge unsaturated zone research promoted by, facilitated by, or presented in connection with the UZIG.

Visible light-induced oxidation of unsaturated components of cutins: a significant process during the senescence of higher plants.

PubMed

Rontani, Jean-François; Rabourdin, Adélaïde; Pinot, Franck; Kandel, Sylvie; Aubert, Claude

2005-02-01

9-Hydroperoxy-18-hydroxyoctadec-10(trans)-enoic and 10-hydroperoxy-18-hydroxyoctadec-8(trans)-enoic acids deriving from type II (i.e. involving 1O2) photooxidation of 18-hydroxyoleic acid were detected after visible light-induced senescence experiments carried out with Petroselinum sativum and subsequent cutin depolymerisation. These results showed that in senescent plants, where the 1O2 formation rate exceeds the quenching capacity of the photoprotective system, 1O2 can migrate outside the chloroplasts and affect the unsaturated components of cutins. Significant amounts of 9,18-dihydroxyoctadec-10(trans)-enoic and 10,18-dihydroxyoctadec-8(trans)-enoic acids resulting from the reduction of these photoproducts of 18-hydroxyoleic acid were also detected in different natural samples. These results well support the significance of the photooxidation of the unsaturated components of higher plant cutins in the natural environment.

Radial flow towards well in leaky unconfined aquifer

NASA Astrophysics Data System (ADS)

Mishra, P. K.; Kuhlman, K. L.

2012-12-01

An analytical solution is developed for three-dimensional flow towards a partially penetrating large- diameter well in an unconfined aquifer bounded below by a leaky aquitard of finite or semi-infinite extent. The analytical solution is derived using Laplace and Hankel transforms, then inverted numerically. Existing solutions for flow in leaky unconfined aquifers neglect the unsaturated zone following an assumption of instantaneous drainage due to Neuman. We extend the theory of leakage in unconfined aquifers by (1) including water flow and storage in the unsaturated zone above the water table, and (2) allowing the finite-diameter pumping well to partially penetrate the aquifer. The investigation of model-predicted results shows that aquitard leakage leads to significant departure from the unconfined solution without leakage. The investigation of dimensionless time-drawdown relationships shows that the aquitard drawdown also depends on unsaturated zone properties and the pumping-well wellbore storage effects.

Combining metabolic engineering and electrocatalysis: Application to the production of polyamides from sugar

DOE PAGES

Suastegui, Miguel; Matthiesen, John E.; Carraher, Jack M.; ...

2016-01-14

Here, biorefineries aim to convert biomass into a spectrum of products ranging from biofuels to specialty chemicals. To achieve economically sustainable conversion, it is crucial to streamline the catalytic and downstream processing steps. In this work, a route that combines bio- and electrocatalysis to convert glucose into bio-based unsaturated nylon-6,6 is reported. An engineered strain of Saccharomyces cerevisiae was used as the initial biocatalyst for the conversion of glucose into muconic acid, with the highest reported muconic acid titer of 559.5 mg L –1 in yeast. Without any separation, muconic acid was further electrocatalytically hydrogenated to 3-hexenedioic acid in 94more » % yield despite the presence of biogenic impurities. Bio-based unsaturated nylon-6,6 (unsaturated polyamide-6,6) was finally obtained by polymerization of 3-hexenedioic acid with hexamethylenediamine.« less

Stimulation by unsaturated fatty acid of squalene uptake in rat liver microsomes.

PubMed

Chin, J; Bloch, K

1985-07-01

Supernatant protein factor (SPF) and anionic phospholipids such as phosphatidylglycerol (PG) stimulate squalene epoxidase activity in rat liver microsomes by promoting [3H]squalene uptake as well as substrate translocation (Chin, J., and K. Bloch. 1984. J. Biol. Chem. 259: 11735-11738). This process is postulated to be membrane-mediated and not carrier-mediated. Here we show that treatment of PG with phospholipase A2 in the presence of bovine serum albumin abolishes the stimulatory effect of SPF on epoxidase activity. Disaturated fatty acyl-PGs are not as effective as egg yolk lecithin PG in the SPF effect. These findings suggest an important role for the unsaturated fatty acid moiety of PG. We also show that at submicellar concentrations, cis-unsaturated fatty acids stimulate microsomal epoxidase activity whereas saturated fatty acids do not. This effect is due to an increase in substrate uptake which in turn may facilitate substrate availability to the enzyme.

Catalyzed formation of α,β-unsaturated ketones or aldehydes from propargylic acetates by a recoverable and recyclable nanocluster catalyst

NASA Astrophysics Data System (ADS)

Li, Man-Bo; Tian, Shi-Kai; Wu, Zhikun

2014-05-01

An active, recoverable, and recyclable nanocluster catalyst, Au25(SR)18-, has been developed to catalyze the formation of α,β-unsaturated ketones or aldehydes from propargylic acetates. The catalytic process has been proposed to be initialized by an SN2' addition of OH-. Moreover, a dramatic solvent effect was observed, for which a rational explanation was provided.An active, recoverable, and recyclable nanocluster catalyst, Au25(SR)18-, has been developed to catalyze the formation of α,β-unsaturated ketones or aldehydes from propargylic acetates. The catalytic process has been proposed to be initialized by an SN2' addition of OH-. Moreover, a dramatic solvent effect was observed, for which a rational explanation was provided. Electronic supplementary information (ESI) available: Experimental procedures, UV-Vis spectra and fluorescence spectra of catalysts, characterization data, and copies of MS spectra. See DOI: 10.1039/c4nr00658e

Study of the effect of surface treatment of kenaf fibre on mechanical properties of kenaf filled unsaturated polyester composite

NASA Astrophysics Data System (ADS)

Salem, I. A. S.; Rozyanty, A. R.; Betar, B. O.; Adam, T.; Mohammed, M.; Mohammed, A. M.

2017-10-01

In this research, unsaturated polyester/kenaf fiber (UP/KF) composites was prepared by using hand lay-up process. The effect of surface treatment of kenaf fiber on mechanical properties of kenaf filled unsaturated polyester composites were studied. Different concentrationsof stearic acid (SA) were applied, i.e. 0, 0.4, and 0.8 wt%. Tensile strength of untreated UP/KF composites was found to be higher for 40 wt% loading of kenaf fiber. The highest tensile strength value was obtained after treatment with 0.4 wt% concentration of stearic acid at 56 MPa and tensile modulus was at 2409 MPa. From the flexural strength result obtained, it is clearly seen that 40 wt% loading of kenaf fiber and treatment with 0.4 wt% concentration of stearic acid give the highest value at 72 MPa and flexural modulus at 3929 MPa.

Modeling a thick unsaturated zone at San Gorgonio Pass, California: lessons learned after five years of artificial recharge

USGS Publications Warehouse

Flint, Alan L.; Ellett, Kevin M.; Christensen, Allen H.; Martin, Peter

2012-01-01

The information flow among the tasks of framework assessment, numerical modeling, model forecasting and hind casting, and system-performance monitoring is illustrated. Results provide an understanding of artificial recharge in high-altitude desert settings where large vertical distances may separate application ponds from their target aquifers.Approximately 3.8 million cubic meters of surface water was applied to spreading ponds from 2003–2007 to artificially recharge the underlying aquifer through a 200-meter thick unsaturated zone in the San Gorgonio Pass area in southern California. A study was conducted between 1997 and 2003, and a numerical model was developed to help determine the suitability of the site for artificial recharge. Ongoing monitoring results indicated that the existing model needed to be modified and recalibrated to more accurately predict artificial recharge at the site. The objective of this work was to recalibrate the model by using observation of the application rates, the rise and fall of the water level above a perching layer, and the approximate arrival time to the water table during the 5-yr monitoring period following initiation of long-term artificial recharge. Continuous monitoring of soil-matric potential, temperature, and water levels beneath the site indicated that artificial recharge reached the underlying water table between 3.75 and 4.5 yr after the initial application of the recharge water. The model was modified to allow the simulation to more adequately match the perching layer dynamics and the time of arrival at the water table. The instrumentation also showed that the lag time between changes in application of water at the surface and the response at the perching layer decreased from about 4 mo to less than 1 mo due to the wet-up of the unsaturated zone and the increase in relative permeability. The results of this study demonstrate the importance of iteratively monitoring and modeling the unsaturated zone in layered alluvial systems in the context of artificial recharge. They show that adequate geologic and hydraulic-property data on perching layers are critical to success. Continuous monitoring in the unsaturated and saturated zones beneath a site provides data to develop and constrain numerical models, better understand local unsaturated zone process, manage artificial recharge operations, and to determine the timing and volume of recoverable water for consumptive use.

Zinc movement in sewage-sludge-treated soils as influenced by soil properties, irrigation water quality, and soil moisture level

USGS Publications Warehouse

Welch, J.E.; Lund, L.J.

1989-01-01

A soil column study was conducted to assess the movement of Zn in sewage-sludge-amended soils. Varables investigated were soil properties, irrigation water quality, and soil moisture level. Bulk samples of the surface layer of six soil series were packed into columns, 10.2 cm in diameter and 110 cm in length. An anaerobically digested municipal sewage sludge was incorporated into the top 20 cm of each column at a rate of 300 mg ha-1. The columns were maintained at moisture levels of saturation and unsaturation and were leached with two waters of different quality. At the termination of leaching, the columns were cut open and the soil was sectioned and analyzed. Zinc movement was evaluated by mass balance accounting and correlation and regression analysis. Zinc movement in the unsaturated columns ranged from 3 to 30 cm, with a mean of 10 cm. The difference in irrigation water quality did not have an effect on Zn movement. Most of the Zn applied to the unsaturated columns remained in the sludge-amended soil layer (96.1 to 99.6%, with a mean of 98.1%). The major portion of Zn leached from the sludge-amended soil layer accumulated in the 0- to 3-cm depth (35.7 to 100%, with a mean of 73.6%). The mean final soil pH values decreased in the order: saturated columns = sludge-amended soil layer > untreated soils > unsaturated columns. Total Zn leached from the sludge-amended soil layer was correlated negatively at P = 0.001 with final pH (r = -0.85). Depth of Zn movement was correlated negatively at P = 0.001 with final pH (r = -0.91). Multiple linear regression analysis showed that the final pH accounted for 72% of the variation in the total amounts of Zn leached from the sludge-amended soil layer of the unsaturated columns and accounted for 82% of the variation in the depth of Zn movement among the unsaturated columns. A significant correlation was not found between Zn and organic carbon in soil solutions, but a negative correlation significant at P = 0.001 was found between pH and Zn (r = -0.61).

Archaeology and public perception of a trans-scientific problem; disposal of toxic wastes in the unsaturated zone

USGS Publications Warehouse

Winograd, Isaac Judah

1986-01-01

Predicting the effects of toxic-waste disposal on the environment over periods of millenia to hundreds of millenia is a transscientific problem; that is, one not fully addressed by quantitative scientific and engineering endeavors. Archaeology is a pertinent adjunct to such predictions in several ways. First, and foremost, archaeological records demonstrate that delicate, as well as durable, objects buried in thick unsaturated zones of arid and semiarid environments may survive intact for millenia to tens of millenia. This successful preservation of Late Paleolithic to Iron Age artifacts provides independent support for the tentative favorable conclusions of earth scientists regarding the general utility of thick unsaturated zones for toxic-waste isolation. By analogy with the archaeological record, solidified toxic wastes of low solubility that are buried in arid unsaturated zones should remain isolated from the environment indefinitely; modern man presumably should be able to improve upon the techniques used by his ancestors to isolate and preserve their sacred and utilitarian objects. Second, archaeological evidence pertinent to the fate of objects buried in unsaturated zones-although qualitative in nature and subject to the limitations of arguments by analogy-is meaningful to the public and to the courts who, with some scientists and engineers, are reluctant to rely exclusively on computer-generated predictions of the effects of buried toxic wastes on the environment. Third, the archaeological record issues a warning that our descendants may intrude into our waste disposal sites and that we must therefore take special measures to minimize such entry and, if it occurs, to warn of the dangers by a variety of symbols. And fourth, archaeology provides a record of durable natural and manmade materials that may prove to be suitable for encapsulation of our wastes and from which we can construct warning markers that will last for millenia. For these four reasons, archaeologists must join with earth scientists, and other scientists and engineers, in addressing the likely fate of solidfied toxic wastes buried in the thick (200-600 m) unsaturated zones of arid and semiarid regions. Indeed, the input of archaeology might be crucial to public acceptance of even the most carefully chosen and technically sound waste repository.

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.

Haematological values in pregnant women in Port Harcourt, Nigeria II: Serum iron and transferrin, total and unsaturated iron binding capacity and some red cell and platelet indices.

PubMed

Amah-Tariah, F S; Ojeka, S O; Dapper, D V

2011-12-20

Previous studies on the normal values of serum iron, unsaturated iron binding capacity, total iron binding capacity, serum transferrin, percent transferrin saturation, red cell distribution width, and various platelet indices: Platelet count, mean platelet volume, platelet distribution width, plateletcrit and platelet larger cell ratio in pregnant subjects in Nigeria are relatively scanty. Present study aims to determine the values of these parameters in apparently healthy pregnant subjects residing in Port Harcourt south eastern Nigeria; and help establish normal reference ranges of these parameters for the population under reference. Cross sectional prospective study involving 220 female subjects attending for the first time, the ante-natal clinics of a tertiary health care facility in Port Harcourt. Subjects were divided into 73, 75 and 72 subjects in the first, second and third trimester of pregnancy respectively. Serum iron and unsaturated iron binding capacity, red cell distribution width, platelet count and platelet distribution width were determined by automated methods; total iron binding capacity, serum transferrin concentrations, percent transferrin saturation, mean platelet volume and plateletcrit were calculated using appropriate formulas. The values of serum iron, unsaturated iron binding capacity, total iron binding capacity and serum transferrin concentrations were found to show significant variations between the various trimesters of pregnancy. However, while serum iron showed significant decreases during pregnancy; unsaturated iron binding capacity, total iron binding capacity and serum transferrin concentrations were found to show significant increases during pregnancy amongst our subjects (p<0.05). By contrast the values of red cell distribution width, platelet count, mean platelet volume, platelet distribution width, plateletcrit and platelet larger cell ratio did not show any significant differences at the different trimesters of pregnancy in our subjects (p>0.05). The present study reports, for the first time, normative values for these parameters in apparently healthy pregnant subjects in Port Harcourt south eastern Nigeria. Apparently, increases in unsaturated and total iron binding capacity and serum transferrin values seen amongst our subjects with increasing gestation may perhaps be a mechanism to ensure a fetal adequate iron delivery on account of the decreasing serum iron concentration with gestation in our subjects. The study suggests that values of serum transferrin are perhaps a more useful screening tool for iron deficiency anemia during pregnancy amongst our subjects.

Possible Climatic Signal Recorded by Alkenone Distributions in Sediments from Freshwater and Saline Lakes on the Skarvsnes and Skallen Areas, Antarctica

NASA Astrophysics Data System (ADS)

Sawada, K.; Takeda, M.; Takano, Y.

2014-12-01

The distribution of long-chain (C37 - C39) alkenones in marine sediment has been well documented to record paleo-sea surface temperatures. The alkenones were also found in sediments of terrestrial saline lakes, and recently the calibrations of alkenone unsaturation indices - temperature have been established in continental areas. Furthermore, these biomarkers have been identified in lacustrine sediments on high-latitudinal terrestrial areas such as Greenland and Antarctica. In the present study, the alkenones were identified in the lacustrine sediment cores in freshwater (Lake Naga-ike) and saline lakes (Lake Suribati and Lake Funazoko) on the Skarvsnes, and a saline lake (Lake Skallen Oh-ike) on the Skallen, Antarctica. Here, we report that the alkenone distribution in the Antarctic lakes was examined as paleotemperature proxy. C37-C38 Tetra- and tri-unsaturated alkenones and C37 tetra- and tri-unsaturated alkenoates are identified in all sediment samples. The C37 di-unsaturated (C37:2) alkenones can be identified in sediments of surface layers (0-15 cm) of Lake Naga-ike and layers of 160-190 cm depth, in which age is ca. 3000 years BP by 14C dating, in Lake Skallen Ohike, and alkenone unsaturation index (UK37) is analyzed from these sediments. By using a calibration obtained from a culture strain Chrysotila lamellosa as reported by Nakamura et al. (2014), paleotemperatures are calculated to be 9.2-15ºC in surface sediments of Lake Naga-ike and 6.8-8.6ºC in Lake Skallen Oh-ike, respectively. The estimated temperatures are concordant with summer temperature of lake waters observed in Lake Naga-ike. Also, the highest concentrations of the alkenones and alkenoates are observed in deeper (older) sediment layers from Lake Naga-ikes, which has not been connected the ocean and intruded sea water. This implies that the alkenones are originated from indigenous biological organism(s) in Antarctic lake water. The class distributions (unsaturation ratios) of alkenones varied with core depths in Lake Naga-ike and Lake Suribati, whereas these are nearly constant with core depths in Lake Funazoko. These variations presumably depended on changes of climatic and environmental conditions in lake water. Thus, it is suggested that the alkenone proxies can be applicable for Antarctic climate changes.

The influence of Na+ and Ca2+ on the migration of colloids or/and ammonia nitrogen in an unsaturated zone medium.

PubMed

Li, HaiMing; Wei, JinBu; Ge, YaChao; Wang, ZhanQuan; Wang, Ye; Li, YingLong

2016-11-01

This experiment was conducted with an indoor sand-column device, the migration of colloids with the presence of Na + and Ca 2+ and the migration of ammonia nitrogen with the presence of Na + , Ca 2+ or/and colloids was studied. The results showed that the migration of colloids was influenced by the ion valence state, different ions with different valence could block the migration of colloids. In addition, the blocking effect of bivalent ions was more obvious than that of monovalent ions. In the presence of Na + and Ca 2+ , the R d value of the ammonia-nitrogen migration process were 1.01 and 1.41, respectively, which indicated that bivalent ions have a greater blocking effect on ammonia-nitrogen migration than monovalent ions. Colloids could also block the ammonia-nitrogen migration, and R d value in the ammonia-nitrogen migration process was 1.17. Moreover, the presence of Na + /colloids and Ca 2+ /colloids could enhance the blocking effect on the ammonia-nitrogen migration, and resulting the R d values at 1.20 and 1.52, respectively. The cohesion of colloids caused by the compaction of its electric double layer with those ions added maybe the key causes of those blocking. Copyright © 2016 Elsevier B.V. All rights reserved.

Response to "Comments on 'Theory for source-responsive and free-surface film modeling of unsaturated flow'"

USGS Publications Warehouse

Nimmo, John R.

2012-01-01

I am grateful to Masciopinto (2012) for raising several issues from my study (Nimmo, 2010) that deserve elaboration or clarification. In this reply, I address these in what I judge to be the order of importance, the main ones being (i) the discrepancy of scales between the two domains that treat preferential and diffuse unsaturated flow, and (ii) the properties that must be evaluated to characterize the medium.

Stereoselective synthesis of unsaturated α-amino acids.

PubMed

Fanelli, Roberto; Jeanne-Julien, Louis; René, Adeline; Martinez, Jean; Cavelier, Florine

2015-06-01

Stereoselective synthesis of unsaturated α-amino acids was performed by asymmetric alkylation. Two methods were investigated and their enantiomeric excess measured and compared. The first route consisted of an enantioselective approach induced by the Corey-Lygo catalyst under chiral phase transfer conditions while the second one involved the hydroxypinanone chiral auxiliary, both implicating Schiff bases as substrate. In all cases, the use of a prochiral Schiff base gave higher enantiomeric excess and yield in the final desired amino acid.

Limited denitrification in glacial deposit aquifers having thick unsaturated zones (Long Island, USA)

USGS Publications Warehouse

Young, Caitlin; Kroeger, Kevin D.; Hanson, Gilbert

2013-01-01

The goal of this study was to demonstrate how the extent of denitrification, which is indirectly related to dissolved organ carbon and directly related to oxygen concentrations, can also be linked to unsaturated-zone thickness, a mappable aquifer property. Groundwater from public supply and monitoring wells in Northport on Long Island, New York state (USA), were analyzed for denitrification reaction progress using dissolved N2/Ar concentrations by membrane inlet mass spectrometry. This technique allows for discernment of small amounts of excess N2, attributable to denitrification. Results show an average 15 % of total nitrogen in the system was denitrified, significantly lower than model predictions of 35 % denitrification. The minimal denitrification is due to low dissolved organic carbon (29.3–41.1 μmol L−1) and high dissolved oxygen concentrations (58–100 % oxygen saturation) in glacial sediments with minimal solid-phase electron donors to drive denitrification. A mechanism is proposed that combines two known processes for aquifer re-aeration in unconsolidated sands with thick (>10 m) unsaturated zones. First, advective flux provides 50 % freshening of pore space oxygen in the upper 2 m due to barometric pressure changes. Then, oxygen diffusion across the water-table boundary occurs due to high volumetric air content in the unsaturated-zone catchment area.

(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.

A generalized groundwater fluctuation model based on precipitation for estimating water table levels of deep unconfined aquifers

NASA Astrophysics Data System (ADS)

Jeong, Jina; Park, Eungyu; Shik Han, Weon; Kim, Kue-Young; Suk, Heejun; Beom Jo, Si

2018-07-01

A generalized water table fluctuation model based on precipitation was developed using a statistical conceptualization of unsaturated infiltration fluxes. A gamma distribution function was adopted as a transfer function due to its versatility in representing recharge rates with temporally dispersed infiltration fluxes, and a Laplace transformation was used to obtain an analytical solution. To prove the general applicability of the model, convergences with previous water table fluctuation models were shown as special cases. For validation, a few hypothetical cases were developed, where the applicability of the model to a wide range of unsaturated zone conditions was confirmed. For further validation, the model was applied to water table level estimations of three monitoring wells with considerably thick unsaturated zones on Jeju Island. The results show that the developed model represented the pattern of hydrographs from the two monitoring wells fairly well. The lag times from precipitation to recharge estimated from the developed system transfer function were found to agree with those from a conventional cross-correlation analysis. The developed model has the potential to be adopted for the hydraulic characterization of both saturated and unsaturated zones by being calibrated to actual data when extraneous and exogenous causes of water table fluctuation are limited. In addition, as it provides reference estimates, the model can be adopted as a tool for surveilling groundwater resources under hydraulically stressed conditions.

Evolution of strain localization in variable-width three-dimensional unsaturated laboratory-scale cut slopes

USGS Publications Warehouse

Morse, Michael S.; Lu, Ning; Wayllace, Alexandra; Godt, Jonathan W.

2017-01-01

To experimentally validate a recently developed theory for predicting the stability of cut slopes under unsaturated conditions, the authors measured increasing strain localization in unsaturated slope cuts prior to abrupt failure. Cut slope width and moisture content were controlled and varied in a laboratory, and a sliding door that extended the height of the free face of the slope was lowered until the cut slope failed. A particle image velocimetry tool was used to quantify soil displacement in the x-y">x-y (horizontal) and x-z">x-z (vertical) planes, and strain was calculated from the displacement. Areas of maximum strain localization prior to failure were shown to coincide with the location of the eventual failure plane. Experimental failure heights agreed with the recently developed stability theory for unsaturated cut slopes (within 14.3% relative error) for a range of saturation and cut slope widths. A theoretical threshold for sidewall influence on cut slope failures was also proposed to quantify the relationship between normalized sidewall width and critical height. The proposed relationship was consistent with the cut slope experiment results, and is intended for consideration in future geotechnical experiment design. The experimental data of evolution of strain localization presented herein provide a physical basis from which future numerical models of strain localization can be validated.

Assessing the fate of explosives derived nitrate in mine waste rock dumps using the stable isotopes of oxygen and nitrogen.

PubMed

Hendry, M Jim; Wassenaar, Leonard I; Barbour, S Lee; Schabert, Marcie S; Birkham, Tyler K; Fedec, Tony; Schmeling, Erin E

2018-05-29

Ammonium nitrate (NH 4 NO 3 ) mixed with fuel oil is a common blasting agent used to fragment rock into workable size fractions at mines throughout the world. The decomposition and oxidation of undetonated explosives can result in high NO 3 - concentrations in waters emanating from waste rock dumps. We used the stable isotopic composition of NO 3 - (δ 15 N- and δ 18 O-NO 3 - ) to define and quantify the controls on NO 3 - composition in waste rock dumps by studying water-unsaturated and saturated conditions at nine coal waste rock dumps located in the Elk Valley, British Columbia, Canada. Estimates of the extent of nitrification of NH 4 NO 3 in oxic zones in the dumps, initial NO 3 - concentrations prior to denitrification, and the extent of NO 3 - removal by denitrification in sub-oxic to anoxic zones are provided. δ 15 N data from unsaturated waste rock dumps confirm NO 3 - is derived from blasting. δ 15 N- and δ 18 O-NO 3 - data show extensive denitrification can occur in saturated waste rock and in localized zones of elevated water saturation and low oxygen concentrations in unsaturated waste rock. At the mine dump scale, the extent of denitrification in the unsaturated waste rock was inferred from water samples collected from underlying rock drains. Copyright © 2018. Published by Elsevier B.V.

Comparison of the skin sensitizing potential of unsaturated compounds as assessed by the murine local lymph node assay (LLNA) and the guinea pig maximization test (GPMT).

PubMed

Kreiling, R; Hollnagel, H M; Hareng, L; Eigler, D; Lee, M S; Griem, P; Dreessen, B; Kleber, M; Albrecht, A; Garcia, C; Wendel, A

2008-06-01

The skin sensitization potential of eight unsaturated and one saturated lipid (bio)chemicals was tested in both the LLNA and the GPMT to address the hypothesis that chemicals with unsaturated carbon-carbon double bonds may result in a higher number of unspecific (false positive) results in the LLNA compared to the GPMT. Seven substances (oleic acid, linoleic acid, linolenic acid, undecylenic acid, maleic acid, squalene and octinol) gave clear positive results in the LLNA (stimulation index (SI)> or = 3) and thus would require labelling as skin sensitizer. Fumaric acid and succinic acid gave clearly negative results. In the GPMT, besides some sporadic skin reactions, reproducible skin reactions indicating an allergic response were found in a few animals for four test substances. Based on the GPMT results, only undecylenic acid would have to be classified and labelled as a skin sensitizer according to the European Dangerous Substance Directive (67/548/EEC) (results for linoleic acid were inconclusive), while the other seven test substances would not require labelling. Possible mechanisms for unspecific skin cell stimulation and lymph node responses are discussed. In conclusion, the suitability of the LLNA for unsaturated compounds bearing structural similarity to the tested substances should be carefully considered and the GPMT should remain available as an accepted test method for skin sensitization hazard identification.

LNAPL Removal from Unsaturated Porous Media using Surfactant Infiltration

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

Zhong, Lirong; Oostrom, Martinus

A series of unsaturated column experiments was performed to evaluate light non-aqueous phase liquid (LNAPL) fate and removal during surfactant solution infiltration. Surfactant-LNAPL phase behavior tests were conducted to optimize the remedial solutions. Packed sand and site sediment columns were first processed to establish representative LNAPL smear zone under unsaturated conditions. Infiltration of low-concentration surfactant was then applied in a stepwise flush mode, with 0.3 column pore volume (PV) of solution in each flush. The influence of infiltrated surfactant solution volume and pH on LNAPL removal was assessed. A LNAPL bank was observed at the very front of the firstmore » surfactant infiltration in each column, indicating that a very low surfactant concentration is needed to reduce the LNAPL-water interfacial tension sufficiently enough to mobilize trapped LNAPL under unsaturated conditions. More LNAPL was recovered as additional steps of surfactant infiltration were applied. Up to 99% LNAPL was removed after six infiltration steps, with less than 2.0 PV of total surfactant solution application, suggesting surfactant infiltration may be an effective method for vadose zone LNAPL remediation. The influence of pH tested in this study (3.99~10.85) was insignificant because the buffering capacity of the sediment kept the pH in the column higher than the zero point charge, pHzpc, of the sediment and therefore the difference between surfactant sorption was negligible.« less

Manipulating the Ordered Nanostructure of Self-Assembled Monoolein and Phytantriol Nanoparticles with Unsaturated Fatty Acids.

PubMed

Tran, Nhiem; Mulet, Xavier; Hawley, Adrian M; Fong, Celesta; Zhai, Jiali; Le, Tu C; Ratcliffe, Julian; Drummond, Calum J

2018-02-27

Mesophase structures of self-assembled lyotropic liquid crystalline nanoparticles are important factors that directly influence their ability to encapsulate and release drugs and their biological activities. However, it is difficult to predict and precisely control the mesophase behavior of these materials, especially in complex systems with several components. In this study, we report the controlled manipulation of mesophase structures of monoolein (MO) and phytantriol (PHYT) nanoparticles by adding unsaturated fatty acids (FAs). By using high throughput formulation and small-angle X-ray scattering characterization methods, the effects of FAs chain length, cis-trans isomerism, double bond location, and level of chain unsaturation on self-assembled systems are determined. Additionally, the influence of temperature on the phase behavior of these nanoparticles is analyzed. We found that in general, the addition of unsaturated FAs to MO and PHYT induces the formation of mesophases with higher Gaussian surface curvatures. As a result, a rich variety of lipid polymorphs are found to correspond with the increasing amounts of FAs. These phases include inverse bicontinuous cubic, inverse hexagonal, and discrete micellar cubic phases and microemulsion. However, there are substantial differences between the phase behavior of nanoparticles with trans FA, cis FAs with one double bond, and cis FAs with multiple double bonds. Therefore, the material library produced in this study will assist the selection and development of nanoparticle-based drug delivery systems with desired mesophase.

Quantification of natural vapor fluxes of trichloroethene in the unsaturated zone at Picatinny Arsenal, New Jersey

USGS Publications Warehouse

Smith, James A.; Tisdale, Amy K.; Cho, H. Jean

1996-01-01

The upward flux of trichloroethene (TCE) vapor through the unsaturated zone above a contaminated, water-table aquifer at Picatinny Arsenal, New Jersey, has been studied under natural conditions over a 12-month period. Vertical gas-phase diffusion fluxes were estimated indirectly by measuring the TCE vapor concentration gradient in the unsaturated zone and using Fick's law to calculate the flux. The total gas-phase flux (e.g., the sum of diffusion and advection fluxes) was measured directly with a vertical flux chamber (VFC). In many cases, the upward TCE vapor flux was several orders of magnitude greater than the upward TCE diffusion flux, suggesting that mechanisms other than steady-state vapor diffusion are contributing to the vertical transport of TCE vapors through the unsaturated zone. The measured total flux of TCE vapor from the subsurface to the atmosphere is approximately 50 kg/yr and is comparable in magnitude to the removal rate of TCE from the aquifer by an existing pump-and-treat system and by discharge into a nearby stream. The net upward flux of TCE is reduced significantly during a storm event, presumably due to the mass transfer of TCE from the soil gas to the infiltrating rainwater and its subsequent downward advection. Several potential problems associated with the measurement of total gas-phase fluxes are discussed.

Effects of medium-chain triacylglycerols on Maillard reaction in bread baking.

PubMed

Toyosaki, Toshiyuki

2018-06-01

To investigate the relationship between the fatty acid composition of medium-chain triacylglycerols (MCTs) and the Maillard reaction induced during bread baking, a comparison with various fatty acids was conducted. Saturated fatty acids had a remarkable inhibitory effect on the amount of advanced glycation end products (AGEs) generated from the Maillard reaction in bread baking compared to unsaturated fatty acids. The amount of AGEs produced by each fatty acid (mg kg -1 ) was as follows: C18:0, 18.7; C12:0, 35.2; C16:0, 21.4; C18:0, 38.2; C18:1, 68.7; C18:2, 80.1; C20:4, 80.8; C22:4, 89.8. Saturated fatty acids were possibly involved in the Maillard reaction and, as a result, acted to inhibit it. In the case of unsaturated fatty acids, amounts of AGEs during the Maillard reaction in baking tended to increase as the degree of unsaturation increased. In other words, there was a positive correlation between the degree of unsaturation and the amount of AGEs. It was also confirmed that the air pore distribution in baked bread was closely related to AGEs. These results led us to conclude that the fatty acid composition of the added lipids also influences properties that determine the tastiness of bread. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Balancing practicality and hydrologic realism: a parsimonious approach for simulating rapid groundwater recharge via unsaturated-zone preferential flow

USGS Publications Warehouse

Mirus, Benjamin B.; Nimmo, J.R.

2013-01-01

The impact of preferential flow on recharge and contaminant transport poses a considerable challenge to water-resources management. Typical hydrologic models require extensive site characterization, but can underestimate fluxes when preferential flow is significant. A recently developed source-responsive model incorporates film-flow theory with conservation of mass to estimate unsaturated-zone preferential fluxes with readily available data. The term source-responsive describes the sensitivity of preferential flow in response to water availability at the source of input. We present the first rigorous tests of a parsimonious formulation for simulating water table fluctuations using two case studies, both in arid regions with thick unsaturated zones of fractured volcanic rock. Diffuse flow theory cannot adequately capture the observed water table responses at both sites; the source-responsive model is a viable alternative. We treat the active area fraction of preferential flow paths as a scaled function of water inputs at the land surface then calibrate the macropore density to fit observed water table rises. Unlike previous applications, we allow the characteristic film-flow velocity to vary, reflecting the lag time between source and deep water table responses. Analysis of model performance and parameter sensitivity for the two case studies underscores the importance of identifying thresholds for initiation of film flow in unsaturated rocks, and suggests that this parsimonious approach is potentially of great practical value.

Palaeoclimate Records in Dryland Dunes: Progress and Remaining Challenges Utilizing the Unsaturated Zone for Palaeomoisture Reconstruction.

NASA Astrophysics Data System (ADS)

Stone, A.

2016-12-01

Reconstructions of past rainfall in dryland regions underpin our understanding the links between climatic forcing and palaeohydrological response. However, there are only few proxies in drylands that record palaeorainfall, or palaeomoisture, in a straightforward manner. The unsaturated zone (USZ) has very significant potential as a novel dryland palaeomoisture archive. The approach is simple, based on variations in the concentration of pore-moisture tracers with depth, representing a hydrostratigraphical record through time. The tracer input is meteoric, with the concentration of this tracer established in the near-surface zone as a function of the level of evapotranspiration before that pore-moisture is transmitted vertically down to the water table. This presentation will highlight key regions where hydrostratigraphies have been successfully applied in drylands. It will also set out challenges regarding the assumptions of the approach, with the intention to stimulate discussion regarding the future development of the unsaturated zone as a palaeoclimate archive over a range of timescales and resolutions. Depending on the rate of moisture flux and the depth of the unsaturated zone, dryland hydrostratigraphies may record (i) broad climatic shifts since the last interglacial at low temporal resolution or multi-millennial length palaeomoisture records with a decadal temporal resolution. USZ hydrostratigraphies may also contain a record of changes in the amount of infiltration (and groundwater recharge) caused by changes to land-use.

Fish oil increases mitochondrial phospholipid unsaturation, upregulating reactive oxygen species and apoptosis in rat colonocytes

NASA Technical Reports Server (NTRS)

Hong, Mee Young; Chapkin, Robert S.; Barhoumi, Rola; Burghardt, Robert C.; Turner, Nancy D.; Henderson, Cara E.; Sanders, Lisa M.; Fan, Yang-Yi; Davidson, Laurie A.; Murphy, Mary E.;

Percolation induced heat transfer in deep unsaturated zones

USGS Publications Warehouse

Lu, N.; LeCain, G.D.

2003-01-01

Subsurface temperature data from a borehole located in a desert wash were measured and used to delineate the conductive and advective heat transfer regimes, and to estimate the percolation quantity associated with the 1997-1998 El Ni??no precipitation. In an arid environment, conductive heat transfer dominates the variation of shallow subsurface temperature most of the time, except during sporadic precipitation periods. The subsurface time-varying temperature due to conductive heat transfer is highly correlated with the surface atmospheric temperature variation, whereas temperature variation due to advective heat transfer is strongly correlated with precipitation events. The advective heat transfer associated with precipitation and infiltration is the focus of this paper. Disruptions of the subsurface conductive temperature regime, associated with the 1997-1998 El Ni??no precipitation, were detected and used to quantify the percolation quantity. Modeling synthesis using a one-dimensional coupled heat and unsaturated flow model indicated that a percolation per unit area of 0.7 to 1.3 m height of water in two weeks during February 1998 was responsible for the observed temperature deviations down to a depth of 35.2 m. The reported study demonstrated quantitatively, for the first time, that the near surface temperature variation due to advective heat transfer can be significant at a depth greater than 10 m in unsaturated soils and can be used to infer the percolation amount in thick unsaturated soils.

Optimality and Conductivity for Water Flow: From Landscapes, to Unsaturated Soils, to Plant Leaves

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

Liu, H.H.

2012-02-23

Optimality principles have been widely used in many areas. Based on an optimality principle that any flow field will tend toward a minimum in the energy dissipation rate, this work shows that there exists a unified form of conductivity relationship for three different flow systems: landscapes, unsaturated soils and plant leaves. The conductivity, the ratio of water flux to energy gradient, is a power function of water flux although the power value is system dependent. This relationship indicates that to minimize energy dissipation rate for a whole system, water flow has a small resistance (or a large conductivity) at amore » location of large water flux. Empirical evidence supports validity of the relationship for landscape and unsaturated soils (under gravity dominated conditions). Numerical simulation results also show that the relationship can capture the key features of hydraulic structure for a plant leaf, although more studies are needed to further confirm its validity. Especially, it is of interest that according to this relationship, hydraulic conductivity for gravity-dominated unsaturated flow, unlike that defined in the classic theories, depends on not only capillary pressure (or saturation), but also the water flux. Use of the optimality principle allows for determining useful results that are applicable to a broad range of areas involving highly non-linear processes and may not be possible to obtain from classic theories describing water flow processes.« less

Ecohydrological factors affecting nitrate concentrations in a phreatic desert aquifer in northwestern China

USGS Publications Warehouse

Gates, J.B.; Böhlke, J.K.; Edmunds, W.M.

2008-01-01

Aerobic conditions in desert aquifers commonly allow high nitrate (NO 3-) concentrations in recharge to persist for long periods of time, an important consideration for N-cycling and water quality. In this study, stable isotopes of NO3- (??15N NO3 and ??18ONO3) were used to trace NO3- cycling processes which affect concentrations in groundwater and unsaturated zone moisture in the arid Badain Jaran Oesert in northwestern China. Most groundwater NO3- appears to be depleted relative to Cl- in rainfall concentrated by evapotranspiration, indicating net N losses. Unsaturated zone NO 3- is generally higher than groundwater NO 3- in terms of both concentration (up to 15 476 ??M, corresponding to 3.6 mg NO3--N per kg sediment) and ratios with Cl-. Isotopic data indicate that the NO3- derives primarily from nitrification, with a minor direct contribution of atmospheric NO3- inferred for some samples, particularly in the unsaturated zone. Localized denitrification in the saturated zone is suggested by isotopic and geochemical indicators in some areas. Anthropogenic inputs appear to be minimal, and variability is attributed to environmental factors. In comparison to other arid regions, the sparseness of vegetation in the study area appears to play an important role in moderating unsaturated zone NO3- accumulation by allowing solute flushing and deterring extensive N2 fixation. ?? 2008 American Chemical Society.

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

PubMed

Srivastava, S K; Tripathi, Abhishek Dutt

2013-10-01

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

Extraction of unsaturated fatty acid-rich oil from common carp (Cyprinus carpio) roe and production of defatted roe hydrolysates with functional, antioxidant, and antibacterial properties.

PubMed

Ghelichi, Sakhi; Shabanpour, Bahareh; Pourashouri, Parastoo; Hajfathalian, Mona; Jacobsen, Charlotte

2018-03-01

Common carp roe is a rich protein and oil source, which is usually discarded with no specific use. The aims of this study were to extract oil from the discarded roe and examine functional, antioxidant, and antibacterial properties of defatted roe hydrolysates (CDRHs) at various degrees of hydrolysis (DH). Gas chromatography of fatty acid methyl esters revealed that common carp roe oil contained high levels of unsaturated fatty acids. The results of high-performance liquid chromatography-mass spectrometry indicated that enzymatic hydrolysis of defatted roe yielded higher content of essential amino acids. CDRHs displayed higher solubility than untreated defatted roe, which increased with DH. Better emulsifying and foaming properties were observed at lower DH and non-isoelectric points. Furthermore, water and oil binding capacity decreased with DH. CDRHs exhibited antioxidant activity both in vitro and in 5% roe oil-in-water emulsions and inhibited the growth of certain bacterial strains. Common carp roe could be a promising source of unsaturated fatty acids and functional bioactive agents. Unsaturated fatty acid-rich oil extracted from common carp roe can be delivered into food systems by roe oil-in-water emulsions fortified by functional, antioxidant, and antibacterial hydrolysates from the defatted roe. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Resilience and reliability of compact vertical-flow treatment wetlands designed for tropical climates.

PubMed

Lombard-Latune, R; Pelus, L; Fina, N; L'Etang, F; Le Guennec, B; Molle, P

2018-06-10

Most of the tropical areas have sanitation problems to contend with. The French system of vertical-flow treatment wetlands (FS-VFTW) fed with raw wastewater could be a good water and sludge management solution. The purpose-adapted tropical design can reduce area requirement to below 1 m 2 /population equivalents (p.e.). The Taupinière FS-VFTW on Martinique Island was built according to this design, with one stage but with a saturated layer at the bottom of the filter and a simplified trickling filter (TF) added for further treatment to meet the high performances targeted. Unsaturated/saturated vertical-flow filters (US/S FS-VFTW) have shown improved performances on total nitrogen, carbon and suspended solids removal in temperate climates, but the performances in tropical conditions remain unknown. Here, we report on real-world-operation in the French Overseas Territories (FOT), the reliability and performances of this VFCW tropical-design. The system experienced loading conditions ranging from 30% to 165% of nominal carbonaceous biological oxygen demand (BOD 5 ), as well as tropical rainstorms that brought over 7 times the nominal hydraulic load. Over a period of 3 years, 29 campaigns collected 24-h flow-proportional samples at each treatment stage (raw wastewater, FS-VFTW outlet, TF outlet). When applied loads were close to nominal values, the US/S FS-VFTW itself guarantees 85/90/60/50% removal and 125/25/40/50 mg/L at the outlet for chemical oxygen demand (COD)/total suspended solids (TSS)/total Kjeldahl nitrogen (TKN)/total nitrogen (TN), respectively. By comparison with US/S systems in mainland France, it appears that the warmer tropical-climate temperatures facilitate both nitrification and denitrification kinetics. Performances in overload conditions confirm that the US/S FS-VFTW remains robust and reliable although COD and TKN removal are impacted, especially after strong tropical rain events. By adding a simple compact trickling filter to a US/S FS-VFTW, the treatment system delivers high-level performances (>95% removal for BOD 5 , COD, TSS and TKN) at less than 1 m 2 /p.e. Copyright © 2018 Elsevier B.V. All rights reserved.

An integrated QSAR-PBK/D modelling approach for predicting detoxification and DNA adduct formation of 18 acyclic food-borne α,β-unsaturated aldehydes

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

Kiwamoto, R., E-mail: reiko.kiwamoto@wur.nl; Spenkelink, A.; Rietjens, I.M.C.M.

Acyclic α,β-unsaturated aldehydes present in food raise a concern because the α,β-unsaturated aldehyde moiety is considered a structural alert for genotoxicity. However, controversy remains on whether in vivo at realistic dietary exposure DNA adduct formation is significant. The aim of the present study was to develop physiologically based kinetic/dynamic (PBK/D) models to examine dose-dependent detoxification and DNA adduct formation of a group of 18 food-borne acyclic α,β-unsaturated aldehydes without 2- or 3-alkylation, and with no more than one conjugated double bond. Parameters for the PBK/D models were obtained using quantitative structure–activity relationships (QSARs) defined with a training set of sixmore » selected aldehydes. Using the QSARs, PBK/D models for the other 12 aldehydes were defined. Results revealed that DNA adduct formation in the liver increases with decreasing bulkiness of the molecule especially due to less efficient detoxification. 2-Propenal (acrolein) was identified to induce the highest DNA adduct levels. At realistic dietary intake, the predicted DNA adduct levels for all aldehydes were two orders of magnitude lower than endogenous background levels observed in disease free human liver, suggesting that for all 18 aldehydes DNA adduct formation is negligible at the relevant levels of dietary intake. The present study provides a proof of principle for the use of QSAR-based PBK/D modelling to facilitate group evaluations and read-across in risk assessment. - Highlights: • Physiologically based in silico models were made for 18 α,β-unsaturated aldehydes. • Kinetic parameters were determined by in vitro incubations and a QSAR approach. • DNA adduct formation was negligible at levels relevant for dietary intake. • The use of QSAR-based PBK/D modelling facilitates group evaluations and read-across.« less

Focused Flow During Infiltration Into Ethanol-Contaminated Unsaturated Porous Media

NASA Astrophysics Data System (ADS)

Jazwiec, A.; Smith, J. E.

2017-12-01

The increasing commercial and industrial use of ethanol, e.g. in biofuels, has generated increased incidents of vadose zone contamination by way of ethanol spills and releases. This has increased the interest in better understanding behaviors of ethanol in unsaturated porous media and it's multiphase interactions in the vadose zone. This study uses highly controlled laboratory experiments in a 2-D (0.6mx0.6mx0.01m) flow cell to investigate water infiltration behaviors into ethanol-contaminated porous media. Ethanol and water were applied by either constant head or constant flux methods onto the surface of sands homogenously packed into the flow cell. The constant flux experiments at both low and high application rates were conducted using a rainulator with a row of hypodermic needles connected to a peristaltic pump. The constant head experiments were conducted using an 8cm diameter tension disk infiltrometer set to both low and high tensions. The presence of ethanol contamination generated solute-dependent capillarity induced focused flow (SCIFF) of water infiltration, which was primarily due to decreases in interfacial tensions at the air-liquid interfaces in the unsaturated sands as a function of ethanol concentration. SCIFF was clearly expressed as an unsaturated water flow phenomenon comprised of narrowly focused vertical flow fingers of water within the initially ethanol contaminated porous media. Using analyses of photos and video, comparisons were made between constant flux and constant head application methods. Further comparisons were made between low and high infiltration rates and the two sand textures used. A high degree of sensitivity to minor heterogeneity in relatively homogeneous sands was also observed. The results of this research have implications for rainfall infiltration into ethanol contaminated vadose zones expressing SCIFF, including implications for associated mass fluxes and the nature of flushing of ethanol from the unsaturated zone to groundwaters.

Suitability of parametric models to describe the hydraulic properties of an unsaturated coarse sand and gravel

USGS Publications Warehouse

Mace, Andy; Rudolph, David L.; Kachanoski , R. Gary

1998-01-01

The performance of parametric models used to describe soil water retention (SWR) properties and predict unsaturated hydraulic conductivity (K) as a function of volumetric water content (θ) is examined using SWR and K(θ) data for coarse sand and gravel sediments. Six 70 cm long, 10 cm diameter cores of glacial outwash were instrumented at eight depths with porous cup ten-siometers and time domain reflectometry probes to measure soil water pressure head (h) and θ, respectively, for seven unsaturated and one saturated steady-state flow conditions. Forty-two θ(h) and K(θ) relationships were measured from the infiltration tests on the cores. Of the four SWR models compared in the analysis, the van Genuchten (1980) equation with parameters m and n restricted according to the Mualem (m = 1 - 1/n) criterion is best suited to describe the θ(h) relationships. The accuracy of two models that predict K(θ) using parameter values derived from the SWR models was also evaluated. The model developed by van Genuchten (1980) based on the theoretical expression of Mualem (1976) predicted K(θ) more accurately than the van Genuchten (1980) model based on the theory of Burdine (1953). A sensitivity analysis shows that more accurate predictions of K(θ) are achieved using SWR model parameters derived with residual water content (θr) specified according to independent measurements of θ at values of h where θ/h ∼ 0 rather than model-fit θr values. The accuracy of the model K(θ) function improves markedly when at least one value of unsaturated K is used to scale the K(θ) function predicted using the saturated K. The results of this investigation indicate that the hydraulic properties of coarse-grained sediments can be accurately described using the parametric models. In addition, data collection efforts should focus on measuring at least one value of unsaturated hydraulic conductivity and as complete a set of SWR data as possible, particularly in the dry range.

Strain localization in usnaturated soils with large deformation

NASA Astrophysics Data System (ADS)

Song, X.; Borja, R. I.

2014-12-01

Strain localization is a ubiquitous feature of granular materials undergoing nonhomogeneous deformation. In unsaturated porous media, how the localized deformation band is formed depends crucially on the degree of saturation, since fluid in the pores of a solid imposes a volume constraint on the deformation of the solid. When fluid flow is involved, the inception of the localized deformation band also depends on the heterogeneity of a material, which is quantified in terms of the spatial variation of density, the degree of saturation, and matric suction. We present a mathematical framework for coupled solid-deformation/fluid-diffusion in unsaturated porous media that takes into account material and geometric nonlinearities [1, 2]. The framework relies on the continuum principle of thermodynamics to identify an effective, or constitutive, stress for the solid matrix, and a water retention law that highlights the interdependence of degree of saturation, suction, and porosity of the material. We discuss the role of heterogeneity, quantified either deterministically or stochastically, on the development of a persistent shear band. We derive bifurcation conditions [3] governing the initiation of such a shear band. This research is inspired by current testing techniques that allow nondestructive and non-invasive measurement of density and the degree of saturation through high-resolution imaging [4]. The numerical simulations under plane strain condition demonstrate that the bifurcation not only manifests itself on the loading response curve and but also in the space of the degree of saturation, specific volume and suction stress. References[1] Song X, Borja RI, Mathematical framework for unsaturated flow in the finite deformation range. Int. J. Numer. Meth. Engng 2014; 97: 658-686. [2] Song X, Borja RI, Finite deformation and fluid flow in unsaturated soils with random heterogeneity. Vadose Zone Journal 2014; doi:10.2136/vzj2013.07.0131. [3] Song X, Borja RI, Instability and bifurcation in partially saturated porous media. 2014. to be submitted. [4] Song X, Strain localization in unsaturated porous media. 2014. Ph.D. Dissertation, Stanford University, California.

Soil water movement in the unsaturated zone of an inland arid region: Mulched drip irrigation experiment

NASA Astrophysics Data System (ADS)

Han, Dongmei; Zhou, Tiantian

2018-04-01

Agricultural irrigation with trans-basin water diversion can effectively relieve the water paucity in arid and semi-arid regions, however, this may be accompanied by eco-environmental problems (e.g., saline soils, rising groundwater levels, water quality problems). The mechanism of soil water movement under irrigation in the unsaturated zone of arid regions is a key scientific problem that should be solved in order to evaluate agricultural water management and further improve current irrigation practices. This study investigated the impact of drip irrigation on soil water movement in the unsaturated zone of a cotton field in an inland arid region (the Karamay Agricultural Development Area), northwest China. Combining in situ observational physical data with temporal variation in stable isotopic compositions of soil water, we described the soil water flow system and mechanism in severe (Plot 1) and mild (Plot 2) saline-alkali cotton fields. The infiltration depths are 0-150 cm for both plots. Drip irrigation scheduling makes no significant contribution to local groundwater recharge, however, groundwater can move into the unsaturated zone through capillary rise during cotton flowering and boll periods. Plot 2 is less prone to having secondary soil salinization than Plot 1 due to the existence of a middle layer (approximately 100 cm thick), which elongated the distance between the root zone and aquifer. Rise in the water table (approximately 60 cm for Plot 1 and 50 cm for Plot 2) could be caused by lateral groundwater flow instead of vertical infiltration. We estimated the soil water storage changes in the unsaturated zone and proposed a conceptual model for deciphering the movement process of soil water. This study provides a scientific basis for determining the rise of groundwater levels and potential development of saline soils and improving agricultural water management in arid regions.

Modeling water infiltration and pesticides transport in unsaturated zone of a sedimentary aquifer

NASA Astrophysics Data System (ADS)

Sidoli, Pauline; Angulo-Jaramillo, Rafael; Baran, Nicole; Lassabatère, Laurent

2015-04-01

Groundwater quality monitoring has become an important environmental, economic and community issue since increasing needs drinking water at the same time with high anthropic pressure on aquifers. Leaching of various contaminants as pesticide into the groundwater is closely bound to water infiltration in the unsaturated zone which whom solute transport can occur. Knowledge's about mechanisms involved in the transfer of pesticides in the deep unsaturated zone are lacking today. This study aims to evaluate and to model leaching of pesticides and metabolites in the unsaturated zone, very heterogeneous, of a fluvio-glacial aquifer, in the South-East of France, where contamination of groundwater resources by pesticides is frequently observed as a consequence of intensive agricultural activities. Water flow and pesticide transport were evaluated from column tests under unsaturated conditions and from adsorption batch experiments onto the predominant lithofacies collected, composed of a mixture of sand and gravel. A maize herbicide, S-metolachlor, applied on the study site and worldwide and its two major degradation products (metolachlor ethanesulfonic acid and metolachlor oxanilic acid) were studied here. A conservative tracer, bromide ion, was used to determine water dispersive parameters of porous media. Elution curves were obtained from pesticide concentrations analyzed by an ultra-performance liquid chromatography system interfaced to a triple quadrupole mass spectrometer and from bromide concentrations measured by ionic chromatography system. Experimental data were implemented into Hydrus to model flow and solute transfer through a 1D profile in the vadose zone. Nonequilibrium solute transport model based on dual-porosity model with mobile and immobile water is fitting correctly elution curves. Water dispersive parameters show flow pattern realized in the mobile phase. Exchanges between mobile and immobile water are very limited. Because of low adsorptions onto fluvio-glacial deposits, retention of S-metolachlor and its ionic metabolites is low in column tests and high mobility was observed meaning these molecules are prone to reach groundwater.

Study on the response of unsaturated soil slope based on the effects of rainfall intensity and slope angle

NASA Astrophysics Data System (ADS)

Ismail, Mohd Ashraf Mohamad; Hamzah, Nur Hasliza

2017-07-01

Rainfall has been considered as the major cause of the slope failure. The mechanism leading to slope failures included the infiltration process, surface runoff, volumetric water content and pore-water pressure of the soil. This paper describes a study in which simulated rainfall events were used with 2-dimensional soil column to study the response of unsaturated soil behavior based on different slope angle. The 2-dimensional soil column is used in order to demonstrate the mechanism of the slope failure. These unsaturated soil were tested with four different slope (15°, 25°, 35° and 45°) and subjected to three different rainfall intensities (maximum, mean and minimum). The following key results were obtained: (1) the stability of unsaturated soil decrease as the rainwater infiltrates into the soil. Soil that initially in unsaturated state will start to reach saturated state when rainwater seeps into the soil. Infiltration of rainwater will reduce the matric suction in the soil. Matric suction acts in controlling soil shear strength. Reduction in matric suction affects the decrease in effective normal stress, which in turn diminishes the available shear strength to a point where equilibrium can no longer be sustained in the slope. (2) The infiltration rate of rainwater decreases while surface runoff increase when the soil nearly achieve saturated state. These situations cause the soil erosion and lead to slope failure. (3) The steepness of the soil is not a major factor but also contribute to slope failures. For steep slopes, rainwater that fall on the soil surface will become surface runoff within a short time compare to the water that infiltrate into the soil. While for gentle slopes, water that becomes surface runoff will move slowly and these increase the water that infiltrate into the soil.

Genetic parameters for milk fatty acids in Danish Holstein cattle based on SNP markers using a Bayesian approach.

PubMed

Krag, Kristian; Poulsen, Nina A; Larsen, Mette K; Larsen, Lotte B; Janss, Luc L; Buitenhuis, Bart

2013-09-11

For several years, in human nutrition there has been a focus on the proportion of unsaturated fatty acids (UFA) and saturated fatty acids (SFA) found in bovine milk. The positive health-related properties of UFA versus SFA have increased the demand for food products with a higher proportion of UFA. To be able to change the UFA and SFA content of the milk by breeding it is important to know whether there is a genetic component underlying the individual FA in the milk. We have estimated the heritability for individual FA in the milk of Danish Holstein. For this purpose we used information of SNP markers instead of the traditional pedigree relationships. Estimates of heritability were moderate within the range of 0.10 for C18:1 trans-11 to 0.34 for C8:0 and C10:0, whereas the estimates for saturated fatty acids and unsaturated fatty acids were 0.14 and 0.18, respectively. Posterior standard deviations were in the range from 0.07 to 0.17. The correlation estimates showed a general pattern of two groups, one group mainly consisting of saturated fatty acids and one group mainly consisting of unsaturated fatty acids. The phenotypic correlation ranged from -0.95 (saturated fatty acids and unsaturated fatty acids) to 0.99 (unsaturated fatty acids and monounsaturated fatty acids) and the genomic correlation for fatty acids ranged from -0.29 to 0.91. The heritability estimates obtained in this study are in general accordance with heritability estimates from studies using pedigree data and/or a genomic relationship matrix in the context of a REML approach. SFA and UFA expressed a strong negative phenotypic correlation and a weaker genetic correlation. This is in accordance with the theory that SFA is synthesized de novo, while UFA can be regulated independently from the regulation of SFA by the feeding regime.

Modeling Raw Sewage Leakage and Transport in the Unsaturated Zone of Carbonate Aquifer Using Carbamazepine as an Indicator

NASA Astrophysics Data System (ADS)

Yakirevich, A.; Kuznetsov, M.; Livshitz, Y.; Gasser, G.; Pankratov, I.; Lev, O.; Adar, E.; Dvory, N. Z.

2016-12-01

Fast contamination of groundwater in karstic aquifers can be caused due to leaky sewers, for example, or overflow from sewer networks. When flowing through a karst system, wastewater has the potential to reach the aquifer in a relatively short time. The Western Mountain Aquifer (Yarkon-Taninim) of Israel is one of the country's major water resources. During late winter 2013, maintenance actions were performed on a central sewage pipe that caused raw sewage to leak into the creek located in the study area. The subsequent infiltration of sewage through the thick ( 100 m) fractured/karst unsaturated zone led to a sharp increase in contaminant concentrations in the groundwater, which was monitored in a well located 29 meters from the center of the creek. Carbamazepine (CBZ) was used as an indicator for the presence of untreated raw sewage and its quantification in groundwater. The ultimate research goal was to develop a mathematical model for quantifying flow and contaminant transport processes in the fractured-porous unsaturated zone and karstified groundwater system. A quasi-3D dual permeability numerical model, representing the 'vadose zone - aquifer' system, was developed by a series of 1D equations solved in variably-saturated zone and by 3D-saturated flow and transport equation in groundwater. The 1D and 3D equations were coupled at the moving phreatic surface. The model was calibrated and applied to a simulated water flow scenario and CBZ transport during and after the observed sewage leakage event. The results of simulation showed that after the leakage stopped, significant amounts of CBZ were retained in the porous matrix of the unsaturated zone below the creek. Water redistribution and slow recharge during the dry summer season contributed to elevated CBZ concentrations in the groundwater in the vicinity of the creek and tens of meters downstream. The resumption of autumn rains enhanced flushing of CBZ from the unsaturated zone and led to an increase in groundwater concentrations.

Thermodynamics of the clusterization process of cis isomers of unsaturated fatty acids at the air/water interface.

PubMed

Vysotsky, Yu B; Belyaeva, E A; Fainerman, V B; Vollhardt, D; Aksenenko, E V; Miller, R

2009-04-02

In the framework of the semiempirical PM3 method, the thermodynamic parameters of cis isomers of unsaturated carboxylic acids at the air/water interface are studied. The model systems used are unsaturated cis fatty acid of the composition Delta = 12-15 and omega = 6-11, where Delta and omega refer to the number of carbon atoms between the functional group and double bond, and that between the double bond and methyl group, respectively. For dimers, trimers, and tetramers of the four acid series, the thermodynamic parameters of clusterization are calculated. It is shown that the position of the double bond does not significantly affect the values of thermodynamic parameters of formation and clusterization of carboxylic acids for equal chain lengths (n = Delta + omega). The calculated results show that for cis unsaturated fatty acid with odd Delta values the spontaneous clusterization threshold corresponds to n = 17-18 carbon atoms in the alkyl chain, while for monounsaturated acids with even Delta values this threshold corresponds to n = 18-19 carbon atoms in the alkyl chain. These differences in the clusterization threshold between the acids with even and odd Delta values are attributed to the formation of additional intermolecular hydrogen bonds between the ketonic oxygen atom of one monomer and the hydrogen atom linked to the alpha-carbon atom of the second monomer for the acids with odd Delta values or between the hydroxyl oxygen atom of one monomer and hydrogen atom linked to the alpha-carbon atom of the second monomer for the acids with even Delta values. The results obtained in the study agree satisfactorily with our experimental data for cis unsaturated nervonic (Delta15, omega9) and erucic acids (Delta13, omega9), and published data for some fatty acids, namely cis-16-heptadecenoic (Delta16, omega1), cis-9-hexadecenoic (Delta7, omega9), cis-11-eicosenoic (Delta11, omega9) and cis-9-octadecenoic acid (Delta9, omega9).

The transport and behaviour of isoproturon in unsaturated chalk cores

NASA Astrophysics Data System (ADS)

Besien, T. J.; Williams, R. J.; Johnson, A. C.

2000-04-01

A batch sorption study, a microcosm degradation study, and two separate column leaching studies were used to investigate the transport and fate of isoproturon in unsaturated chalk. The column leaching studies used undisturbed core material obtained from the field by dry percussion drilling. Each column leaching study used 25 cm long, 10 cm wide unsaturated chalk cores through which a pulse of isoproturon and bromide was eluted. The cores were set-up to simulate conditions in the unsaturated zone of the UK Chalk aquifer by applying a suction of 1 kPa (0.1 m H 2O) to the base of each column, and eluting at a rate corresponding to an average recharge rate through the unsaturated Chalk. A dye tracer indicated that the flow was through the matrix under these conditions. The results from the first column study showed high recovery rates for both isoproturon (73-92%) and bromide (93-96%), and that isoproturon was retarded by a factor of about 1.23 relative to bromide. In the second column study, two of the four columns were eluted with non-sterile groundwater in place of the sterile groundwater used on all other columns, and this study showed high recovery rates for bromide (85-92%) and lower recovery rates for isoproturon (66-79% — sterile groundwater, 48-61% — non-sterile groundwater). The enhanced degradation in the columns eluted with non-sterile groundwater indicated that groundwater microorganisms had increased the degradation rate within these columns. Overall, the reduced isoproturon recovery in the second column study was attributed to increased microbial degradation as a result of the longer study duration (162 vs. 105 days). The breakthrough curves (BTCs) for bromide had a characteristic convection-dispersion shape and were accurately simulated with the minimum of calibration using a simple convection-dispersion model (LEACHP). However, the isoproturon BTCs had an unusual shape and could not be accurately simulated.

Towards a simple representation of chalk hydrology in land surface modelling

NASA Astrophysics Data System (ADS)

Rahman, Mostaquimur; Rosolem, Rafael

2017-01-01

Modelling and monitoring of hydrological processes in the unsaturated zone of chalk, a porous medium with fractures, is important to optimize water resource assessment and management practices in the United Kingdom (UK). However, incorporating the processes governing water movement through a chalk unsaturated zone in a numerical model is complicated mainly due to the fractured nature of chalk that creates high-velocity preferential flow paths in the subsurface. In general, flow through a chalk unsaturated zone is simulated using the dual-porosity concept, which often involves calibration of a relatively large number of model parameters, potentially undermining applications to large regions. In this study, a simplified parameterization, namely the Bulk Conductivity (BC) model, is proposed for simulating hydrology in a chalk unsaturated zone. This new parameterization introduces only two additional parameters (namely the macroporosity factor and the soil wetness threshold parameter for fracture flow activation) and uses the saturated hydraulic conductivity from the chalk matrix. The BC model is implemented in the Joint UK Land Environment Simulator (JULES) and applied to a study area encompassing the Kennet catchment in the southern UK. This parameterization is further calibrated at the point scale using soil moisture profile observations. The performance of the calibrated BC model in JULES is assessed and compared against the performance of both the default JULES parameterization and the uncalibrated version of the BC model implemented in JULES. Finally, the model performance at the catchment scale is evaluated against independent data sets (e.g. runoff and latent heat flux). The results demonstrate that the inclusion of the BC model in JULES improves simulated land surface mass and energy fluxes over the chalk-dominated Kennet catchment. Therefore, the simple approach described in this study may be used to incorporate the flow processes through a chalk unsaturated zone in large-scale land surface modelling applications.

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

PubMed

Cohen, D E; Carey, M C

1991-08-01

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

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.

Evaluation of used fuel disposition in clay-bearing rock

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

Jove-Colon, Carlos F.; Hammond, Glenn Edward; Kuhlman, Kristopher L.

The R&D program from the DOE Used Fuel Disposition Campaign (UFDC) has documented key advances in coupled Thermal-Hydrological-Mechanical-Chemical (THMC) modeling of clay to simulate its complex dynamic behavior in response to thermal and hydrochemical feedbacks. These efforts have been harnessed to assess the isolation performance of heat-generating nuclear waste in a deep geological repository in clay/shale/argillaceous rock formations. This report describes the ongoing disposal R&D efforts on the advancement and refinement of coupled THMC process models, hydrothermal experiments on barrier clay interactions, used fuel and canister material degradation, thermodynamic database development, and reactive transport modeling of the near-field under non-isothermalmore » conditions. These play an important role to the evaluation of sacrificial zones as part of the EBS exposure to thermally-driven chemical and transport processes. Thermal inducement of chemical interactions at EBS domains enhances mineral dissolution/precipitation but also generates mineralogical changes that result in mineral H2O uptake/removal (hydration/dehydration reactions). These processes can result in volume changes that can affect the interface / bulk phase porosities and the mechanical (stress) state of the bentonite barrier. Characterization studies on bentonite barrier samples from the FEBEX-DP international activity have provided important insight on clay barrier microstructures (e.g., microcracks) and interactions at EBS interfaces. Enhancements to the used fuel degradation model outlines the need to include the effects of canister corrosion due the strong influence of H2 generation on the source term.« less

Hydraulic characterization of " Furcraea andina

NASA Astrophysics Data System (ADS)

Rivera-Velasquez, M. F.; Fallico, C.; Molinari, A.; Santillan, P.; Salazar, M.

2012-04-01

The present level of pollution, increasingly involving groundwaters, constitutes a serious risk for environment and human health. Therefore the remediation of saturated and unsaturated soils, removing pollutant materials through innovative and economic bio-remediation techniques is more frequently required. Recent studies on natural fiber development have shown the effectiveness of these fibers for removal of some heavy metals, due to the lignin content in the natural fibers which plays an important role in the adsorption of metal cations (Lee et al., 2004; Troisi et al., 2008; C. Fallico, 2010). In the context of remediation techniques for unsaturated and/or saturated zone, an experimental approach for the hydraulic characterization of the "Furcraea andina" (i.e., Cabuya Blanca) fiber was carried out. This fiber is native to Andean regions and grows easily in wild or cultivated form in the valleys and hillsides of Colombia, Ecuador, and Peru. Fibers of "Furcraea andina" were characterized by experimental tests to determine their hydraulic conductivity or permeability and porosity in order to use this medium for bioremediation of contaminated aquifer exploiting the physical, chemical and microbial capacity of natural fiber in heavy metal adsorption. To evaluate empirically the hydraulic conductivity, laboratory tests were carried out at constant head specifically on the fibers manually extracted. For these tests we used a flow cell (used as permeameter), containing the "Furcraea andina" fibers to be characterized, suitably connected by a tygon pipe to a Marriott's bottle, which had a plastic tube that allow the adjustment of the hydraulic head for different tests to a constant value. By this experiment it was also possible to identify relationships that enable the estimation of permeability as a function of density, i.e. of the compaction degree of the fibers. Our study was carried out for three values of hydraulic head (H), namely 10, 18, and 25 cm and for each constant head we repeated the test for three different rate of fiber compaction within the flow cell, corresponding to three different densities (146 kg/m3, 200 kg/m3 and 240 kg/m3). We observed that with increasing density of the fibers there is an increase of hydraulic conductivity. The importance of the experimental results on permeability acquires greater relevance when compared to the values of hydraulic conductivity already known from the literature for different soils types. In this study, special attention has been given to the value of hydraulic conductivity of this fiber, considering that in the framework of groundwater remediation strategies if the hydraulic conductivity in the barrier is lower than that of the surrounding aquifer, the plume may change its natural pathway, bypassing the barrier and veering towards larger hydraulic conductivity. Reference • Lee, B. G. and Rowell, R. M.: Removal of heavy metal ions from aqueous solutions using lignocellulosic fibers, J. Natural Fibers, 1, 97-108, 2004. • Troisi, S., Fallico, C., Straface, S., and Mazzuca, L.: Biodreni per la bonifica di siti contaminati realizzati con fibre naturali liberiane ad elevato sviluppo superficiale. Brevetto dell'Università della Calabria (n.: CS2008A00018), 2008. • C. Fallico, S. Troisi, A. Molinari, and M. F. Rivera.: Characterization of broom fibers for PRB in the remediation of aquifers contaminated by heavy metals, Biogeosciences journal , 7, 2545-2556, 2010

A Pauson-Khand-type reaction between alkynes and olefinic aldehydes catalyzed by rhodium/cobalt heterobimetallic nanoparticles: an olefinic aldehyde as an olefin and CO source.

PubMed

Park, Kang Hyun; Jung, Il Gu; Chung, Young Keun

2004-04-01

Co/Rh (Co:Rh = 2:2) heterobimetallic nanoparticles derived from Co(2)Rh(2)(CO)(12) react with alkynes and alpha,beta-unsaturated aldehydes such as acrolein, crotonaldehyde, and cinnamic aldehyde and release products resulting from [2 + 2 + 1]cycloaddition of alkyne, carbon monoxide, and alkene. alpha,beta-Unsaturated aldehydes act as a CO and alkene source. These reactions produce 2-substituted cyclopentenones.

The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds.

PubMed

Kelsen, Vinciane; Wendt, Bianca; Werkmeister, Svenja; Junge, Kathrin; Beller, Matthias; Chaudret, Bruno

2013-04-28

The performance of well-defined ultrasmall iron(0) nanoparticles (NPs) as catalysts for the selective hydrogenation of unsaturated C-C and C=X bonds is reported. Monodisperse iron nanoparticles of about 2 nm size are synthesized by the decomposition of {Fe(N[Si(CH3)3]2)2}2 under dihydrogen. They are found to be active for the hydrogenation of various alkenes and alkynes under mild conditions and weakly active for C=O bond hydrogenation.

Recent Developments in the Addition of Phosphinylidene-Containing Compounds to Unactivated Unsaturated Hydrocarbons: Phosphorus-Carbon Bond-Formation via Hydrophosphinylation and Related Processes

PubMed Central

Coudray, Laëtitia

2012-01-01

Summary The reactions of phosphinylidene-containing compounds with unactivated unsaturated hydrocarbons are reviewed. The review is organized by phosphorus-containing functional group types. Free-radical and metal-catalyzed additions of R1R2P(O)H to alkenes, alkynes, and related compounds, deliver functionalized organophosphorus compounds RP(O)R1R2, including H-phosphinates, phosphinates, tertiary phosphine oxides, and phosphonates. The review covers the literature up to February 2008. PMID:23308039

(E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation.

PubMed

Shi, Renyi; Zhang, Hua; Lu, Lijun; Gan, Pei; Sha, Yuchen; Zhang, Heng; Liu, Qiang; Beller, Matthias; Lei, Aiwen

2015-02-21

A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO.

Structure, bonding, and reactivity of reactant complexes and key intermediates.

PubMed

Soriano, Elena; Marco-Contelles, José

2011-01-01

Complexes of Pt and Au (gold(III) and cationic gold(I)) have shown an exceptional ability to promote a variety of organic transformations of unsaturated precursors due to their peculiar Lewis acid properties: the alkynophilic character of these soft metals and the π-acid activation of unsaturated groups promotes the intra- or intermolecular attack of a nucleophile. In this chapter we summarize the computational data reported on the structure, bonding, and reactivity of the reactant π-complexes and also on the key intermediate species.

Production of metal particles and clusters

NASA Technical Reports Server (NTRS)

Mcmanus, S. P.

1982-01-01

The feasibility of producing novel metals or metal clusters in a low gravity environment was studied. The production of coordinately unsaturated metal carbonyls by thermolysis or photolysis of stable metal carbonyls has the potential to generate novel catalysts by this technique. Laser irradiation of available metal carbonyls was investigated. It is found that laser induced decomposition of metal carbonyls is feasible for producing a variety of coordinately unsaturated species. Formation of clustered species does occur but is hampered by weak metal-metal bonds.

Cooperative dual catalysis: application to the highly enantioselective conjugate cyanation of unsaturated imides.

PubMed

Sammis, Glenn M; Danjo, Hiroshi; Jacobsen, Eric N

2004-08-18

Cooperative heterobimetallic catalysis was used as a design principle to achieve a highly reactive system for the enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides. A dual-catalyst pathway involving chiral (salen)Al complex 1b and chiral (pybox)Er complex 4b provides measurable improvements in rates and enantioselectivities relative to single-catalyst systems. Mechanistic studies point to a cooperative bimetallic mechanism involving activation of the imide by the Al complex and activation of cyanide by the Er complex.

Addition of CF3 across unsaturated moieties: a powerful functionalization tool

PubMed Central

2014-01-01

In the last few years, the efficient introduction of trifluoromethyl groups in organic molecules has become a major research focus. This review highlights the recent developments enabling the incorporation of CF3 groups across unsaturated moieties, preferentially alkenes, and the mechanistic scenarios governing these transformations. We have specially focused on methods involving the simultaneous formation of C–CF3 and C–C or C–heteroatom bonds by formal addition reactions across π-systems, as such difunctionalization processes hold valuable synthetic potential. PMID:24789472

Polymeric Beads for Organic Coatings

DTIC Science & Technology

1982-10-31

Clear Solid Polymeric Beads A solid polymeric bead is comprised of a sol id mass of polymerized unsaturated polyester/styrene resin mixture . 2. lear...than the current unsaturated polyester resin . For example, a bead male from acrylic resin could be more trans- - parent, more durable and provide more...0.44 Isopropyl Alcohol I 11.26 I 1 .73 60% Wt. Alkyd Resin - Volume I 251.26 i 30.52 " Sol ids 51% 1 I Anti.-Skinning Agent I 0.90 I 0.12 Mineral

Simple one-pot conversion of aldehydes and ketones to enals.

PubMed

Valenta, Petr; Drucker, Natalie A; Bode, Jeffrey W; Walsh, Patrick J

2009-05-21

A simple and efficient method to convert aldehydes into alpha,beta-unsaturated aldehydes with a two-carbon homologation is presented. Hydroboration of ethoxy acetylene with BH(3).SMe(2) generates tris(ethoxyvinyl) borane. Transmetalation with diethylzinc, addition to aldehydes or ketones, and acidic workup affords enals. When the addition is quenched with anilinium hydrochloride, 1,2-dithioglycol, or acetic anhydride, the unsaturated imine, dithiolane, or 1,1-diacetate is isolated in high yield. These transformations can be performed in a one-pot procedure.

Effects of long-term high-saturated and unsaturated fatty acid diets on relaxation and contraction of renal arteries in insulin resistant rats.

PubMed

Gao, Yu; Song, Guang-Yao; Ma, Hui-Juan; Zhang, Wen-Jie; Zhou, Yu

2007-06-25

The present study was designed to investigate the effects of high-saturated and high-unsaturated fatty acid diets on relaxation and contraction of the renal arteries in insulin resistance (IR) rats. Wistar rats were fed normal chow diet (control), high-saturated fatty acid diet or high-unsaturated fatty acid diet for 6 months (n=14 in each group). IR was evaluated by glucose infusion rate (GIR) of hyperinsulinemic euglycemic clamp. Blood pressure was measured via the tail-cuff method. Body weight (BW), plasma total triglyceride (TG), free fatty acid (FFA), insulin, fasting blood glucose (FBG) and nitric oxide metabolite (NO2(-)/NO3(-)) were compared among the three groups. The rats were sacrificed and the renal arterial rings were placed in the physiological tissue baths for measurement of vascular response to various agents. After the arterial rings were constricted with 3 mmol/L noradrenaline (NA), endothelium-dependent vasorelaxation to acetylcholine (ACh) and endothelium-independent vasorelaxation to sodium nitroprusside (NTP) were measured. Endothelium-dependent vasorelaxation to ACh was also observed in renal arterial rings incubated with L-arginine (L-Arg), N(omega)-nitro-L-arginine (L-NNA) and methylene blue (MB), respectively. Arterial contractility was evaluated from concentration-response curves to 10 nmol/L-100 micromol/L NA. Saturated or unsaturated fatty acids led to moderate rises in blood pressure (P<0.05). It was associated with higher levels of plasma lipids and lower whole body insulin sensitivity (P<0.01). There were no significant differences in BW, FBG, TG, insulin and FFA between saturated and unsaturated fatty acid-fed rats. A decrease in endothelium-dependent vasorelaxation of the renal arteries in saturated and unsaturated fatty acid-fed rats was observed (P<0.01), but there was no marked difference between the two high-fatty acid diet groups. Endothelium-dependent vasorelaxation was increased when the arteries were incubated with L-Arg and decreased when incubated with L-NNA and MB in both high-fatty acid diet groups (P<0.05, P<0.01). But no difference was found before and after incubation with L-Arg, L-NNA and MB in the control rats. In the mean time, endothelium-independent maximal vasorelaxation response of renal arteries to NTP and renal arterial contractile responses to cumulative dose of NA were assayed, and there was no difference among the three groups (P>0.05). Endothelium-dependent vasorelaxation was negatively correlated with systolic blood pressure and TG, and positively correlated with NO2(-)/NO3(-) and GIR. There was a significantly negative correlation between FFA and NO2(-)/NO3(-). The present study suggests that both high-saturated and unsaturated fatty acid diets result in hypertension associated with significantly decreased endothelium-dependent vasorelaxation, dyslipidemia and IR, and that decreased endothelium-dependent vasorelaxation induced by high fatty acid diets is associated with impaired L-Arg-NO-cGMP pathways.

Quasi‐steady centrifuge method for unsaturated hydraulic properties

USGS Publications Warehouse

Caputo, Maria C.; Nimmo, John R.

2005-01-01

We have developed the quasi‐steady centrifuge (QSC) method as a variation of the steady state centrifuge method that can be implemented simply and inexpensively with greater versatility in terms of sample size and other features. It achieves these advantages by somewhat relaxing the criterion for steadiness of flow through the sample. This compromise entails an increase in measurement uncertainty but to a degree that is tolerable in most applications. We have tested this new approach with an easily constructed apparatus to establish a quasi‐steady flow of water in unsaturated porous rock samples spinning in a centrifuge, obtaining measurements of unsaturated hydraulic conductivity and water retention that agree with results of other methods. The QSC method is adaptable to essentially any centrifuge suitable for hydrogeologic applications, over a wide range of sizes and operating speeds. The simplified apparatus and greater adaptability of this method expands the potential for exploring situations that are common in nature but have been the subject of few laboratory investigations.

Identification of the toxic compounds produced by Sargassum thunbergii to red tide microalgae

NASA Astrophysics Data System (ADS)

Wang, Renjun; Wang, You; Tang, Xuexi

2012-09-01

The inhibitory effects of methanol extracts from the tissues of three macroalgal species on the growths of three marine red tide microalgae were assessed under laboratory conditions. Extracts of Sargassum thunbergii (Mertens ex Roth) Kuntz tissue had stronger inhibitory effects than those of either Sargassum pallidum (Turner) C. Agardh or Sargassum kjellmanianum Yendo on the growths of Heterosigma akashiwo (Hada) Hada, Skeletonema costatum (Grev.) Grev, and Prorocentrum micans Ehrenberg. Methanol extracts of S. thunbergii were further divided into petroleum ether, ethyl acetate, butanol, and distilled water phases by liquid-liquid fractionation. The petroleum ether and ethyl acetate fractions had strong algicidal effects on the microalgae. Gas chromatography-mass spectrometry analyses of these two phases identified nine fatty acids, most of which were unsaturated fatty acids. In addition, pure compounds of four of the nine unsaturated fatty acids had effective concentrations below 5 mg/L. Therefore, unsaturated fatty acids are a component of the allelochemicals in S. thunbergii tissue.

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.

Effects of Chain Length and Degree of Unsaturation of Fatty Acids on Structure and in Vitro Digestibility of Starch-Protein-Fatty Acid Complexes.

PubMed

Zheng, Mengge; Chao, Chen; Yu, Jinglin; Copeland, Les; Wang, Shuo; Wang, Shujun

2018-02-28

The effects of chain length and degree of unsaturation of fatty acids (FAs) on structure and in vitro digestibility of starch-protein-FA complexes were investigated in model systems. Studies with the rapid visco analyzer (RVA) showed that the formation of ternary complex resulted in higher viscosities than those of binary complex during the cooling and holding stages. The results of differential scanning calorimetry (DSC), Raman, and X-ray diffraction (XRD) showed that the structural differences for ternary complexes were much less than those for binary complexes. Starch-protein-FA complexes presented lower in vitro enzymatic digestibility compared with starch-FAs complexes. We conclude that shorter chain and lower unsaturation FAs favor the formation of ternary complexes but decrease the thermal stability of these complexes. FAs had a smaller effect on the ordered structures of ternary complexes than on those of binary complexes and little effect on enzymatic digestibility of both binary and ternary complexes.

Saturated and unsaturated fat induce hepatic insulin resistance independently of TLR-4 signaling and ceramide synthesis in vivo.

PubMed

Galbo, Thomas; Perry, Rachel J; Jurczak, Michael J; Camporez, João-Paulo G; Alves, Tiago C; Kahn, Mario; Guigni, Blas A; Serr, Julie; Zhang, Dongyan; Bhanot, Sanjay; Samuel, Varman T; Shulman, Gerald I

2013-07-30

Hepatic insulin resistance is a principal component of type 2 diabetes, but the cellular and molecular mechanisms responsible for its pathogenesis remain unknown. Recent studies have suggested that saturated fatty acids induce hepatic insulin resistance through activation of the toll-like receptor 4 (TLR-4) receptor in the liver, which in turn transcriptionally activates hepatic ceramide synthesis leading to inhibition of insulin signaling. In this study, we demonstrate that TLR-4 receptor signaling is not directly required for saturated or unsaturated fat-induced hepatic insulin resistance in both TLR-4 antisense oligonucleotide treated and TLR-4 knockout mice, and that ceramide accumulation is not dependent on TLR-4 signaling or a primary event in hepatic steatosis and impairment of insulin signaling. Further, we show that both saturated and unsaturated fats lead to hepatic accumulation of diacylglycerols, activation of PKCε, and impairment of insulin-stimulated IRS-2 signaling. These data demonstrate that saturated fat-induced insulin resistance is independent of TLR-4 activation and ceramides.

Synthesis of improved polyester resins

NASA Technical Reports Server (NTRS)

Mcleod, A. H.; Delano, C. B.

1979-01-01

Eighteen aromatic unsaturated polyester prepolymers prepared by a modified interfacial condensation technique were investigated for their solubility in vinyl monomers and ability to provide high char yield forming unsaturated polyester resins. The best resin system contained a polyester prepolymer of phthalic, fumaric and diphenic acids reacted with 2,7-naphthalene diol and 9,9-bis(4-hydroxyphenyl)fluorene. This prepolymer is very soluble in styrene, divinyl benzene, triallyl cyanurate, diallyl isophthalate and methylvinylpyridine. It provided anaerobic char yields as high as 41 percent at 800 C. The combination of good solubility and char yield represents a significant improvement over state-of-the-art unsaturated polyester resins. The majority of the other prepolymers had only low or no solubility in vinyl monomers. Graphite composites from this prepolymer with styrene were investigated. The cause for the observed low shear strengths of the composites was not determined, however 12-week aging of the composites at 82 C showed that essentially no changes in the composites had occurred.

Direct current resistivity profiling to study distribution of water in the unsaturated zone near the Amargosa Desert Research Site, Nevada

USGS Publications Warehouse

Abraham, Jared D.; Lucius, Jeffrey E.

2004-01-01

In order to study the distribution of water in the unsaturated zone and potential for ground-water recharge near the Amargosa Desert Research Site south of Beatty, Nevada, the U.S. Geological Survey collected direct-current resistivity measurements along three profiles in May 2003 using an eight-channel resistivity imaging system. Resistivity data were collected along profiles across the ADRS, across a poorly incised (distributary) channel system of the Amargosa River southwest of the ADRS, and across a well-incised flood plain of the Amargosa River northwest of the ADRS.This report describes results of an initial investigation to estimate the distribution of water in the unsaturated zone and to evaluate the shallow subsurface stratigraphy near the ADRS. The geophysical method of dc resistivity was employed by using automated data collection with numerous electrodes. "Cross sections" of resistivity, produced by using an inversion algorithm on the field data, at the three field sites are presented and interpreted.

General criteria for the validity of the Buckingham-Darcy Flow Law

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

Sposito, G.

A detailed, first-principles study is undertaken on the exact equation of linear momentum balance for water in an unsaturated soil. An approximate momentum balance equation (Raats and Klute) demonstrates that the flow of water through a rigid, homogeneous, isotropic, unsaturated soil will obey the Buckingham-Darcy Law within 10/sup -12/ to 10/sup -5/ sec after a gradient in the total potential of soil water has been applied. The Raats-Klute equation will be accurate if (1) the water mass density and mass flux density vector constitute a complete set of strongly coupled, macroscopic dynamical variables, and (2) the time scale over whichmore » these 2 variables change significantly is much longer than that over which any other dynamic quantities vary. If these 2 conditions are met, then, according to statistical mechanics, the flow of water through unsaturated soil will be described accurately over all macroscopic intervals by the Buckingham-Darcy law.« less

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.

Generation of dense plume fingers in saturated-unsaturated homogeneous porous media

NASA Astrophysics Data System (ADS)

Cremer, Clemens J. M.; Graf, Thomas

2015-02-01

Flow under variable-density conditions is widespread, occurring in geothermal reservoirs, at waste disposal sites or due to saltwater intrusion. The migration of dense plumes typically results in the formation of vertical plume fingers which are known to be triggered by material heterogeneity or by variations in source concentration that causes the density variation. Using a numerical groundwater model, six perturbation methods are tested under saturated and unsaturated flow conditions to mimic heterogeneity and concentration variations on the pore scale in order to realistically generate dense fingers. A laboratory-scale sand tank experiment is numerically simulated, and the perturbation methods are evaluated by comparing plume fingers obtained from the laboratory experiment with numerically simulated fingers. Dense plume fingering for saturated flow can best be reproduced with a spatially random, time-constant perturbation of the solute source. For unsaturated flow, a spatially and temporally random noise of solute concentration or a random conductivity field adequately simulate plume fingering.

High-quality unsaturated zone hydraulic property data for hydrologic applications

USGS Publications Warehouse

Perkins, Kimberlie; Nimmo, John R.

2009-01-01

In hydrologic studies, especially those using dynamic unsaturated zone moisture modeling, calculations based on property transfer models informed by hydraulic property databases are often used in lieu of measured data from the site of interest. Reliance on database-informed predicted values has become increasingly common with the use of neural networks. High-quality data are needed for databases used in this way and for theoretical and property transfer model development and testing. Hydraulic properties predicted on the basis of existing databases may be adequate in some applications but not others. An obvious problem occurs when the available database has few or no data for samples that are closely related to the medium of interest. The data set presented in this paper includes saturated and unsaturated hydraulic conductivity, water retention, particle-size distributions, and bulk properties. All samples are minimally disturbed, all measurements were performed using the same state of the art techniques and the environments represented are diverse.

Light intensity and N/P nutrient affect the accumulation of lipid and unsaturated fatty acids by Chlorella sp.

PubMed

Guo, Xiaoyi; Su, Gaomin; Li, Zheng; Chang, Jingyu; Zeng, Xianhai; Sun, Yong; Lu, Yinghua; Lin, Lu

2015-09-01

In this study, different light intensities (80, 160, 240 and 320 μmol/m(2) s) and various mediums including control medium (CM), N/P rich medium (NPM), N rich medium (NM), and P rich medium (PM) were applied for cultivation of Chlorella sp. It was revealed that cultivation of Chlorella sp. in CM under the light intensity of 320 μmol/m(2) s led to a lipid content up to 30% enhancement, which was higher than the results of other cases. A rather high unsaturated fatty acid (UFA) content of 7.5% and unsaturated fatty acid/total fatty acid (UFA/TFA) ratio of 0.73 were obtained under 320 μmol/m(2) s in CM, indicating that the CM-320 system was applicable for the generation of UFA. Moreover, Chlorella sp. cultivated in PM under 320 μmol/m(2) s provided higher TFA content (7.3%), which was appropriate for biofuel production. Copyright © 2015 Elsevier Ltd. All rights reserved.

A semi-analytical solution for slug tests in an unconfined aquifer considering unsaturated flow

NASA Astrophysics Data System (ADS)

Sun, Hongbing

2016-01-01

A semi-analytical solution considering the vertical unsaturated flow is developed for groundwater flow in response to a slug test in an unconfined aquifer in Laplace space. The new solution incorporates the effects of partial penetrating, anisotropy, vertical unsaturated flow, and a moving water table boundary. Compared to the Kansas Geological Survey (KGS) model, the new solution can significantly improve the fittings of the modeled to the measured hydraulic heads at the late stage of slug tests in an unconfined aquifer, particularly when the slug well has a partially submerged screen and moisture drainage above the water table is significant. The radial hydraulic conductivities estimated with the new solution are comparable to those from the KGS, Bouwer and Rice, and Hvorslev methods. In addition, the new solution also can be used to examine the vertical conductivity, specific storage, specific yield, and the moisture retention parameters in an unconfined aquifer based on slug test data.

Effect of the spectral emission energy of various UV sources on photochemical curing of unsaturated oligomeric ester coatings

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

Skubin, V.K.; Sazonov, A.P.; Torgonenko, V.A.

1988-11-10

In this paper, using the example of unsaturated oligomeric esters, the effect of UV radiation of various domestic sources on the rate of curing of coatings is investigated. For the investigations a 60% styrene solution of PN-15 grade unsaturated oligomeric ester based on an equimolar ratio of maleic anhydride and oxypropylated diphenylenepropene was used. Isobutyl ether of benzoin served as the photoinitiator. The following lamps were used as radiation sources: electrodeless high-frequency lamps of continuous action with additions of mercury, cadmium, and phosphorus; a DRKS-500 mercury-xenon-arc lamp; and a DRT-1000 tubular mercury-arc lamp. When choosing UV sources to increase themore » efficiency of photochemical decay of the initiator and the rate of curing of the coating it is necessary first of all to be guided by the distribution of the spectral energy of the lamp radiation and the UV absorption spectrum of the photoinitiator.« less

Effects of substrate fatty acids on products of lecithin hydrolysis and acyl-CoA-independent transacylation with cholesterol by aortic enzyme preparations.

PubMed

Patelski, J; Pioruńska-Stolzmann, M

1985-01-01

The acyl composition of substrates and products of enzymatic hydrolysis and transacylation of lecithin with cholesterol in the arterial wall was investigated. Saturated acyl residues predominated in lysolecithin and unsaturated ones in acids released by hydrolysis of egg lecithin. In the reaction system with cholesterol, saturated acyls predominated in both lysolecithin and acids released whereas unsaturated ones were more abundant in newly formed acylcholesterols. Mainly unsaturated acyls were present in the hydrolysis products from soybean lecithin in the reaction systems with and without cholesterol. For acylcholesterols formed in the presence of either lecithin, the percent values are in the numerical order of C18:2 greater than C18:1 greater than C16:0 greater than or equal to C18:0. It It is concluded that acyl preferences and interactions in the enzyme-catalyzed reactions studied may contribute to the different accumulation and removal of the compounds involved from the artery.

Maleate/vinyl ether UV-cured coatings: Effects of composition on curing and properties

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

Noren, G.K.

1996-10-01

The effect of the composition of the maleate polyester and the vinyl ether terminated compound on their UV-curing and properties has been investigated. Linear unsaturated polyester resins based on maleic anhydride and 1,5-pentane diol were synthesized. The molecular weight of the unsaturated polyesters was varied by changing the ratio of maleic anhydride to 1,5-pentane diol and the double bond equivalent weight was varied by replacing maleic anhydride with succinic anhydride. Coating formulations containing these unsaturated polyesters, triethylene glycol divinyl ether and a free radical photoinitiator were crosslinked in the presence of UV light. The coatings were very brittle, exhibiting tensilemore » strengths in the range of 1.5-4.0 MPa and elongations of only 3-7%. Diethyl maleate and isobutyl vinyl ether were effective diluents for reducing viscosity but reduced the cure speed. A vinyl ether urethane oligomer was synthesized and enhanced the flexibility and toughness of the coatings when substituted for triethylene glycol divinyl ether.« less

Lewis super-acid catalyzed cyclizations: a new route to fragrance compounds.

PubMed

Coulombel, Lydie; Grau, Fanny; Weïwer, Michel; Favier, Isabelle; Chaminade, Xavier; Heumann, Andreas; Bayón, J Carles; Aguirre, Pedro A; Duñach, Elisabet

2008-06-01

This review deals with the application of Lewis super acids such as Al(III), In(III), and Sn(IV) triflates and triflimidates as catalysts in the synthesis of fragrance materials. Novel catalytic reactions involving C-C and C-heteroatom bond-forming reactions, as well as cycloisomerization processes are presented. In particular, Sn(IV) and Al(III) triflates were employed as catalysts in the selective cyclization of unsaturated alcohols to cyclic ethers, as well as in the cyclization of unsaturated carboxylic acids to lactones. The addition of thiols and thioacids to non-activated olefins, both in intra- and intermolecular versions, was efficiently catalyzed by In(III) derivatives. Sn(IV) Triflimidates catalyzed the cycloisomerization of highly substituted 1,6-dienes to gem-dimethyl-substituted cyclohexanes bearing an isopropylidene substituent. The hydroformylation of these unsaturated substrates, catalyzed by a Rh(I) complex with a bulky phosphite ligand, selectively afforded the corresponding linear aldehydes. The olfactory evaluation of selected heterocycles, carbocycles, and aldehydes synthesized is also discussed.

Effects of α-Glycerophosphate and of Palmityl-Coenzyme A on Lipid Synthesis in Yeast Extracts

PubMed Central

White, David; Klein, Harold P.

1966-01-01

White, David (Ames Research Center, Moffett Field, Calif.), and Harold P. Klein. Effects of α-glycerophosphate and of palmityl-coenzyme A on lipid synthesis in yeast extracts. J. Bacteriol. 91:1218–1223. 1966.—The incorporation of acetate into fatty acids, but not into nonsaponifiable lipids, was stimulated by α-glycerophosphate in a supernatant fraction of Saccharomyces cerevisiae, obtained after centrifugation at 86,000 × g for 60 min. There was a pronounced effect at concentrations below 2 mm, but at concentrations above 5 mm α-glycerophosphate was relatively less stimulatory. α-Glycerophosphate markedly increased the percentage of esterified fatty acids among the products, and the formation of both saturated and unsaturated fatty acids was stimulated. Palmityl-coenzyme A inhibited fatty acid synthesis, affecting the formation of unsaturated acids more severely than saturated acids. In the presence of sufficient α-glycerophosphate to alleviate these inhibitions, palmityl-coenzyme A still reduced the formation of certain unsaturated fatty acids. PMID:5929752

Phospholipid Chain Interactions with Cholesterol Drive Domain Formation in Lipid Membranes.

PubMed

Bennett, W F Drew; Shea, Joan-Emma; Tieleman, D Peter

2018-06-05

Cholesterol is a key component of eukaryotic membranes, but its role in cellular biology in general and in lipid rafts in particular remains controversial. Model membranes are used extensively to determine the phase behavior of ternary mixtures of cholesterol, a saturated lipid, and an unsaturated lipid with liquid-ordered and liquid-disordered phase coexistence. Despite many different experiments that determine lipid-phase diagrams, we lack an understanding of the molecular-level driving forces for liquid phase coexistence in bilayers with cholesterol. Here, we use atomistic molecular dynamics computer simulations to address the driving forces for phase coexistence in ternary lipid mixtures. Domain formation is directly observed in a long-timescale simulation of a mixture of 1,2-distearoyl-sn-glycero-3-phosphocholine, unsaturated 1,2-dilinoleoyl-sn-glycero-3-phosphocholine, and cholesterol. Free-energy calculations for the exchange of the saturated and unsaturated lipids between the ordered and disordered phases give insight into the mixing behavior. We show that a large energetic contribution to domain formation is favorable enthalpic interactions of the saturated lipid in the ordered phase. This favorable energy for forming an ordered, cholesterol-rich phase is opposed by a large unfavorable entropy. Martini coarse-grained simulations capture the unfavorable free energy of mixing but do not reproduce the entropic contribution because of the reduced representation of the phospholipid tails. Phospholipid tails and their degree of unsaturation are key energetic contributors to lipid phase separation. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Distribution of gases in the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Illinois

USGS Publications Warehouse

Striegl, Robert G.

1988-01-01

The unsaturated zone is a medium that provides pneumatic communication for the movement of gases from wastes buried in landfills to the atmosphere, biota, and groundwater. Gases in unsaturated glacial and eolian deposits near a waste-disposal trench at the low-level radioactive-waste disposal site near Sheffield, Bureau County, Illinois, were identified, and the spatial and temporal distributions of the partial pressures of those gases were determined for the period January 1984 through January 1986. Methods for the collection and analyses of the gases are described, as are geologic and hydrologic characteristics of the unsaturated zone that affect gas transport. The identified gases, which are of natural and of waste origin, include nitrogen, oxygen, and argon, carbon dioxide, methane, propane, butane, tritiated water vapor, 14carbon dioxide, and 222 radon. Concentrations of methane and 14carbon dioxide originated at the waste, as shown by partial-pressure gradients of the gases; 14carbon dioxide partial pressures exceeded natural background partial pressures by factors greater than 1 million at some locations. Variations in partial pressures of oxygen and carbon dioxide were seasonal among piezometers because of increased root and soil-microbe respiration during summer. Variations in methane and 14carbon dioxide partial pressures were apparently related to discrete releases from waste sources at unpredictable intervals of time. No greater than background partial pressures for tritiated water vapor or 222 radon were measured. (USGS)

Characterization of Phospholipids in Insulin Secretory Granules and Mitochondria in Pancreatic Beta Cells and Their Changes with Glucose Stimulation*

PubMed Central

MacDonald, Michael J.; Ade, Lacmbouh; Ntambi, James M.; Ansari, Israr-Ul H.; Stoker, Scott W.

2015-01-01

The lipid composition of insulin secretory granules (ISG) has never previously been thoroughly characterized. We characterized the phospholipid composition of ISG and mitochondria in pancreatic beta cells without and with glucose stimulation. The phospholipid/protein ratios of most phospholipids containing unsaturated fatty acids were higher in ISG than in whole cells and in mitochondria. The concentrations of negatively charged phospholipids, phosphatidylserine, and phosphatidylinositol in ISG were 5-fold higher than in the whole cell. In ISG phosphatidylserine, phosphatidylinositol, phosphatidylethanolamine, and sphingomyelin, fatty acids 12:0 and 14:0 were high, as were phosphatidylserine and phosphatidylinositol containing 18-carbon unsaturated FA. With glucose stimulation, the concentration of many ISG phosphatidylserines and phosphatidylinositols increased; unsaturated fatty acids in phosphatidylserine increased; and most phosphatidylethanolamines, phosphatidylcholines, sphingomyelins, and lysophosphatidylcholines were unchanged. Unsaturation and shorter fatty acid length in phospholipids facilitate curvature and fluidity of membranes, which favors fusion of membranes. Recent evidence suggests that negatively charged phospholipids, such as phosphatidylserine, act as coupling factors enhancing the interaction of positively charged regions in SNARE proteins in synaptic or secretory vesicle membrane lipid bilayers with positively charged regions in SNARE proteins in the plasma membrane lipid bilayer to facilitate docking of vesicles to the plasma membrane during exocytosis. The results indicate that ISG phospholipids are in a dynamic state and are consistent with the idea that changes in ISG phospholipids facilitate fusion of ISG with the plasma membrane-enhancing glucose-stimulated insulin exocytosis. PMID:25762724

Effects of carbon dioxide variations in the unsaturated zone on water chemistry in a glacial-outwash aquifer

USGS Publications Warehouse

Lee, R.W.

1997-01-01

The research site at Otis Air Base, Cape Cod, Massachusetts, has been developed for hydrogeological and geochemical studies of sewage-effluent contaminated groundwater since 1982. Research of hydrologic properties, transport, and chemical and biological processes is ongoing, but the origin of background water chemistry has not been determined. The principal geochemical process giving rise to the observed background water chemistry is CO2-controlled hydrolysis of Na feldspar. Geochemical modeling demonstrated that CO2 sources could vary over the project area. Analyses of unsaturated zone gases showed variations in CO2 which were dependent on land use and vegetative cover in the area of groundwater recharge. Measurements of CO2 in unsaturated-zone gases showed that concentrations of total inorganic C in recharge water should range from about 0.035 to 1.0 mmoles/L in the vicinity of Otis Air Base. Flux of CO2 from the unsaturated zone varied for a principal land uses, ranging from 86 gC/m2/yr for low vegetated areas to 1630 gC/m2/yr for a golf course. Carbon dioxide flux from woodlands was 220 gC/m2/yr, lower than reported fluxes of 500 to 600 gC/m2/yr for woodlands in a similar climate. Carbon dioxide flux from grassy areas was 540 gC/m2/yr, higher than reported fluxes of 230 to 490 gC/m2/yr for grasslands in a similar climate.

Anacardic Acid Constituents from Cashew Nut Shell Liquid: NMR Characterization and the Effect of Unsaturation on Its Biological Activities

PubMed Central

Morais, Selene M.; Silva, Katherine A.; Araujo, Halisson; Vieira, Icaro G.P.; Alves, Daniela R.; Fontenelle, Raquel O.S.; Silva, Artur M.S.

2017-01-01

Anacardic acids are the main constituents of natural cashew nut shell liquid (CNSL), obtained via the extraction of cashew shells with hexane at room temperature. This raw material presents high technological potential due to its various biological properties. The main components of CNSL are the anacardic acids, salicylic acid derivatives presenting a side chain of fifteen carbon atoms with different degrees of unsaturation (monoene–15:1, diene–15:2, and triene–15:3). Each constituent was isolated by column chromatography using silica gel impregnated with silver nitrate. The structures of the compounds were characterized by nuclear magnetic resonance through complete and unequivocal proton and carbon assignments. The effect of the side chain unsaturation was also evaluated in relation to antioxidant, antifungal and anticholinesterase activities, and toxicity against Artemia salina. The triene anacardic acid provided better results in antioxidant activity assessed by the inhibition of the free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH), higher cytotoxicity against A. salina, and acetylcholinesterase (AChE) inhibition. Thus, increasing the unsaturation of the side chain of anacardic acid increases its action against free radicals, AChE enzyme, and A. salina nauplii. In relation to antifungal activity, an inverse result was obtained, and the linearity of the molecule plays an important role, with monoene being the most active. In conclusion, the changes in structure of anacardic acids, which cause differences in polarity, contribute to the increase or decrease in the biological activity assessed. PMID:28300791

Prediction of unsaturated flow and water backfill during infiltration in layered soils

NASA Astrophysics Data System (ADS)

Cui, Guotao; Zhu, Jianting

2018-02-01

We develop a new analytical infiltration model to determine water flow dynamics around layer interfaces during infiltration process in layered soils. The model mainly involves the analytical solutions to quadratic equations to determine the flux rates around the interfaces. Active water content profile behind the wetting front is developed based on the solution of steady state flow to dynamically update active parameters in sharp wetting front infiltration equations and to predict unsaturated flow in coarse layers before the front reaches an impeding fine layer. The effect of water backfill to saturate the coarse layers after the wetting front encounters the impeding fine layer is analytically expressed based on the active water content profiles. Comparison to the numerical solutions of the Richards equation shows that the new model can well capture water dynamics in relation to the arrangement of soil layers. The steady state active water content profile can be used to predict the saturation state of all layers when the wetting front first passes through these layers during the unsteady infiltration process. Water backfill effect may occur when the unsaturated wetting front encounters a fine layer underlying a coarse layer. Sensitivity analysis shows that saturated hydraulic conductivity is the parameter dictating the occurrence of unsaturated flow and water backfill and can be used to represent the coarseness of soil layers. Water backfill effect occurs in coarse layers between upper and lower fine layers when the lower layer is not significantly coarser than the upper layer.

The soil physics contributions of Edgar Buckingham

USGS Publications Warehouse

Nimmo, J.R.; Landa, E.R.

2005-01-01

During 1902 to 1906 as a soil physicist at the USDA Bureau of Soils (BOS), Edgar Buckingham originated the concepts of matric potential, soil-water retention curves, specific water capacity, and unsaturated hydraulic conductivity (K) as a distinct property of a soil. He applied a formula equivalent to Darcy's law (though without specific mention of Darcy's work) to unsaturated flow. He also contributed significant research on quasi-empirical formulas for K as a function of water content, water flow in capillary crevices and in thin films, and scaling. Buckingham's work on gas flow in soils produced paradigms that are consistent with our current understanding. His work on evaporation elucidated the concept of self-mulching and produced sound and sometimes paradoxical generalizations concerning conditions that favor or retard evaporation. Largely overshadowing those achievements, however, is that he launched a theory, still accepted today, that could predict transient water content as a function of time and space. Recently discovered documents reveal some of the arguments Buckingham had with BOS officials, including the text of a two-paragraph conclusion of his famous 1907 report on soil water, and the official letter documenting rejection of that text. Strained interpersonal relations motivated the departure of Buckingham and other brilliant physicists (N.E. Dorsey, F.H. King, and Lyman Briggs) from the BOS during 1903 to 1906. Given that Buckingham and his BOS colleagues had been rapidly developing the means of quantifying unsaturated flow, these strained relations probably slowed the advancement of unsaturated flow theory. ?? Soil Science Society of America.

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.

Microwave-assisted cationic polymerization of palm olein and their urea inclusion products

NASA Astrophysics Data System (ADS)

Soegijono, Bambang; Farid, Muhamad; Alim Mas'ud, Zainal

2018-01-01

Cationic polymerization is affected by the relative amount of unsaturated bond (C=C) in the compound. The enrichment of an unsaturated triglyceride fraction from oils may be performed using urea inclusion techniques. In this study, palm olein was enriched-unsaturated fraction using urea-methanol system. The palm olein and its urea-inclusion products were cationic polymerized with ethereal boron trifluoride catalyst and followed by irradiation using a commercial microwave (microwave-assisted). The microwave irradiated products were cured at 110 °C for 24 hours. Fatty acid composition of the palm olein and its urea-inclusion products were analyzed by gas chromatography. Iodine numbers, functional groups, and ultraviolet absorption spectra of all palm olein origin, urea inclusion products and polymerization products were analyzed using titrimetric, ultraviolet spectrophotometric, and Fourier Transform infrared spectrophotometric methods. Differential scanning calorimetric (DSC) was used to observe the thermal characteristics of the polymer. Urea-inclusion process increased the unsaturated fatty acid components as indicated by the increased iodine number, intensity of alkene band absorptions in the infrared spectra, and the absorbance of the ultraviolet spectra. The polymer formation is converting the C=C group to C-C, which is indicated by the opposite of the urea inclusion process. The curing process results in reformation of new C=C bonds that were similar to that of the urea inclusion process. The DSC thermogram curve shows that the enrichment process improves the thermal stability of the polymer formed.

A topological substructural molecular design approach for predicting mutagenesis end-points of alpha, beta-unsaturated carbonyl compounds.

PubMed

Pérez-Garrido, Alfonso; Helguera, Aliuska Morales; López, Gabriel Caravaca; Cordeiro, M Natália D S; Escudero, Amalio Garrido

2010-01-31

Chemically reactive, alpha, beta-unsaturated carbonyl compounds are common environmental pollutants able to produce a wide range of adverse effects, including, e.g. mutagenicity. This toxic property can often be related to chemical structure, in particular to specific molecular substructures or fragments (alerts), which can then be used in specialized software or expert systems for predictive purposes. In the past, there have been many attempts to predict the mutagenicity of alpha, beta-unsaturated carbonyl compounds through quantitative structure activity relationships (QSAR) but considering only one exclusive endpoint: the Ames test. Besides, even though those studies give a comprehensive understanding of the phenomenon, they do not provide substructural information that could be useful forward improving expert systems based on structural alerts (SAs). This work reports an evaluation of classification models to probe the mutagenic activity of alpha, beta-unsaturated carbonyl compounds over two endpoints--the Ames and mammalian cell gene mutation tests--based on linear discriminant analysis along with the topological Substructure molecular design (TOPS-MODE) approach. The obtained results showed the better ability of the TOPS-MODE approach in flagging structural alerts for the mutagenicity of these compounds compared to the expert system TOXTREE. Thus, the application of the present QSAR models can aid toxicologists in risk assessment and in prioritizing testing, as well as in the improvement of expert systems, such as the TOXTREE software, where SAs are implemented. 2009 Elsevier Ireland Ltd. All rights reserved.