Carbonate-silicate liquid immiscibility in the mantle propels kimberlite magma ascent

NASA Astrophysics Data System (ADS)

Kamenetsky, Vadim S.; Yaxley, Gregory M.

2015-06-01

Kimberlite is a rare volcanic rock renowned as the major host of diamonds and originated at the base of the subcontinental lithospheric mantle. Although kimberlite magmas are dense in crystals and deeply-derived rock fragments, they ascend to the surface extremely rapidly, enabling diamonds to survive. The unique physical properties of kimberlite magmas depend on the specific compositions of their parental melts that, in absence of historical eruptions and due to pervasive alteration of kimberlite rocks, remain highly debatable. We explain exceptionally rapid ascent of kimberlite magma from mantle depths by combining empirical data on the essentially carbonatite composition of the kimberlite primary melts and experimental evidence on interaction of the carbonate liquids with mantle minerals. Our experimental study shows that orthopyroxene is completely dissolved in a Na2CO3 melt at 2.0-5.0 GPa and 1000-1200 °C. The dissolution of orthopyroxene results in homogeneous silicate-carbonate melt at 5.0 GPa and 1200 °C, and is followed by unmixing of carbonate and carbonated silicate melts and formation of stable magmatic emulsion at lower pressures and temperatures. The dispersed silicate melt has a significant capacity for storing a carbonate component in the deep mantle (13 wt% CO2 at 2.0 GPa). We envisage that this component reaches saturation and is gradually released as CO2 bubbles, as the silicate melt globules are transported upwards through the lithosphere by the carbonatite magma. The globules of unmixed, CO2-rich silicate melt are continuously produced upon further reaction between the natrocarbonatite melt and mantle peridotite. On decompression the dispersed silicate melt phase ensures a continuous supply of CO2 bubbles that decrease density and increase buoyancy and promote rapid ascent of the magmatic emulsion.

Thioredoxin-linked redox control of metabolism in Methanocaldococcus jannaschii, an evolutionarily deeply-rooted hyperthermophilic methanogenic archaeon

USDA-ARS?s Scientific Manuscript database

Thioredoxin (Trx), a small redox protein, controls multiple processes in eukaryotes and bacteria by changing the thiol redox status of selected proteins. We have investigated this aspect in methanarchaea. These ancient methanogens produce methane almost exclusively from H2 plus CO2 carried approxima...

Characterising the physical and chemical properties of a young Class 0 protostellar core embedded in the Orion B9 filament

NASA Astrophysics Data System (ADS)

Miettinen, O.

2016-08-01

Deeply embedded low-mass protostars can be used as testbeds to study the early formation stages of solar-type stars, and the prevailing chemistry before the formation of a planetary system. The present study aims to characterise further the physical and chemical properties of the protostellar core Orion B9-SMM3. The Atacama Pathfinder EXperiment (APEX) telescope was used to perform a follow-up molecular line survey of SMM3. The observations were done using the single pointing (frequency range 218.2-222.2 GHz) and on-the-fly mapping methods (215.1-219.1 GHz). These new data were used in conjunction with our previous data taken by the APEX and Effelsberg 100 m telescopes. The following species were identified from the frequency range 218.2-222.2 GHz: ^{13}CO, C^{18}O, SO, para-H2CO, and E1-type CH3OH. The mapping observations revealed that SMM3 is associated with a dense gas core as traced by DCO+ and p-H2CO. Altogether three different p-H2CO transitions were detected with clearly broadened linewidths (Δ v˜8.2-11 km s^{-1} in FWHM). The derived p-H2CO rotational temperature, 64±15 K, indicates the presence of warm gas. We also detected a narrow p-H2CO line (Δ v=0.42 km s^{-1}) at the systemic velocity. The p-H2CO abundance for the broad component appears to be enhanced by two orders of magnitude with respect to the narrow line value ({˜}3×10^{-9} versus {˜}2×10^{-11}). The detected methanol line shows a linewidth similar to those of the broad p-H2CO lines, which indicates their coexistence. The CO isotopologue data suggest that the CO depletion factor decreases from {˜}27±2 towards the core centre to a value of {˜}8±1 towards the core edge. In the latter position, the N2D+/N2H+ ratio is revised down to 0.14±0.06. The origin of the subfragments inside the SMM3 core we found previously can be understood in terms of the Jeans instability if non-thermal motions are taken into account. The estimated fragmentation timescale, and the derived chemical abundances suggest that SMM3 is a few times 105 yr old, in good agreement with its Class 0 classification inferred from the spectral energy distribution analysis. The broad p-H2CO and CH3OH lines, and the associated warm gas provide the first clear evidence of a molecular outflow driven by SMM3.

Designing a Deeply Digital Science Curriculum: Supporting Teacher Learning and Implementation with Organizing Technologies

ERIC Educational Resources Information Center

Leary, Heather; Severance, Samuel; Penuel, William R.; Quigley, David; Sumner, Tamara; Devaul, Holly

2016-01-01

This paper examines the impacts of technology (e.g., Chromebooks, Google Drive) on teacher learning and student activity in the development and implementation of a deeply digital high school biology unit. Using design-based implementation research, teachers co-designed with researchers and curriculum specialists a student-centered unit aligned to…

Regional-scale advective, diffusive, and eruptive dynamics of CO2 and brine leakage through faults and wellbores

NASA Astrophysics Data System (ADS)

Jung, Na-Hyun; Han, Weon Shik; Han, Kyungdoe; Park, Eungyu

2015-05-01

Regional-scale advective, diffusive, and eruptive transport dynamics of CO2 and brine within a natural analogue in the northern Paradox Basin, Utah, were explored by integrating numerical simulations with soil CO2 flux measurements. Deeply sourced CO2 migrates through steeply dipping fault zones to the shallow aquifers predominantly as an aqueous phase. Dense CO2-rich brine mixes with regional groundwater, enhancing CO2 dissolution. Linear stability analysis reveals that CO2 could be dissolved completely within only 500 years. Assigning lower permeability to the fault zones induces fault-parallel movement, feeds up-gradient aquifers with more CO2, and impedes down-gradient fluid flow, developing anticlinal CO2 traps at shallow depths (<300 m). The regional fault permeability that best reproduces field spatial CO2 flux variation is estimated 1 × 10-17 ≤ kh < 1 × 10-16 m2 and 5 × 10-16 ≤ kv < 1 × 10-15 m2. The anticlinal trap serves as an essential fluid source for eruption at Crystal Geyser. Geyser-like discharge sensitively responds to varying well permeability, radius, and CO2 recharge rate. The cyclic behavior of wellbore CO2 leakage decreases with time.

Alteration of fault rocks by CO2-bearing fluids with implications for sequestration

NASA Astrophysics Data System (ADS)

Luetkemeyer, P. B.; Kirschner, D. L.; Solum, J. G.; Naruk, S.

2011-12-01

Carbonates and sulfates commonly occur as primary (diagenetic) pore cements and secondary fluid-mobilized veins within fault zones. Stable isotope analyses of calcite, formation fluid, and fault zone fluids can help elucidate the carbon sources and the extent of fluid-rock interaction within a particular reservoir. Introduction of CO2 bearing fluids into a reservoir/fault system can profoundly affect the overall fluid chemistry of the reservoir/fault system and may lead to the enhancement or degradation of porosity within the fault zone. The extent of precipitation and/or dissolution of minerals within a fault zone can ultimately influence the sealing properties of a fault. The Colorado Plateau contains a number of large carbon dioxide reservoirs some of which leak and some of which do not. Several normal faults within the Paradox Basin (SE Utah) dissect the Green River anticline giving rise to a series of footwall reservoirs with fault-dependent columns. Numerous CO2-charged springs and geysers are associated with these faults. This study seeks to identify regional sources and subsurface migration of CO2 to these reservoirs and the effect(s) faults have on trap performance. Data provided in this study include mineralogical, elemental, and stable isotope data for fault rocks, host rocks, and carbonate veins that come from two localities along one fault that locally sealed CO2. This fault is just tens of meters away from another normal fault that has leaked CO2-charged waters to the land surface for thousands of years. These analyses have been used to determine the source of carbon isotopes from sedimentary derived carbon and deeply sourced CO2. XRF and XRD data taken from several transects across the normal faults are consistent with mechanical mixing and fluid-assisted mass transfer processes within the fault zone. δ13C range from -6% to +10% (PDB); δ18O values range from +15% to +24% (VSMOW). Geochemical modeling software is used to model the alteration productions of fault rocks from fluids of various chemistries coming from several different reservoirs within an active CO2-charged fault system. These results are compared to data obtained in the field.

Magma transport and olivine crystallization depths in Kīlauea’s East Rift Zone inferred from experimentally rehomogenized melt inclusions

USGS Publications Warehouse

Tuohy, Robin M; Wallace, Paul J.; Loewen, Matthew W; Swanson, Don; Kent, Adam J R

2016-01-01

Concentrations of H2O and CO2 in olivine-hosted melt inclusions can be used to estimate crystallization depths for the olivine host. However, the original dissolved CO2concentration of melt inclusions at the time of trapping can be difficult to measure directly because in many cases substantial CO2 is transferred to shrinkage bubbles that form during post-entrapment cooling and crystallization. To investigate this problem, we heated olivine from the 1959 Kīlauea Iki and 1960 Kapoho (Hawai‘i) eruptions in a 1-atm furnace to temperatures above the melt inclusion trapping temperature to redissolve the CO2 in shrinkage bubbles. The measured CO2 concentrations of the experimentally rehomogenized inclusions (⩽590 ppm for Kīlauea Iki [n=10]; ⩽880 ppm for Kapoho, with one inclusion at 1863 ppm [n=38]) overlap with values for naturally quenched inclusions from the same samples, but experimentally rehomogenized inclusions have higher within-sample median CO2 values than naturally quenched inclusions, indicating at least partial dissolution of CO2 from the vapor bubble during heating. Comparison of our data with predictions from modeling of vapor bubble formation and published Raman data on the density of CO2 in the vapor bubbles suggests that 55-85% of the dissolved CO2 in the melt inclusions at the time of trapping was lost to post-entrapment shrinkage bubbles. Our results combined with the Raman data demonstrate that olivine from the early part of the Kīlauea Iki eruption crystallized at <6 km depth, with the majority of olivine in the 1-3 km depth range. These depths are consistent with the interpretation that the Kīlauea Iki magma was supplied from Kīlauea’s summit magma reservoir (∼2-5 km depth). In contrast, olivine from Kapoho, which was the rift zone extension of the Kīlauea Iki eruption, crystallized over a much wider range of depths (∼1-16 km). The wider depth range requires magma transport during the Kapoho eruption from deep beneath the summit region and/or from deep beneath Kīlauea’s east rift zone. The deeply derived olivine crystals and their host magma mixed with stored, more evolved magma in the rift zone, and the mixture was later erupted at Kapoho.

Magma transport and olivine crystallization depths in Kīlauea's east rift zone inferred from experimentally rehomogenized melt inclusions

NASA Astrophysics Data System (ADS)

Tuohy, Robin M.; Wallace, Paul J.; Loewen, Matthew W.; Swanson, Donald A.; Kent, Adam J. R.

2016-07-01

Concentrations of H2O and CO2 in olivine-hosted melt inclusions can be used to estimate crystallization depths for the olivine host. However, the original dissolved CO2 concentration of melt inclusions at the time of trapping can be difficult to measure directly because in many cases substantial CO2 is transferred to shrinkage bubbles that form during post-entrapment cooling and crystallization. To investigate this problem, we heated olivine from the 1959 Kīlauea Iki and 1960 Kapoho (Hawai'i) eruptions in a 1-atm furnace to temperatures above the melt inclusion trapping temperature to redissolve the CO2 in shrinkage bubbles. The measured CO2 concentrations of the experimentally rehomogenized inclusions (⩽590 ppm for Kīlauea Iki [n = 10]; ⩽880 ppm for Kapoho, with one inclusion at 1863 ppm [n = 38]) overlap with values for naturally quenched inclusions from the same samples, but experimentally rehomogenized inclusions have higher within-sample median CO2 values than naturally quenched inclusions, indicating at least partial dissolution of CO2 from the vapor bubble during heating. Comparison of our data with predictions from modeling of vapor bubble formation and published Raman data on the density of CO2 in the vapor bubbles suggests that 55-85% of the dissolved CO2 in the melt inclusions at the time of trapping was lost to post-entrapment shrinkage bubbles. Our results combined with the Raman data demonstrate that olivine from the early part of the Kīlauea Iki eruption crystallized at <6 km depth, with the majority of olivine in the 1-3 km depth range. These depths are consistent with the interpretation that the Kīlauea Iki magma was supplied from Kīlauea's summit magma reservoir (∼2-5 km depth). In contrast, olivine from Kapoho, which was the rift zone extension of the Kīlauea Iki eruption, crystallized over a much wider range of depths (∼1-16 km). The wider depth range requires magma transport during the Kapoho eruption from deep beneath the summit region and/or from deep beneath Kīlauea's east rift zone. The deeply derived olivine crystals and their host magma mixed with stored, more evolved magma in the rift zone, and the mixture was later erupted at Kapoho.

REDOR solid-state NMR as a probe of the membrane locations of membrane-associated peptides and proteins

NASA Astrophysics Data System (ADS)

Jia, Lihui; Liang, Shuang; Sackett, Kelly; Xie, Li; Ghosh, Ujjayini; Weliky, David P.

2015-04-01

Rotational-echo double-resonance (REDOR) solid-state NMR is applied to probe the membrane locations of specific residues of membrane proteins. Couplings are measured between protein 13CO nuclei and membrane lipid or cholesterol 2H and 31P nuclei. Specific 13CO labeling is used to enable unambiguous assignment and 2H labeling covers a small region of the lipid or cholesterol molecule. The 13CO-31P and 13CO-2H REDOR respectively probe proximity to the membrane headgroup region and proximity to specific insertion depths within the membrane hydrocarbon core. One strength of the REDOR approach is use of chemically-native proteins and membrane components. The conventional REDOR pulse sequence with 100 kHz 2H π pulses is robust with respect to the 2H quadrupolar anisotropy. The 2H T1's are comparable to the longer dephasing times (τ's) and this leads to exponential rather than sigmoidal REDOR buildups. The 13CO-2H buildups are well-fitted to A × (1 - e-γτ) where A and γ are fitting parameters that are correlated as the fraction of molecules (A) with effective 13CO-2H coupling d = 3γ/2. The REDOR approach is applied to probe the membrane locations of the "fusion peptide" regions of the HIV gp41 and influenza virus hemagglutinin proteins which both catalyze joining of the viral and host cell membranes during initial infection of the cell. The HIV fusion peptide forms an intermolecular antiparallel β sheet and the REDOR data support major deeply-inserted and minor shallowly-inserted molecular populations. A significant fraction of the influenza fusion peptide molecules form a tight hairpin with antiparallel N- and C-α helices and the REDOR data support a single peptide population with a deeply-inserted N-helix. The shared feature of deep insertion of the β and α fusion peptide structures may be relevant for fusion catalysis via the resultant local perturbation of the membrane bilayer. Future applications of the REDOR approach may include samples that contain cell membrane extracts and use of lower temperatures and dynamic nuclear polarization to reduce data acquisition times.

Turmoil at Turrialba Volcano (Costa Rica): Degassing and eruptive processes inferred from high-frequency gas monitoring.

PubMed

de Moor, J Maarten; Aiuppa, A; Avard, G; Wehrmann, H; Dunbar, N; Muller, C; Tamburello, G; Giudice, G; Liuzzo, M; Moretti, R; Conde, V; Galle, B

2016-08-01

Eruptive activity at Turrialba Volcano (Costa Rica) has escalated significantly since 2014, causing airport and school closures in the capital city of San José. Whether or not new magma is involved in the current unrest seems probable but remains a matter of debate as ash deposits are dominated by hydrothermal material. Here we use high-frequency gas monitoring to track the behavior of the volcano between 2014 and 2015 and to decipher magmatic versus hydrothermal contributions to the eruptions. Pulses of deeply derived CO 2 -rich gas (CO 2 /S total  > 4.5) precede explosive activity, providing a clear precursor to eruptive periods that occurs up to 2 weeks before eruptions, which are accompanied by shallowly derived sulfur-rich magmatic gas emissions. Degassing modeling suggests that the deep magmatic reservoir is ~8-10 km deep, whereas the shallow magmatic gas source is at ~3-5 km. Two cycles of degassing and eruption are observed, each attributed to pulses of magma ascending through the deep reservoir to shallow crustal levels. The magmatic degassing signals were overprinted by a fluid contribution from the shallow hydrothermal system, modifying the gas compositions, contributing volatiles to the emissions, and reflecting complex processes of scrubbing, displacement, and volatilization. H 2 S/SO 2 varies over 2 orders of magnitude through the monitoring period and demonstrates that the first eruptive episode involved hydrothermal gases, whereas the second did not. Massive degassing (>3000 T/d SO 2 and H 2 S/SO 2  > 1) followed, suggesting boiling off of the hydrothermal system. The gas emissions show a remarkable shift to purely magmatic composition (H 2 S/SO 2  < 0.05) during the second eruptive period, reflecting the depletion of the hydrothermal system or the establishment of high-temperature conduits bypassing remnant hydrothermal reservoirs, and the transition from phreatic to phreatomagmatic eruptive activity.

Turmoil at Turrialba Volcano (Costa Rica): Degassing and eruptive processes inferred from high‐frequency gas monitoring

PubMed Central

Aiuppa, A.; Avard, G.; Wehrmann, H.; Dunbar, N.; Muller, C.; Tamburello, G.; Giudice, G.; Liuzzo, M.; Moretti, R.; Conde, V.; Galle, B.

2016-01-01

Abstract Eruptive activity at Turrialba Volcano (Costa Rica) has escalated significantly since 2014, causing airport and school closures in the capital city of San José. Whether or not new magma is involved in the current unrest seems probable but remains a matter of debate as ash deposits are dominated by hydrothermal material. Here we use high‐frequency gas monitoring to track the behavior of the volcano between 2014 and 2015 and to decipher magmatic versus hydrothermal contributions to the eruptions. Pulses of deeply derived CO2‐rich gas (CO2/Stotal > 4.5) precede explosive activity, providing a clear precursor to eruptive periods that occurs up to 2 weeks before eruptions, which are accompanied by shallowly derived sulfur‐rich magmatic gas emissions. Degassing modeling suggests that the deep magmatic reservoir is ~8–10 km deep, whereas the shallow magmatic gas source is at ~3–5 km. Two cycles of degassing and eruption are observed, each attributed to pulses of magma ascending through the deep reservoir to shallow crustal levels. The magmatic degassing signals were overprinted by a fluid contribution from the shallow hydrothermal system, modifying the gas compositions, contributing volatiles to the emissions, and reflecting complex processes of scrubbing, displacement, and volatilization. H2S/SO2 varies over 2 orders of magnitude through the monitoring period and demonstrates that the first eruptive episode involved hydrothermal gases, whereas the second did not. Massive degassing (>3000 T/d SO2 and H2S/SO2 > 1) followed, suggesting boiling off of the hydrothermal system. The gas emissions show a remarkable shift to purely magmatic composition (H2S/SO2 < 0.05) during the second eruptive period, reflecting the depletion of the hydrothermal system or the establishment of high‐temperature conduits bypassing remnant hydrothermal reservoirs, and the transition from phreatic to phreatomagmatic eruptive activity. PMID:27774371

Turmoil at Turrialba Volcano (Costa Rica): Degassing and eruptive processes inferred from high-frequency gas monitoring

NASA Astrophysics Data System (ADS)

de Moor, J. Maarten; Aiuppa, A.; Avard, G.; Wehrmann, H.; Dunbar, N.; Muller, C.; Tamburello, G.; Giudice, G.; Liuzzo, M.; Moretti, R.; Conde, V.; Galle, B.

2016-08-01

Eruptive activity at Turrialba Volcano (Costa Rica) has escalated significantly since 2014, causing airport and school closures in the capital city of San José. Whether or not new magma is involved in the current unrest seems probable but remains a matter of debate as ash deposits are dominated by hydrothermal material. Here we use high-frequency gas monitoring to track the behavior of the volcano between 2014 and 2015 and to decipher magmatic versus hydrothermal contributions to the eruptions. Pulses of deeply derived CO2-rich gas (CO2/Stotal > 4.5) precede explosive activity, providing a clear precursor to eruptive periods that occurs up to 2 weeks before eruptions, which are accompanied by shallowly derived sulfur-rich magmatic gas emissions. Degassing modeling suggests that the deep magmatic reservoir is 8-10 km deep, whereas the shallow magmatic gas source is at 3-5 km. Two cycles of degassing and eruption are observed, each attributed to pulses of magma ascending through the deep reservoir to shallow crustal levels. The magmatic degassing signals were overprinted by a fluid contribution from the shallow hydrothermal system, modifying the gas compositions, contributing volatiles to the emissions, and reflecting complex processes of scrubbing, displacement, and volatilization. H2S/SO2 varies over 2 orders of magnitude through the monitoring period and demonstrates that the first eruptive episode involved hydrothermal gases, whereas the second did not. Massive degassing (>3000 T/d SO2 and H2S/SO2 > 1) followed, suggesting boiling off of the hydrothermal system. The gas emissions show a remarkable shift to purely magmatic composition (H2S/SO2 < 0.05) during the second eruptive period, reflecting the depletion of the hydrothermal system or the establishment of high-temperature conduits bypassing remnant hydrothermal reservoirs, and the transition from phreatic to phreatomagmatic eruptive activity.

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

Guliyev, I.A.; Aliyev, A.A.; Rahmanov, R.R.

Azerbaijan is a classic region for the study of mud volcanism. Of the 700 mud volcanoes known in the world, 220 are in Azerbaijan. These are of great interest, not least in relation to oil and gas exploration since they give information on subsurface sediments beyond the reach of drilling. Mud volcanoes are clearly visible on satellite images. They are confined to structural lineaments and associated fractures. Changes in the morphology of some mud volcanoes post-eruption can be detected from a series of images pre-dating and post-dating eruptions. Mud volcanoes are notable for gradients of temperature that are by anmore » order of magnitude or a factor of 102 greater than the temperature gradients established elsewhere. The gases of mud volcanoes consist mainly of methane (95-100%). There are small amounts of C{sub 2-6}, CO{sub 2}, N{sub 2}, He and Ar. The isotopic composition of carbon (ICC) within the methane varies from -61.29. to -35.W{close_quotes} which is isotopically heavier than the methane from producing fields. The ICC of the CO{sub 2} has a very wide range (from -49.6% to +23.1%), indicating several sources of its formation. The isotopically superheavy CO{sub 2} (+5%) is especially interesting. Oils from mud volcanoes are typically severely biodegraded. Their ICC ranges from -24.76% to -28.2%. A relationship between {partial_derivative}{sup l3}C of oils and ages of accumulations has been established. Waters of mud volcanoes are lightly mineralised, containing chiefly bicarbonates and sodium. The hydrogen composition of the water is abnormally heavy. Ejected rocks from mud volcanoes range in age from Cretaceous - Pliocene. Their study suggests that deeply buried reservoirs maintain good poroperm characteristics because of relatively little catagenesis.« less

Implications of Deep Decarbonization for Carbon Cycle Science

NASA Astrophysics Data System (ADS)

Jones, A. D.; Williams, J.; Torn, M. S.

2016-12-01

The energy-system transformations required to achieve deep decarbonization in the United States, defined as a reduction of greenhouse gas emissions of 80% or more below 1990 levels by 2050, have profound implications for carbon cycle science, particularly with respect to 4 key objectives: understanding and enhancing the terrestrial carbon sink, using bioenergy sustainably, controlling non-CO2 GHGs, and emissions monitoring and verification. (1) As a source of mitigation, the terrestrial carbon sink is pivotal but uncertain, and changes in the expected sink may significantly affect the overall cost of mitigation. Yet the dynamics of the sink under changing climatic conditions, and the potential to protect and enhance the sink through land management, are poorly understood. Policy urgently requires an integrative research program that links basic science knowledge to land management practices. (2) Biomass resources can fill critical energy needs in a deeply decarbonized system, but current understanding of sustainability and lifecycle carbon aspects is limited. Mitigation policy needs better understanding of the sustainable amount, types, and cost of bioenergy feedstocks, their interactions with other land uses, and more efficient and reliable monitoring of embedded carbon. (3) As CO2 emissions from energy decrease under deep decarbonization, the relative share of non-CO2 GHGs grows larger and their mitigation more important. Because the sources tend to be distributed, variable, and uncertain, they have been under-researched. Policy needs a better understanding of mitigation priorities and costs, informed by deeper research in key areas such as fugitive CH4, fertilizer-derived N2O, and industrial F-gases. (4) The M&V challenge under deep decarbonization changes with a steep decrease in the combustion CO2 sources due to widespread electrification, while a greater share of CO2 releases is net-carbon-neutral. Similarly, gas pipelines may carry an increasing share of methane from biogenic or other net carbon-neutral sources. Improved lifecycle analysis will be needed to verify carbon neutrality, while the signal-to-noise challenge for attributing CO2 to fossil or biogenic fuels becomes more challenging.

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

Kawamura, Yoshiyuki

The radiative forcing of the greenhouse gases has been studied being based on computational simulations or the observation of the real atmosphere meteorologically. In order to know the greenhouse effect more deeply and to study it from various viewpoints, the study on it in a laboratory scale is important. We have developed a direct measurement system for the infrared back radiation from the carbon dioxide (CO{sub 2}) gas. The system configuration is similar with that of the practical earth-atmosphere-space system. Using this system, the back radiation from the CO{sub 2} gas was directly measured in a laboratory scale, which roughlymore » coincides with meteorologically predicted value.« less

Aqueous Geochemical Dynamics at the Coast Range Ophiolite Microbial Observatory and The Case for Subsurface Mixing of Regional Groundwaters

NASA Astrophysics Data System (ADS)

Cardace, D.; Schrenk, M. O.; McCollom, T. M.; Hoehler, T. M.

2017-12-01

Serpentinization is the aqueous alteration (or hydration) of olivine and pyroxene minerals in ultramafic rocks, occurring in the seabed and ultramafic units on continents, such as at the Coast Range Ophiolite (CRO) in northern California, USA. Mineral products of serpentinization include serpentine, magnetite, brucite, talc, oxyhydroxides, carbonates, and diverse clay minerals. Such mineral transformations generate extremely high pH solutions with characteristic cation and dissolved metal loads, transmitting CH4, H2, and CO gas mixtures from depth; deep life in ultramafic terrains is thought to be fueled by chemical energy derived from these geochemical reactions. The installation of 8 groundwater monitoring wells in the CRO has allowed frequent monitoring since 2011. Influx of deeply sourced, serpentinization-influenced waters is evidenced by related geochemical shifts (e.g., pH, oxidation-reduction potential), but is apparently mixing with other, regionally important groundwater types. Evaluation salinity loads in concert with other parameters, we model the mixing scenario of this site of ongoing scientific study and experimentation.

Elevated CO{sub 2} and leaf shape: Are dandelions getting toothier?

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

Thomas, S.C.; Bazzaz, F.A.

1996-01-01

Heteroblastic leaf development in Taraxacum officinale is compared between plants grown under ambient (350 ppm) vs. elevated (700 ppm) CO{sub 2} levels. Leaves of elevated CO{sub 2} plants exhibited more deeply incised leaf margins and relatively more slender leaf laminae than leaves of ambient CO{sub 2} plants. These differences were found to be significant in allometric analyses that controlled for differences in leaf size, as well as analyses that controlled for leaf development order. The effects of elevated CO{sub 2} on leaf shape were most pronounced when plants were grown individually, but detectable differences were also found in plants grownmore » at high density. Although less dramatic than in Taraxacum, significant effects of elevated CO{sub 2} on leaf shape were also found in two other weedy rosette species, Plantago major and Rumex crispus. These observations support the long-standing hypothesis that leaf carbohydrate level plays an important role in regulating heteroblastic leaf development, though elevated CO{sub 2} may also affect leaf development through direct hormonal interactions or increased leaf water potential. In Taraxacum, pronounced modifications of leaf shape were found at CO{sub 2} levels predicted to occur within the next century. 33 refs., 5 figs.« less

Carbon Dioxide Emissions Effects of Grid-Scale Electricity Storage in a Decarbonizing Power System

DOE PAGES

Craig, Michael T.; Jaramillo, Paulina; Hodge, Bri-Mathias

2018-01-03

While grid-scale electricity storage (hereafter 'storage') could be crucial for deeply decarbonizing the electric power system, it would increase carbon dioxide (CO 2) emissions in current systems across the United States. To better understand how storage transitions from increasing to decreasing system CO 2 emissions, we quantify the effect of storage on operational CO 2 emissions as a power system decarbonizes under a moderate and strong CO 2 emission reduction target through 2045. Under each target, we compare the effect of storage on CO 2 emissions when storage participates in only energy, only reserve, and energy and reserve markets. Wemore » conduct our study in the Electricity Reliability Council of Texas (ERCOT) system and use a capacity expansion model to forecast generator fleet changes and a unit commitment and economic dispatch model to quantify system CO 2 emissions with and without storage. We find that storage would increase CO 2 emissions in the current ERCOT system, but would decrease CO 2 emissions in 2025 through 2045 under both decarbonization targets. Storage reduces CO 2 emissions primarily by enabling gas-fired generation to displace coal-fired generation, but also by reducing wind and solar curtailment. We further find that the market in which storage participates drives large differences in the magnitude, but not the direction, of the effect of storage on CO 2 emissions.« less

Carbon Dioxide Emissions Effects of Grid-Scale Electricity Storage in a Decarbonizing Power System

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

Craig, Michael T.; Jaramillo, Paulina; Hodge, Bri-Mathias

While grid-scale electricity storage (hereafter 'storage') could be crucial for deeply decarbonizing the electric power system, it would increase carbon dioxide (CO 2) emissions in current systems across the United States. To better understand how storage transitions from increasing to decreasing system CO 2 emissions, we quantify the effect of storage on operational CO 2 emissions as a power system decarbonizes under a moderate and strong CO 2 emission reduction target through 2045. Under each target, we compare the effect of storage on CO 2 emissions when storage participates in only energy, only reserve, and energy and reserve markets. Wemore » conduct our study in the Electricity Reliability Council of Texas (ERCOT) system and use a capacity expansion model to forecast generator fleet changes and a unit commitment and economic dispatch model to quantify system CO 2 emissions with and without storage. We find that storage would increase CO 2 emissions in the current ERCOT system, but would decrease CO 2 emissions in 2025 through 2045 under both decarbonization targets. Storage reduces CO 2 emissions primarily by enabling gas-fired generation to displace coal-fired generation, but also by reducing wind and solar curtailment. We further find that the market in which storage participates drives large differences in the magnitude, but not the direction, of the effect of storage on CO 2 emissions.« less

Carbon dioxide emissions effects of grid-scale electricity storage in a decarbonizing power system

NASA Astrophysics Data System (ADS)

Craig, Michael T.; Jaramillo, Paulina; Hodge, Bri-Mathias

2018-01-01

While grid-scale electricity storage (hereafter ‘storage’) could be crucial for deeply decarbonizing the electric power system, it would increase carbon dioxide (CO2) emissions in current systems across the United States. To better understand how storage transitions from increasing to decreasing system CO2 emissions, we quantify the effect of storage on operational CO2 emissions as a power system decarbonizes under a moderate and strong CO2 emission reduction target through 2045. Under each target, we compare the effect of storage on CO2 emissions when storage participates in only energy, only reserve, and energy and reserve markets. We conduct our study in the Electricity Reliability Council of Texas (ERCOT) system and use a capacity expansion model to forecast generator fleet changes and a unit commitment and economic dispatch model to quantify system CO2 emissions with and without storage. We find that storage would increase CO2 emissions in the current ERCOT system, but would decrease CO2 emissions in 2025 through 2045 under both decarbonization targets. Storage reduces CO2 emissions primarily by enabling gas-fired generation to displace coal-fired generation, but also by reducing wind and solar curtailment. We further find that the market in which storage participates drives large differences in the magnitude, but not the direction, of the effect of storage on CO2 emissions.

Geochemical features of the geothermal fluids from the Mapamyum non-volcanic geothermal system (Western Tibet, China)

NASA Astrophysics Data System (ADS)

Wang, Peng; Chen, Xiaohong; Shen, Licheng; Wu, Kunyu; Huang, Mingzhi; Xiao, Qiong

2016-06-01

Mapamyum geothermal field (MGF) in western Tibet is one of largest geothermal areas characterized by the occurrence of hydrothermal explosions on the Tibetan Plateau. The geochemical properties of hydrothermal water in the MGF system were investigated to trace the origin of the solutes and to determine the equilibrium temperatures of the feeding reservoir. The study results show that the geochemistry of hydrothermal waters in the MGF system is mainly of the Na-HCO3 type. The chemical components of hydrothermal waters are mainly derived from the minerals in the host rocks (e.g., K-feldspar, albite, Ca-montmorillonite, and Mg-montmorillonite). The hydrothermal waters are slightly supersaturated or undersaturated with respect to aragonite, calcite, dolomite, chalcedony and quartz (saturation indices close to 0), but are highly undersaturated with respect to gypsum and anhydrite (saturation indices < 0). Mixing models and Na-K-Mg ternary diagrams show that strong mixing between cold meteoric water and deeply-seated thermal fluids occurred during the upward flowing process. δD and δ18O data confirm that the meteoric water acts as the water source of the geothermal waters. An 220 °C equilibrated reservoir temperature of hydrothermal spring waters was calculated via both the Na-K-Mg ternary diagrams and the cationic chemical geothermometers. The logpCO2 of hydrothermal waters in the MGF system ranges from - 2.59 to - 0.57 and δ13C of the total dissolved inorganic carbon ranges from - 5.53‰ to - 0.94‰, suggesting that the carrier CO2 in hydrothermal water are mainly of a magmatic or metamorphic CO2 origin.

Supercritical CO2 uptake by nonswelling phyllosilicates

PubMed Central

Tokunaga, Tetsu K.; Ashby, Paul D.; Kim, Yongman; Voltolini, Marco; Gilbert, Benjamin; DePaolo, Donald J.

2018-01-01

Interactions between supercritical (sc) CO2 and minerals are important when CO2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO2), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO2, can increase CO2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO2 uptake constitutes a previously unrecognized potential trapping mechanism. PMID:29339499

Supercritical CO2 uptake by nonswelling phyllosilicates.

PubMed

Wan, Jiamin; Tokunaga, Tetsu K; Ashby, Paul D; Kim, Yongman; Voltolini, Marco; Gilbert, Benjamin; DePaolo, Donald J

2018-01-30

Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2 , can increase CO 2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism. Copyright © 2018 the Author(s). Published by PNAS.

Supercritical CO 2 uptake by nonswelling phyllosilicates

DOE PAGES

Wan, Jiamin; Tokunaga, Tetsu K.; Ashby, Paul D.; ...

2018-01-16

Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubationmore » with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2, can increase CO 2 storage capacity by up to ~30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism.« less

Experimental determination of dissolved CO2 content in nominally anhydrous andesitic melts at graphite/diamond saturation - Remobilization of deeply subducted reduced carbon via partial melts of MORB-like eclogite

NASA Astrophysics Data System (ADS)

Eguchi, J.; Dasgupta, R.

2015-12-01

Experimental phase relations of carbonated lithologies [1] and geochemistry of deep diamonds [2] suggest that deep recycling of carbon has likely been efficient for a significant portion of Earth's history. Both carbonates and organic carbon subduct into the mantle, but with gradual decrease of fO2 with depth [3] most carbon in deep mantle rocks including eclogite could be diamond/graphite [4]. Previous studies investigated the transfer of CO2 from subducted eclogite to the ambient mantle by partial melting in the presence of carbonates, i.e., by generation of carbonate-rich melts [5]. However, the transfer of carbon from subducted eclogite to the mantle can also happen, perhaps more commonly, by extraction of silicate partial melt in the presence of reduced carbon; yet, CO2 solubility in eclogite-derived andesitic melt at graphite/diamond saturation remains unconstrained. CO2content of eclogite melts is also critical as geochemistry of many ocean island basalts suggest the presence of C and eclogite in their source regions [6]. In the present study we determine CO2 concentration in a model andesitic melt [7] at graphite/diamond saturation at conditions relevant for partial melting of eclogite in the convecting upper mantle. Piston cylinder and multi anvil experiments were conducted at 1-6 GPa and 1375-1550 °C using Pt/Gr double capsules. Oxygen fugacity was monitored with Pt-Fe sensors in the starting mix. Completed experiments at 1-3 GPa show that CO2 concentration increases with increasing P, T, and fO2 up to ~0.3 wt%. Results were used to develop empirical and thermodynamic models to predict CO2 concentration in partial melts of graphite saturated eclogite. This allowed us to quantify the extent to which CO2 can mobilize from eclogitic heterogeneities at graphite/diamond saturated conditions. With estimates of eclogite contribution to erupted basaltic lavas, the models developed here allow us to put constraints on the flux of CO2 to mantle source regions coming from subducted crust and investigate the possible role this process may play in the deep carbon cycle. [1] Dasgupta (2013) RiMG. [2] Shirey, et al. (2013) RiMG. [3] Frost & McCammon (2008) Ann Rev Earth Plan Sci. [4] Stagno, et al. (2015) CMP. [5] Kiseeva, et al. (2012) JPet. [6] Mallik & Dasgupta (2014) G3. [7] Spandler, et al. (2008) JPet.

Impacts of elevated atmospheric CO2 on nutrient content of important food crops

NASA Astrophysics Data System (ADS)

Dietterich, Lee H.; Zanobetti, Antonella; Kloog, Itai; Huybers, Peter; Leakey, Andrew D. B.; Bloom, Arnold J.; Carlisle, Eli; Fernando, Nimesha; Fitzgerald, Glenn; Hasegawa, Toshihiro; Holbrook, N. Michele; Nelson, Randall L.; Norton, Robert; Ottman, Michael J.; Raboy, Victor; Sakai, Hidemitsu; Sartor, Karla A.; Schwartz, Joel; Seneweera, Saman; Usui, Yasuhiro; Yoshinaga, Satoshi; Myers, Samuel S.

2015-07-01

One of the many ways that climate change may affect human health is by altering the nutrient content of food crops. However, previous attempts to study the effects of increased atmospheric CO2 on crop nutrition have been limited by small sample sizes and/or artificial growing conditions. Here we present data from a meta-analysis of the nutritional contents of the edible portions of 41 cultivars of six major crop species grown using free-air CO2 enrichment (FACE) technology to expose crops to ambient and elevated CO2 concentrations in otherwise normal field cultivation conditions. This data, collected across three continents, represents over ten times more data on the nutrient content of crops grown in FACE experiments than was previously available. We expect it to be deeply useful to future studies, such as efforts to understand the impacts of elevated atmospheric CO2 on crop macro- and micronutrient concentrations, or attempts to alleviate harmful effects of these changes for the billions of people who depend on these crops for essential nutrients.

Impacts of elevated atmospheric CO2 on nutrient content of important food crops

PubMed Central

Dietterich, Lee H.; Zanobetti, Antonella; Kloog, Itai; Huybers, Peter; Leakey, Andrew D. B.; Bloom, Arnold J.; Carlisle, Eli; Fernando, Nimesha; Fitzgerald, Glenn; Hasegawa, Toshihiro; Holbrook, N. Michele; Nelson, Randall L.; Norton, Robert; Ottman, Michael J.; Raboy, Victor; Sakai, Hidemitsu; Sartor, Karla A.; Schwartz, Joel; Seneweera, Saman; Usui, Yasuhiro; Yoshinaga, Satoshi; Myers, Samuel S.

2015-01-01

One of the many ways that climate change may affect human health is by altering the nutrient content of food crops. However, previous attempts to study the effects of increased atmospheric CO2 on crop nutrition have been limited by small sample sizes and/or artificial growing conditions. Here we present data from a meta-analysis of the nutritional contents of the edible portions of 41 cultivars of six major crop species grown using free-air CO2 enrichment (FACE) technology to expose crops to ambient and elevated CO2 concentrations in otherwise normal field cultivation conditions. This data, collected across three continents, represents over ten times more data on the nutrient content of crops grown in FACE experiments than was previously available. We expect it to be deeply useful to future studies, such as efforts to understand the impacts of elevated atmospheric CO2 on crop macro- and micronutrient concentrations, or attempts to alleviate harmful effects of these changes for the billions of people who depend on these crops for essential nutrients. PMID:26217490

The Impact of Online Faculty Characteristics on Student Satisfaction via the Community of Inquiry Framework

ERIC Educational Resources Information Center

Patrizi, Larry A.

2010-01-01

This study examined the relationship between student satisfaction with faculty characteristics via the community of inquiry (CoI) framework. The CoI framework includes cognitive presence, social presence, and teaching presence. Subsets of teaching presence were explored more deeply by including subsets facilitation of discourse and direct…

Note: Measurement system for the radiative forcing of greenhouse gases in a laboratory scale.

PubMed

Kawamura, Yoshiyuki

2016-01-01

The radiative forcing of the greenhouse gases has been studied being based on computational simulations or the observation of the real atmosphere meteorologically. In order to know the greenhouse effect more deeply and to study it from various viewpoints, the study on it in a laboratory scale is important. We have developed a direct measurement system for the infrared back radiation from the carbon dioxide (CO2) gas. The system configuration is similar with that of the practical earth-atmosphere-space system. Using this system, the back radiation from the CO2 gas was directly measured in a laboratory scale, which roughly coincides with meteorologically predicted value.

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

Wan, Jiamin; Tokunaga, Tetsu K.; Ashby, Paul D.

Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubationmore » with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2, can increase CO 2 storage capacity by up to ~30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism.« less

Thickness-, Composition-, and Magnetic-Field-Dependent Complex Impedance Spectroscopy of Granular-Type-Barrier Co/Co-Al2O3/Co MTJs

NASA Astrophysics Data System (ADS)

Tuan, Nguyen Anh; Anh, Nguyen Tuan; Nga, Nguyen Tuyet; Tue, Nguyen Anh; Van Cuong, Giap

2016-06-01

The alternating-current (ac) electrical properties of granular-type-barrier magnetic tunnel junctions (GBMTJs) based on Co/Co x (Al2O3)1- x ( t)/Co trilayer structures have been studied using complex impedance spectroscopy (CIS). Their CIS characteristics were investigated in external magnetic fields varying from 0 kOe to 3 kOe as a function of Co composition x at 10 at.%, 25 at.%, and 35 at.%, with barrier layer thickness t of 20 nm to 90 nm. The influence of these factors on the behaviors of the ac impedance response of the GBMTJs was deeply investigated and attributed to the dielectric or conducting nature of the Co-Al2O3 barrier layer. The most remarkable typical phenomena observed in these behaviors, even appearing paradoxical, include lower impedance for thicker t for each given x, a declining trend of Z with increasing x, a clear decrease of Z with H, and especially a partition of Z into zones according to the H value. All these effects are analyzed and discussed to demonstrate that diffusion-type and mass-transfer-type phenomena can be inferred from processes such as spin tunneling and Coulomb or spin blockade in the Co-Al2O3 barrier layer.

Colorimetric detection of copper ions in sub-micromolar concentrations using a triarylamine-linked resin bead.

PubMed

Thomas, Tony George; Sreenath, Kesavapillai; Gopidas, Karical R

2012-11-21

The triarylamine derivative ETPA reacts with Cu(2+) to give deeply colored, stable radical cations in acetonitrile solution. ETPA was immobilized on to a tentagel resin bead which was then used for the fabrication of a simple device capable of the colorimetric detection of submicromolar concentrations of Cu(2+) ions in water. The naked eye detection limit reported here for Cu(2+) is one of the lowest ever reported for small molecule sensors.

Crossing Boundaries: Co-Op Students Relearning to Write

ERIC Educational Resources Information Center

Brent, Doug

2012-01-01

This article reviews the deeply conflicted literature on learning transfer, especially as it applies to rhetorical knowledge and skill. It then describes a study in which six students are followed through their first co-op work term to learn about which resources they draw on as they enter a new environment of professional writing. It suggests…

CO2 outburst events in relation to seismicity: Constraints from microscale geochronology, geochemistry of late Quaternary vein carbonates, SW Turkey

NASA Astrophysics Data System (ADS)

Ünal-İmer, Ezgi; Uysal, I. Tonguç; Zhao, Jian-Xin; Işık, Veysel; Shulmeister, James; İmer, Ali; Feng, Yue-Xing

2016-08-01

Vein and breccia carbonates precipitated in a highly fractured/faulted carbonate bedrock in SW Turkey were investigated through high-resolution U-series geochronology, microstructural and geochemical studies including C-O-Sr isotope and rare-earth element and yttrium (REY) analyses. Petrographical observations and geochronological data are interpreted as evidence that the calcite veins formed through a crack-seal mechanism, mostly accompanied/initiated by intensive hydraulic fracturing of the host limestone in response to high-pressure fluids, which is manifested by multi-stage breccia deposits. Microscale U-series dates (272.6-20.5 kyr) and geochemical compositions of the vein/breccia samples provide information on the timing and mechanism of the vein formation and identify the source of CO2-bearing fluids responsible for the carbonate precipitation. δ18OVPDB and δ13CVPDB values of the calcite veins range between -5.9 and -1.7‰, and -10.6 and -4.6‰, respectively. The isotopic compositions of the veins show highly fluctuating values as calcite grew successively perpendicular to vein walls, which, in combination with microstructural and geochronological constraints, are interpreted to reflect episodic CO2 degassing events associated with seismic and aseismic deformation. Oxygen and Sr isotope compositions (δ18OVPDB: -5.9 to -1.7‰; 87Sr/86Sr: 0.7082 to 0.7085) together with REY concentrations indicate deep infiltration of meteoric waters with various degrees of interactions mostly with the host limestone and siliciclastic parts of the basement rocks. Oxygen and carbon isotope compositions suggest CO2 degassing through intensive limestone dissolution. While majority of the veins display similar Post-Archaean Australian Shale (PAAS)-normalised REY variations, some of the veins show positive EuPAAS anomalies, which could be indicative of contributions from a deeply derived, heated, and reduced fluid component, giving rise to multiple fluid sources for the calcite veins. Vein calcite formed in fault-induced fractures offers insights into structural features, genetic characterisation of the parental fluids, and late Quaternary degassing of subsurface CO2 accumulations.

Structural Insight into Methyl-Coenzyme M Reductase Chemistry using Coenzyme B Analogues†,‡

PubMed Central

Cedervall, Peder E.; Dey, Mishtu; Pearson, Arwen R.; Ragsdale, Stephen W.; Wilmot, Carrie M.

2011-01-01

Methyl-coenzyme M reductase (MCR) catalyzes the final and rate-limiting step in methane biogenesis; the reduction of methyl-coenzyme M (methyl-SCoM) by coenzyme B (CoBSH) to methane and a heterodisulfide (CoBS-SCoM). Crystallographic studies show that the active site is deeply buried within the enzyme, and contains a highly reduced nickel-tetrapyrrole, coenzyme F430. Methyl-SCoM must enter the active site prior to CoBSH, as species derived from analogues of methyl-SCoM are always observed bound to the F430 nickel in the deepest part of the 30 Å long substrate channel that leads from the protein surface to the active site. The seven-carbon mercaptoalkanoyl chain of CoBSH binds within a 16 Å predominantly hydrophobic part of the channel close to F430, with the CoBSH thiolate lying closest to the nickel at a distance of 8.8 Å. It has previously been suggested that binding of CoBSH initiates catalysis by inducing a conformational change that moves methyl-SCoM closer to the nickel promoting cleavage of the C-S bond of methyl-SCoM. In order to better understand the structural role of CoBSH early in the MCR mechanism, we have determined crystal structures of MCR in complex with four different CoBSH analogues; pentanoyl-, hexanoyl-, octanoyl- and nonanoyl- derivatives of CoBSH (CoB5SH, CoB6SH, CoB8SH and CoB9SH respectively). The data presented here reveal that the shorter CoB5SH mercaptoalkanoyl chain overlays with that of CoBSH, but terminates two units short of the CoBSH thiolate position. In contrast, the mercaptoalkanoyl chain of CoB6SH adopts a different conformation, such that its thiolate is coincident with the position of the CoBSH thiolate. This is consistent with the observation that CoB6SH is a slow substrate. A labile water in the substrate channel was found to be a sensitive indicator for the presence of CoBSH and HSCoM. The longer CoB8SH and CoB9SH analogues can be accommodated in the active site through exclusion of this water. These analogues react with Ni(III)-methyl; a proposed MCR catalytic intermediate of methanogenesis. The CoB8SH thiolate is 2.6 Å closer to the nickel than that of CoBSH, but the additional carbon of CoB9SH only decreases the nickel thiolate distance a further 0.3 Å. Although the analogues did not induce any structural changes in the substrate channel, the thiolates appeared to preferentially bind at two distinct positions in the channel; one being the previously observed CoBSH thiolate position, and the other being at a hydrophobic annulus of residues that lines the channel proximal to the nickel. PMID:20707311

Impacts of elevated atmospheric CO₂ on nutrient content of important food crops.

PubMed

Dietterich, Lee H; Zanobetti, Antonella; Kloog, Itai; Huybers, Peter; Leakey, Andrew D B; Bloom, Arnold J; Carlisle, Eli; Fernando, Nimesha; Fitzgerald, Glenn; Hasegawa, Toshihiro; Holbrook, N Michele; Nelson, Randall L; Norton, Robert; Ottman, Michael J; Raboy, Victor; Sakai, Hidemitsu; Sartor, Karla A; Schwartz, Joel; Seneweera, Saman; Usui, Yasuhiro; Yoshinaga, Satoshi; Myers, Samuel S

2015-01-01

One of the many ways that climate change may affect human health is by altering the nutrient content of food crops. However, previous attempts to study the effects of increased atmospheric CO2 on crop nutrition have been limited by small sample sizes and/or artificial growing conditions. Here we present data from a meta-analysis of the nutritional contents of the edible portions of 41 cultivars of six major crop species grown using free-air CO2 enrichment (FACE) technology to expose crops to ambient and elevated CO2 concentrations in otherwise normal field cultivation conditions. This data, collected across three continents, represents over ten times more data on the nutrient content of crops grown in FACE experiments than was previously available. We expect it to be deeply useful to future studies, such as efforts to understand the impacts of elevated atmospheric CO2 on crop macro- and micronutrient concentrations, or attempts to alleviate harmful effects of these changes for the billions of people who depend on these crops for essential nutrients.

Ferredoxin:thioredoxin reductase (FTR) links the regulation of oxygenic photosynthesis to deeply rooted bacteria.

PubMed

Balsera, Monica; Uberegui, Estefania; Susanti, Dwi; Schmitz, Ruth A; Mukhopadhyay, Biswarup; Schürmann, Peter; Buchanan, Bob B

2013-02-01

Uncovered in studies on photosynthesis 35 years ago, redox regulation has been extended to all types of living cells. We understand a great deal about the occurrence, function, and mechanism of action of this mode of regulation, but we know little about its origin and its evolution. To help fill this gap, we have taken advantage of available genome sequences that make it possible to trace the phylogenetic roots of members of the system that was originally described for chloroplasts-ferredoxin, ferredoxin:thioredoxin reductase (FTR), and thioredoxin as well as target enzymes. The results suggest that: (1) the catalytic subunit, FTRc, originated in deeply rooted microaerophilic, chemoautotrophic bacteria where it appears to function in regulating CO(2) fixation by the reverse citric acid cycle; (2) FTRc was incorporated into oxygenic photosynthetic organisms without significant structural change except for addition of a variable subunit (FTRv) seemingly to protect the Fe-S cluster against oxygen; (3) new Trxs and target enzymes were systematically added as evolution proceeded from bacteria through the different types of oxygenic photosynthetic organisms; (4) an oxygenic type of regulation preceded classical light-dark regulation in the regulation of enzymes of CO(2) fixation by the Calvin-Benson cycle; (5) FTR is not universally present in oxygenic photosynthetic organisms, and in certain early representatives is seemingly functionally replaced by NADP-thioredoxin reductase; and (6) FTRc underwent structural diversification to meet the ecological needs of a variety of bacteria and archaea.

Coastal and Submesoscale Process Studies for ASIRI and Data Serving for ASIRI Participants

DTIC Science & Technology

2014-09-30

spatial distributions of Chlorophyll fluorescence, colored dissolved organic matter (CDOM), and apparent oxygen utilization (AOU). It is evident that...Vertical section of tem perature (left) and salinity (right) w ith density in black contours, from 4 long tracks surveyed in Leg 2 (N ovem ber 2013) from...vertical derivative of the downwelling light is proportional to the radiant heating rate at depth. This figure shows that deeply penetrating blue

Microbial acetogenesis as a source of organic acids in ancient Atlantic Coastal Plain sediments

USGS Publications Warehouse

Chapelle, F.H.; Bradley, P.M.

1996-01-01

Field and laboratory evidence shows that deeply buried (90-888 m) fine-grained sediments of the Atlantic Coastal Plain contain viable acetogenic microorganisms, and that these microorganisms actively produce organic acids. Concentrations of formate, acetate, and propionate in pore waters extracted from fine-grained sediments ranged from 50 ??M to 5 mM and were much higher than in adjacent pore waters associated with sandy sediments (<2 ??M). Laboratory studies showed that asceptically cored fine-grained sediments incubated under a H2 atmosphere produced formate and acetate, and that H14CO-3 was converted to 14C-acetate and 14C-formate over time. An enrichment culture of these acetogenic microorganisms was recovered from one long-term incubation that showed the presence of several morphologically distinct gram-positive, rod-shaped bacteria. These microorganisms were capable of growth under autotrophic (H2 + CO2), heterotrophic (syringate), and mixotrophic (H2 + CO2 + syringate) conditions. These results suggest that microbial acetogenesis, rather than abiotic processes, is the most important organic acid-producing mechanism during low-temperature (???30 ??C) diagenesis of Atlantic Coastal Plain sediments.

The HVT technique and the 'uncertainty' relation for central potentials

NASA Astrophysics Data System (ADS)

Grypeos, M. E.; Koutroulos, C. G.; Oyewumi, K. J.; Petridou, Th

2004-08-01

The quantum mechanical hypervirial theorems (HVT) technique is used to treat the so-called 'uncertainty' relation for quite a general class of central potential wells, including the (reduced) Poeschl-Teller and the Gaussian one. It is shown that this technique is quite suitable in deriving an approximate analytic expression in the form of a truncated power series expansion for the dimensionless product Pnl equiv langr2rangnllangp2rangnl/planck2, for every (deeply) bound state of a particle moving non-relativistically in the well, provided that a (dimensionless) parameter s is sufficiently small. Attention is also paid to a number of cases, among the limited existing ones, in which exact analytic or semi-analytic expressions for Pnl can be derived. Finally, numerical results are given and discussed.

CO2 conversion in non-thermal plasma and plasma/g-C3N4 catalyst hybrid processes

NASA Astrophysics Data System (ADS)

Lu, Na; Sun, Danfeng; Zhang, Chuke; Jiang, Nan; Shang, Kefeng; Bao, Xiaoding; Li, Jie; Wu, Yan

2018-03-01

Carbon dioxide conversion at atmosphere pressure and low temperature has been studied in a cylindrical dielectric barrier discharge (DBD) reactor. Pure CO2 feed flows to the discharge zone and typical filamentary discharges were obtained in each half-cycle of the applied voltage. The gas temperature increased with discharge time and discharge power, which was found to affect the CO2 decomposition deeply. As the DBD reactor was cooled to ambient temperature, both the conversion of CO2 and the CO yield were enhanced. Especially the energy efficiencies changed slightly with the increase of discharge power and were much higher in cooling condition comparing to those without cooling. At a discharge power of 40 W, the energy efficiency under cooling condition was approximately six times more than that without cooling. Gas flow rate was observed to affect CO2 conversion and 0.1 L min-1 was obtained as optimum gas flow rate under cooling condition. In addition, the CO2 conversion rate in plasma/g-C3N4 catalyst hybrid system was twice times as that in plasma-alone system. In case of cooling, the existence of g-C3N4 catalyst contributed to a 47% increase of CO2 conversion compared to the sole plasma process. The maximum energy-efficiency with g-C3N4 was 0.26 mmol kJ-1 at 20 W, which increased by 157% compared to that without g-C3N4. The synergistic effect of DBD plasma with g-C3N4 on pure CO2 conversion was verified.

C-13/C-12 of atmospheric CO2 in the Amazon basin - Forest and river sources

NASA Technical Reports Server (NTRS)

Quay, Paul; King, Stagg; Wilbur, Dave; Richey, Jeffrey; Wofsy, Steven

1989-01-01

Results are presented of measurements of the CO2 concentrations and C-13/C-12 ratios in CO2 in air samples collected from within the Amazonian rain forest and over the Amazon river between 1982 and 1987. Results indicate the presence of a diurnal cycle in the CO2 concentration and the C-13/C-12 ratio. It was found that the CO2 input to air in the forest was derived from the soil respiration, and the CO2 input to air over the Amazon river was derived from the degassing of CO2 from the river. It was also found that plants growing at heights lower than 7 m assimilate soil-derived CO2 with a low C-13/C-12 ratio.

Covariation of deep Southern Ocean oxygenation and atmospheric CO2 through the last ice age.

PubMed

Jaccard, Samuel L; Galbraith, Eric D; Martínez-García, Alfredo; Anderson, Robert F

2016-02-11

No single mechanism can account for the full amplitude of past atmospheric carbon dioxide (CO2) concentration variability over glacial-interglacial cycles. A build-up of carbon in the deep ocean has been shown to have occurred during the Last Glacial Maximum. However, the mechanisms responsible for the release of the deeply sequestered carbon to the atmosphere at deglaciation, and the relative importance of deep ocean sequestration in regulating millennial-timescale variations in atmospheric CO2 concentration before the Last Glacial Maximum, have remained unclear. Here we present sedimentary redox-sensitive trace-metal records from the Antarctic Zone of the Southern Ocean that provide a reconstruction of transient changes in deep ocean oxygenation and, by inference, respired carbon storage throughout the last glacial cycle. Our data suggest that respired carbon was removed from the abyssal Southern Ocean during the Northern Hemisphere cold phases of the deglaciation, when atmospheric CO2 concentration increased rapidly, reflecting--at least in part--a combination of dwindling iron fertilization by dust and enhanced deep ocean ventilation. Furthermore, our records show that the observed covariation between atmospheric CO2 concentration and abyssal Southern Ocean oxygenation was maintained throughout most of the past 80,000 years. This suggests that on millennial timescales deep ocean circulation and iron fertilization in the Southern Ocean played a consistent role in modifying atmospheric CO2 concentration.

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

Dooley, James J.

Shaffer’s (2010) article reports on the long term impact of less than perfect retention of anthropogenic CO2 stored in deep geologic reservoirs and in the ocean. The central thesis of this article is predicated on two deeply flawed assumptions. The first and most glaring is the implicit assumption that society has only one means of reducing greenhouse gas emissions, carbon dioxide capture and storage (CCS). Secondly, there is absolutely no geophysical nor geomechanical basis for assuming an exponential decay of CO2 stored in deep geologic formations as done by Schaffer. Shaffer’s analysis of the impact of leakage from anthropogenic CO2more » stored in deep geologic reservoirs are based upon two fundamentally flawed assumptions and therefore the reported results as well as the public policy conclusions presented in the paper need to be read with this understanding in mind as far less CO2 stored below ground because society drew upon a broad portfolio of advanced energy technologies over the coming century coupled with a more technically accurate conceptualization of CO2 storage in the deep subsurface and the important role of secondary and tertiary trapping mechanisms would have yield a far less pessimistic view of the potential role that CCS can play in a broader portfolio of societal responses to the very serious threat posed by climate change.« less

Synthesis of octahedral like Cu-BTC derivatives derived from MOF calcined under different atmosphere for application in CO oxidation

NASA Astrophysics Data System (ADS)

Yang, Yiqiong; Dong, Han; Wang, Yin; He, Chi; Wang, Yuxin; Zhang, Xiaodong

2018-02-01

A series of octahedral structure Cu-BTC derivatives were successfully achieved through direct calcination of copper based metal organic framework Cu-BTC under different atmosphere (CO reaction gas, oxidizing gas O2, reducing gas H2, inert gas Ar). The Cu-BTC derivatives were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), laser Raman spectroscopy (LRS), N2 adsorption-desorption isotherm, element analysis, H2-temperature program reduction (H2-TPR) and X-ray photoelectron spectroscopic (XPS). It is found that Cu-BTC derivative derived from MOF calcined under reaction gas/O2 (Cu-BTC-CO/Cu-BTC-O) only retain Cu2O and CuO species. In addition, a weak Cu-BTC structure and Cu particles were observed on Cu-BTC derivative derived from MOF calcined under H2 (Cu-BTC-H). Obviously differently, Cu-BTC derivative derived from MOF calcined under Ar (Cu-BTC-Ar) still retains good MOF structure. The catalytic performance for CO oxidation over Cu-BTC derivatives was studied. It was found that Cu-BTC-CO showed a smaller specific surface area (8.0 m2/g), but presented an excellent catalytic performance, long-term stability and cycling stability with a complete CO conversion temperature (T100) of 140 °C, which was ascribed to the higher Cu2O/CuO ratio, good low temperature reduction behavior and a high quantity of surface active oxygen species.

Microbial association with the dynamics of particulate organic carbon in response to the amendment of elevated CO2-derived wheat residue into a Mollisol.

PubMed

Wang, Yanhong; Yu, Zhenhua; Li, Yansheng; Wang, Guanghua; Liu, Junjie; Liu, Judong; Liu, Xiaobing; Jin, Jian

2017-12-31

As the chemical quality of crop residue is likely to be affected by elevated CO 2 (eCO 2 ), residue amendments may influence soil organic carbon (SOC) sequestration. However, in Mollisols, the dynamics of the SOC fractions in response to amendment with wheat residue produced under eCO 2 and the corresponding microbial community composition remain unknown. Such investigation is essential to residue management, which affects the soil quality and productivity of future farming systems. To narrow this knowledge gap, 13 C-labeled shoot and root residue derived from ambient CO 2 (aCO 2 ) or eCO 2 were amended into Mollisols and incubated for 200days. The soil was sampled during the incubation period to determine the residue-C retained in the three SOC fractions, i.e., coarse intra-aggregate particulate organic C (coarse iPOC), fine iPOC and mineral-associated organic C (MOC). The soil bacterial community was assessed using a MiSeq sequencing instrument. The results showed that the increase in SOC concentrations attributable to the application of the wheat residue primarily occurred in the coarse iPOC fraction. Compared with the aCO 2 -derived shoot residue, the amendment of eCO 2 -derived shoot residue resulted in greater SOC concentrations, whereas no significant differences (P>0.05) were observed between the aCO 2 - and eCO 2 -derived roots. Principal coordinates analysis (PCoA) showed that the residue amendment significantly (P≤0.05) altered the bacterial community composition compared with the non-residue amendment. Additionally, the bacterial community in the aCO 2 -derived shoot treatment differed from those in the other residue treatments until day 200 of the incubation period. The eCO 2 -derived shoot treatment significantly increased (P≤0.05) the relative abundances of the genera Acidobacteriaceae_(Subgroup_1)_uncultured, Bryobacter, Candidatus_Solibacter, Gemmatimonas and Nitrosomonadaceae_uncultured, whereas the opposite trend was observed in Nonomuraea, Actinomadura, Streptomyces and Arthrobacter (P≤0.05). These results imply that the response of the microbial community to the eCO 2 -derived shoot treatment is associated with its contribution to the POC fractions. Copyright © 2017 Elsevier B.V. All rights reserved.

Mantle to Surface Fluid Transfer Above a Flat Slab Subduction Zone: Isotopic Evidence from Hot Springs in the Cordillera Blanca, Peru

NASA Astrophysics Data System (ADS)

Newell, D. L.; Jessup, M. J.; Hilton, D. R.; Shaw, C. A.; Hughes, C. A.

2015-12-01

Thermal springs in the Cordillera Blanca, Peru, provide geochemical evidence for deeply circulated hydrothermal fluids that carry significant mantle-derived helium. The Cordillera Blanca is a ~200 km-long NNW-SSE trending mountain range in the Peruvian Andes located above an amagmatic flat-slab subduction segment. The west side of the range is bounded by the Cordillera Blanca detachment that preserves a progression of top to the west ductile shear to brittle normal faulting since ~5 Ma. We report aqueous and stable isotope geochemical results from fluid and gas samples collected in 2013 and 2015 from 13 hot springs emanating from the Cordillera Blanca detachment and associated hanging wall faults. Most springs are vigorously bubbling (degassing), and range in temperature, pH, and conductivity from 17-89 °C, 5.95-8.87, and 0.17-21.5 mS, respectively. The hottest springs issue directly from the northern segment of the detachment. Geochemically, springs are CO2-rich, alkaline-chloride to alkaline-carbonate waters, with elevated trace metal contents including Fe, Cu, As, Zn, Sb, and Tl. Notably, As contents are ≤11 ppm, indicating that thermal waters may be adversely impacting local water quality. Water δ18O and δD, trends in elemental chemistry, and cation geothermometry collectively demonstrate mixing of hot (200-260 °C) saline fluid with cold meteoric recharge along the fault. Helium isotope ratios (3He/4He) for dissolved gases in the hot springs range from 0.62 to 1.98 RC/RA, indicating the presence of ~25% mantle-derived helium, assuming mixing of an asthenospheric end-member with the crustal helium reservoir. CO2/3He and carbon stable isotope ratios indicate a carbon source derived from mixing of crustal sources with minor mantle carbon. Overall, the volatile signature overlaps with orogen-wide datasets where crustal overprinting has modified mantle contributions at active arc volcanoes. Given the long duration since active magmatism in the Cordillera Blanca region, we suggest that mantle helium was mobilized from the continental mantle-lithosphere by metasomatic fluids derived from slab dehydration. These spring data thus reveal a mantle to surface connection and highlight the role of detachment faults in compressional orogens for fluid transfer in the crust.

High-Performance Sodium Metal Anodes Enabled by a Bifunctional Potassium Salt.

PubMed

Shi, Qiuwei; Zhong, Yiren; Wu, Min; Wang, Hongzhi; Wang, Hailiang

2018-04-12

Developing Na metal anodes that can be deeply cycled with high efficiency for a long time is a prerequisite for rechargeable Na metal batteries to be practically useful despite their notable advantages in theoretical energy density and potential low cost. Their high chemical reactivity with the electrolyte and tendency for dendrite formation are two major issues limiting the reversibility of Na metal electrodes. In this work, we introduce for the first time potassium bis(trifluoromethylsulfonyl)imide (KTFSI) as a bifunctional electrolyte additive to stabilize Na metal electrodes, in which the TFSI - anions decompose into lithium nitride and oxynitrides to render a desirable solid electrolyte interphase layer while the K + cations preferentially adsorb onto Na protrusions and provide electrostatic shielding to suppress dendritic deposition. Through the cooperation of the cations and anions, we have realized Na metal electrodes that can be deeply cycled at a capacity of 10 mAh cm -2 for hundreds of hours. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spirituality, Religion, and Peace Education

ERIC Educational Resources Information Center

Brantmeier, Edward J., Ed.; Lin, Jing, Ed.; Miller, John P., Ed.

2010-01-01

"Spirituality, Religion, and Peace Education" attempts to deeply explore the universal and particular dimensions of education for inner and communal peace. This co-edited book contains fifteen chapters on world spiritual traditions, religions, and their connections and relevance to peacebuilding and peacemaking. This book examines the…

A Novel Hand-Held Optical Imager with Real-Time Co-registration Facilities toward Diagnostic Mammography

DTIC Science & Technology

2010-01-01

hence not differentiable from the background. A multilocation scanning ap- proach is currently developed in our laboratory for differentiating deeply...after subtracting the excitation back- ground signal. On applying our multilocation scanning approach, the targets were differentiable under

A Deeply Branching Thermophilic Bacterium with an Ancient Acetyl-CoA Pathway Dominates a Subsurface Ecosystem

PubMed Central

Takami, Hideto; Noguchi, Hideki; Takaki, Yoshihiro; Uchiyama, Ikuo; Toyoda, Atsushi; Nishi, Shinro; Chee, Gab-Joo; Arai, Wataru; Nunoura, Takuro; Itoh, Takehiko; Hattori, Masahira; Takai, Ken

2012-01-01

A nearly complete genome sequence of Candidatus ‘Acetothermum autotrophicum’, a presently uncultivated bacterium in candidate division OP1, was revealed by metagenomic analysis of a subsurface thermophilic microbial mat community. Phylogenetic analysis based on the concatenated sequences of proteins common among 367 prokaryotes suggests that Ca. ‘A. autotrophicum’ is one of the earliest diverging bacterial lineages. It possesses a folate-dependent Wood-Ljungdahl (acetyl-CoA) pathway of CO2 fixation, is predicted to have an acetogenic lifestyle, and possesses the newly discovered archaeal-autotrophic type of bifunctional fructose 1,6-bisphosphate aldolase/phosphatase. A phylogenetic analysis of the core gene cluster of the acethyl-CoA pathway, shared by acetogens, methanogens, some sulfur- and iron-reducers and dechlorinators, supports the hypothesis that the core gene cluster of Ca. ‘A. autotrophicum’ is a particularly ancient bacterial pathway. The habitat, physiology and phylogenetic position of Ca. ‘A. autotrophicum’ support the view that the first bacterial and archaeal lineages were H2-dependent acetogens and methanogenes living in hydrothermal environments. PMID:22303444

Co2(CO)8-catalyzed intramolecular hetero-Pauson-Khand reaction of alkynecarbodiimide: synthesis of (+/-)-physostigmine.

PubMed

Mukai, Chisato; Yoshida, Tatsunori; Sorimachi, Mao; Odani, Akira

2006-01-05

[reaction: see text] Herein we describe a novel Co(2)(CO)(8)-catalyzed intramolecular aza-Pauson-Khand-type reaction of alkynecarbodiimide derivatives affords pyrrolo[2,3-b]indol-2-one ring systems in reasonable yields. This is the first reported Co(2)(CO)(8) successfully applied in the hetero-Pauson-Khand reaction. Significantly, the transformation of one of our pyrrolo[2,3-b]indol-2-one derivatives into the indole alkaloid, (+/-)-physostigmine, was completed in a highly stereoselective manner.

[Quantitative estimation source of urban atmospheric CO2 by carbon isotope composition].

PubMed

Liu, Wei; Wei, Nan-Nan; Wang, Guang-Hua; Yao, Jian; Zeng, You-Shi; Fan, Xue-Bo; Geng, Yan-Hong; Li, Yan

2012-04-01

To effectively reduce urban carbon emissions and verify the effectiveness of currently project for urban carbon emission reduction, quantitative estimation sources of urban atmospheric CO2 correctly is necessary. Since little fractionation of carbon isotope exists in the transportation from pollution sources to the receptor, the carbon isotope composition can be used for source apportionment. In the present study, a method was established to quantitatively estimate the source of urban atmospheric CO2 by the carbon isotope composition. Both diurnal and height variations of concentrations of CO2 derived from biomass, vehicle exhaust and coal burning were further determined for atmospheric CO2 in Jiading district of Shanghai. Biomass-derived CO2 accounts for the largest portion of atmospheric CO2. The concentrations of CO2 derived from the coal burning are larger in the night-time (00:00, 04:00 and 20:00) than in the daytime (08:00, 12:00 and 16:00), and increase with the increase of height. Those derived from the vehicle exhaust decrease with the height increase. The diurnal and height variations of sources reflect the emission and transport characteristics of atmospheric CO2 in Jiading district of Shanghai.

[Combined CO2 and Nd-YAG laser in neurosurgical practice. A 1st experience apropos of 40 intracranial procedures].

PubMed

Roux, F X; Leriche, B; Cioloca, C; Devaux, B; Turak, B; Nohra, G

1992-01-01

The authors present their experience concerning the use of Combolaser (Lasermatic, Finland), in neurosurgery. This laser-unit combines two wavelengths (CO2 and 1.06 Nd-YAG) which are emitted simultaneously and coaxially. During the last 12 months, 40 patients harbouring an intracranial tumor were operated upon with such a combolaser unit: 8 infra-tentorial, 32 supra-tentorial, 17 were meningiomas. The mean output power used during the procedures was 3-5 w for both CO2 and Nd-YAG beams. The authors discuss the advantages and inconveniences of such a laser; and they compare it with the other laser-units they have been using for the last 10 years: CO2-Laser, 1.06 Nd-YAG and 1.32 Nd-YAG laser. The main inconvenience of this unit is linked to the utilization of the articulated arm which conducts the CO2 laser beam. This drawback should be avoided or limited by the use of a fiber microguide, which will conduct both CO2 and Nd-YAG beams simultaneously. The principal contribution of a combined-laser unit is the quality of the haemostasis associated to a very good vaporization and cutting effect. When both wavelengths are synchronized, the combined laser beams penetrate into the nervous parenchyma more deeply than the only CO2 laser beam would with the same parameters. The vaporization effect is identical to that obtained with the isolated CO2 laser; the quality of haemostasis is limited to the effects of the Nd-YAG laser. Another advantage must be emphasized: the possibility of utilizing separately the CO2 laser and the 1.06 Nd-YAG.

Biological formation of ethane and propane in the deep marine subsurface.

PubMed

Hinrichs, Kai-Uwe; Hayes, John M; Bach, Wolfgang; Spivack, Arthur J; Hmelo, Laura R; Holm, Nils G; Johnson, Carl G; Sylva, Sean P

2006-10-03

Concentrations and isotopic compositions of ethane and propane in cold, deeply buried sediments from the southeastern Pacific are best explained by microbial production of these gases in situ. Reduction of acetate to ethane provides one feasible mechanism. Propane is enriched in (13)C relative to ethane. The amount is consistent with derivation of the third C from inorganic carbon dissolved in sedimentary pore waters. At typical sedimentary conditions, the reactions yield free energy sufficient for growth. Relationships with competing processes are governed mainly by the abundance of H(2). Production of C(2) and C(3) hydrocarbons in this way provides a sink for acetate and hydrogen but upsets the general belief that hydrocarbons larger than methane derive only from thermal degradation of fossil organic material.

Biological formation of ethane and propane in the deep marine subsurface

PubMed Central

Hinrichs, Kai-Uwe; Hayes, John M.; Bach, Wolfgang; Spivack, Arthur J.; Hmelo, Laura R.; Holm, Nils G.; Johnson, Carl G.; Sylva, Sean P.

2006-01-01

Concentrations and isotopic compositions of ethane and propane in cold, deeply buried sediments from the southeastern Pacific are best explained by microbial production of these gases in situ. Reduction of acetate to ethane provides one feasible mechanism. Propane is enriched in 13C relative to ethane. The amount is consistent with derivation of the third C from inorganic carbon dissolved in sedimentary pore waters. At typical sedimentary conditions, the reactions yield free energy sufficient for growth. Relationships with competing processes are governed mainly by the abundance of H2. Production of C2 and C3 hydrocarbons in this way provides a sink for acetate and hydrogen but upsets the general belief that hydrocarbons larger than methane derive only from thermal degradation of fossil organic material. PMID:16990430

Metal-Organic Frameworks Derived Porous Core/Shell Structured ZnO/ZnCo2O4/C Hybrids as Anodes for High-Performance Lithium-Ion Battery.

PubMed

Ge, Xiaoli; Li, Zhaoqiang; Wang, Chengxiang; Yin, Longwei

2015-12-09

Metal-organic frameworks (MOFs) derived porous core/shell ZnO/ZnCo2O4/C hybrids with ZnO as a core and ZnCo2O4 as a shell are for the first time fabricated by using core/shell ZnCo-MOF precursors as reactant templates. The unique MOFs-derived core/shell structured ZnO/ZnCo2O4/C hybrids are assembled from nanoparticles of ZnO and ZnCo2O4, with homogeneous carbon layers coated on the surface of the ZnCo2O4 shell. When acting as anode materials for lithium-ion batteries (LIBs), the MOFs-derived porous ZnO/ZnCo2O4/C anodes exhibit outstanding cycling stability, high Coulombic efficiency, and remarkable rate capability. The excellent electrochemical performance of the ZnO/ZnCo2O4/C LIB anodes can be attributed to the synergistic effect of the porous structure of the MOFs-derived core/shell ZnO/ZnCo2O4/C and homogeneous carbon layer coating on the surface of the ZnCo2O4 shells. The hierarchically porous core/shell structure offers abundant active sites, enhances the electrode/electrolyte contact area, provides abundant channels for electrolyte penetration, and also alleviates the structure decomposition induced by Li(+) insertion/extraction. The carbon layers effectively improve the conductivity of the hybrids and thus enhance the electron transfer rate, efficiently prevent ZnCo2O4 from aggregation and disintegration, and partially buffer the stress induced by the volume change during cycles. This strategy may shed light on designing new MOF-based hybrid electrodes for energy storage and conversion devices.

Authigenic carbon entombed in methane-soaked sediments from the northeastern transform margin of the Guaymas Basin, Gulf of California

NASA Astrophysics Data System (ADS)

Paull, Charles K.; Ussler, William; Peltzer, Edward T.; Brewer, Peter G.; Keaten, Rendy; Mitts, Patrick J.; Nealon, Jeffrey W.; Greinert, Jens; Herguera, Juan-Carlos; Elena Perez, M.

2007-06-01

Extensive ROV-based sampling and exploration of the seafloor was conducted along an eroded transform-parallel fault scarp on the northeastern side of the Guaymas Basin in the Gulf of California to observe the nature of fluids venting from the seafloor, measure the record left by methane-venting on the carbonates from this area, and determine the association with gas hydrate. One gas vent vigorous enough to generate a water-column gas plume traceable for over 800 m above the seafloor was found to emanate from a ˜10-cm-wide orifice on the eroded scarp face. Sediment temperature measurements and topography on a sub-bottom reflector recorded in a transform-parallel seismic reflection profile identified a subsurface thermal anomaly beneath the gas vent. Active chemosynthetic biological communities (CBCs) and extensive authigenic carbonates that coalesce into distinct chemoherm structures were encountered elsewhere along the eroded transform-parallel scarp. The carbon isotopic composition of methane bubbles flowing vigorously from the gas vent (-53.6±0.8‰ PDB) is comparable to methane found in sediment cores taken within the CBCs distributed along the scarp (-51.9±8.1‰ PDB). However, the δ13C value of the CO 2 in the vent gas (+12.4±1.1‰ PDB) is very distinct from those for dissolved inorganic carbon (DIC) (-35.8‰ to -2.9‰ PDB) found elsewhere along the scarp, including underneath CBCs. The δ13C values of the carbonate-rich sediments and rocks exposed on the seafloor today also span an unusually large range (-40.9‰ to +12.9‰ PDB) and suggest two distinct populations of authigenic carbonate materials were sampled. Unconsolidated sediments and some carbonate rocks, which have lithologic evidence for near-seafloor formation, have negative δ13C values, while carbonate rocks that clearly formed in the subsurface have positive δ13C values (up to +23.0‰) close to that measured for CO 2 in the vent gas. There appears to be two carbon sources for the authigenic carbonates: (1) deeply-sourced, isotopically heavy CO 2 (˜+12‰); and (2) isotopically light DIC derived from local anaerobic oxidation of methane at the sulfate-methane interface in the shallow subsurface. Addition of isotopically light methane-derived carbon at the seafloor may completely mask the isotopically heavy CO 2 signature (+12.4‰) in the underlying sediments. Thus, the authigenic carbonates may have formed from the same methane- and carbon dioxide-bearing fluid, but under different migration and alteration conditions, depending on how it migrated through the sediment column.

Xylem transport of root-derived CO2: An alternative flux pathway of substantial importance for understanding the components of ecosystem respiration

NASA Astrophysics Data System (ADS)

Aubrey, D. P.; Teskey, R. O.

2011-12-01

Forest ecosystem respiration releases one of the largest annual CO2 fluxes of the global carbon cycle and is dominated by belowground autotrophic and heterotrophic contributions. A mechanistic understanding of forest respiratory flux pathways is imperative to understanding carbon cycling in forests. We recently demonstrated that, on a daily basis, the amount of CO2 that fluxes upward from tree root systems into stems via the xylem stream rivals the amount of CO2 diffusing from the soil surface. However, our original observations were limited to only four individual eastern cottonwood (Populus deltoides L.) trees over a single week where environmental conditions remained similar. Here, we expand our investigation to an entire growing season using nine trees. We calculated the internal transport of root-derived CO2 as the product of sap flow and dissolved CO2 concentration ([CO2]) in the xylem at the base of the stem and measured soil CO2 efflux using the [CO2] gradient approach. We then compared the magnitude of these two flux pathways throughout the growing season. The internal transport of root-derived CO2 was equivalent to one-third of the total belowground respiration throughout the growing season. This indicates that autotrophic respiration was substantially higher than previously estimated, and also higher than heterotrophic soil respiration. The quantity of internally transported CO2 was influenced by both seasonal and daily environmental factors that influenced sap flow rates. We observed high concentrations of CO2 in xylem sap which ranged from 1% to 20% [CO2] among and within individual trees through time. Our results provide evidence that belowground autotrophic respiration consumes a larger amount-and stem respiration consumes a smaller amount-of carbohydrates than previously realized. The magnitude of the internal pathway for root-derived CO2 flux highlights the inadequacy of using the CO2 efflux from the soil surface to the atmosphere alone to measure root respiration. We suggest the internal transport of root-derived CO2 should be measured concurrently with CO2 efflux to the atmosphere to more fully understand the components of ecosystem respiration.

Interactions of acylated methylglucoside derivatives with CO2: simulation and calculations.

PubMed

Chang, H H; Cao, R X; Yang, C C; Wei, W L; Pang, X Y; Qiao, Y

2016-01-01

Carbohydrates have drawn considerable interest from researchers recently due to their affinity for CO2. However, most of the research in this field has focused on peracetylated derivatives. Compared with acetylated carbohydrates, which have already been studied in depth, methyl D-glucopyranoside derivatives are more stable and could have additional applications. Thus, in the present work, ab initio calculations were performed to elucidate the characteristics of the interactions of methylglucoside derivatives with CO2, and to investigate how the binding energy (ΔE) is affected by isomerization or the introduction of various acyl groups. Four methyl D-glucopyranosides (each with two anomers) bearing acetyl, propionyl, butyryl, and isobutyryl moieties, respectively, were designed as substrates, and the 1:1 complexes of a CO2 molecule with each of these sugar substrates were modeled. The results indicate that ΔE is mainly influenced by interaction distance and the number of negatively charged donors or interacting pairs in the complex; the structure of the acyl group present in the substrate is a secondary influence. Except in the case of methyl 2-O-acetyl-D-glucopyranose, the ΔE values of the α- and β-anomers of each methylglucoside were found to be almost the same. Therefore, we would expect the CO2 affinities of the four derivatives studied here to be as strong as or even stronger than that of peracetylated D-glucopyranose. Graphical Abstract The binding energy between methyl D-glucopyranoside derivatives with various substituted acyl groups and CO2 are evaluated by ab initio calculations. The strong interaction between these methyl dglucopyranoside derivatives and CO2 showed the potential of their application for CO2 capture.

Fluid challenge: tracking changes in cardiac output with blood pressure monitoring (invasive or non-invasive).

PubMed

Lakhal, Karim; Ehrmann, Stephan; Perrotin, Dominique; Wolff, Michel; Boulain, Thierry

2013-11-01

To assess whether invasive and non-invasive blood pressure (BP) monitoring allows the identification of patients who have responded to a fluid challenge, i.e., who have increased their cardiac output (CO). Patients with signs of circulatory failure were prospectively included. Before and after a fluid challenge, CO and the mean of four intra-arterial and oscillometric brachial cuff BP measurements were collected. Fluid responsiveness was defined by an increase in CO ≥10 or ≥15% in case of regular rhythm or arrhythmia, respectively. In 130 patients, the correlation between a fluid-induced increase in pulse pressure (Δ500mlPP) and fluid-induced increase in CO was weak and was similar for invasive and non-invasive measurements of BP: r² = 0.31 and r² = 0.29, respectively (both p < 0.001). For the identification of responders, invasive Δ500mlPP was associated with an area under the receiver-operating curve (AUC) of 0.82 (0.74-0.88), similar (p = 0.80) to that of non-invasive Δ500mlPP [AUC of 0.81 (0.73-0.87)]. Outside large gray zones of inconclusive values (5-23% for invasive Δ500mlPP and 4-35% for non-invasive Δ500mlPP, involving 35 and 48% of patients, respectively), the detection of responsiveness or unresponsiveness to fluid was reliable. Cardiac arrhythmia did not impair the performance of invasive or non-invasive Δ500mlPP. Other BP-derived indices did not outperform Δ500mlPP. As evidenced by large gray zones, BP-derived indices poorly reflected fluid responsiveness. However, in our deeply sedated population, a high increase in invasive pulse pressure (>23%) or even in non-invasive pulse pressure (>35%) reliably detected a response to fluid. In the absence of a marked increase in pulse pressure (<4-5%), a response to fluid was unlikely.

A Generalized Hydrodynamic-Impact Theory for the Loads and Motions of Deeply Immersed Prismatic Bodies

NASA Technical Reports Server (NTRS)

Markey, Melvin F.

1959-01-01

A theory is derived for determining the loads and motions of a deeply immersed prismatic body. The method makes use of a two-dimensional water-mass variation and an aspect-ratio correction for three-dimensional flow. The equations of motion are generalized by using a mean value of the aspect-ratio correction and by assuming a variation of the two-dimensional water mass for the deeply immersed body. These equations lead to impact coefficients that depend on an approach parameter which, in turn, depends upon the initial trim and flight-path angles. Comparison of experiment with theory is shown at maximum load and maximum penetration for the flat-bottom (0 deg dead-rise angle) model with bean-loading coefficients from 36.5 to 133.7 over a wide range of initial conditions. A dead-rise angle correction is applied and maximum-load data are compared with theory for the case of a model with 300 dead-rise angle and beam-loading coefficients from 208 to 530.

Application research of CO2 laser cutting natural stone plates

NASA Astrophysics Data System (ADS)

Ma, Lixiu; Song, Jijiang

2009-08-01

Now, the processing of natural stone plates is the high performance sawing machine primarily,many researchers deeply studied the processing characters in the sawing process and the strength characters during the processing. In order to realize the profiled-processing and pattern- carving of the natural stone, It lays a solid foundation for the laser cutting and the pattern-carving technology of natural stone plate. The working principle, type and characteristics of laser cutting are briefly described. The paper selects 6 kinds stone plates of natural taken as experimental sample,the experimental sample was China Shanxi Black, Old Spain Golden Yellow, New Spain Golden Yellow, Jazz White, Maple Leaf Red, Cream White respectively. Use high power CO2 laser cutting system,the stone plates cutting experiment of 6 kinds different hardness, the best working speed are obtained,The experimental results indicate that: The laser cutting speed has no correlation with the ingredient content of stone plate.

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

Jennings, Ryan de Montmollin; Moran, James J.; Jay, Zackary J.

Biological fixation of CO 2 is the primary mechanism of C reduction in natural systems, and provides a diverse suite of organic compounds utilized by chemoorganoheterotrophs. The extent and mechanisms of CO 2 fixation were evaluated across a comprehensive set of high-temperature, chemotrophic microbial communities in Yellowstone National Park by combining metagenomic and stable 13C isotope analyses. Fifteen geothermal sites representing three distinct habitat types (iron-oxide mats, anoxic sulfur sediments, and filamentous ‘streamer’ communities) were investigated. Genes of the 3-hydroxypropionate/4-hydroxybutyrate, dicarboxylate/4-hydroxybutyrate, and reverse tricarboxylic acid CO 2 fixation pathways were identified in assembled genome sequence corresponding to the predominant Crenarchaeotamore » and Aquificales observed across this habitat range. Stable 13C analyses of dissolved inorganic and organic C (DIC, DOC), and possible landscape C sources were used to interpret the 13C content of microbial community samples. Isotope mixing models showed that the minimum amounts of autotrophic C in microbial biomass were > 50 % in the majority of communities analyzed, but were also dependent on the amounts of heterotrophy and/or accumulation of landscape C. Furthermore, the significance of CO 2 as a C source in these communities provides a foundation for understanding metabolic linkages among autotrophs and heterotrophs, community assembly and succession, and the likely coevolution of deeply-branching thermophiles.« less

Highly Dispersed Metal Carbide on ZIF-Derived Pyridinic-N-Doped Carbon for CO2 Enrichment and Selective Hydrogenation.

PubMed

Li, Yunhua; Cai, Xiaohu; Chen, Sijing; Zhang, Hua; Zhang, Kevin H L; Hong, Jinqing; Chen, Binghui; Kuo, Dong-Hau; Wang, Wenju

2018-03-22

Catalytic conversion of CO 2 into chemicals is a critical issue for energy and environmental research. Among such reactions, converting CO 2 into CO has been regarded as a significant foundation to generate a liquid fuels and chemicals on a large scale. In this work, zeolitic imidazolate framework-derived N-doped carbon-supported metal carbide catalysts (M/ZIF-8-C; M=Ni, Fe, Co and Cu) with highly dispersed metal carbide were prepared for selective CO 2 hydrogenation. Under the same metal loadings, catalytic activity for CO 2 hydrogenation to CO follows the order: Ni/ZIF-8-C≈Fe/ZIF-8-C>Co/ZIF-8-C>Cu/ZIF-8-C. These catalysts are composed of carbide or metal supported on pyridinic N sites within the N-doped carbon structure. ZIF-8-derived pyridinic nitrogen and carbide effect CO 2 adsorption, whereas dispersed Ni or Fe carbide and metal species serve as an active site for CO 2 hydrogenation. The supported Ni catalyst exhibits extraordinary catalytic performance, which results from high dispersion of the metal and exposure of the carbide. Based on high-sensitivity low-energy ion scattering (HS-LEIS) and line scan results, density functional theory (DFT) was used to understand reaction mechanism of selective CO 2 hydrogenation over Ni/ZIF-8-C. The product CO is derived mainly from the direct cleavage of C-O bonds in CO 2 * rather than decomposition of COOH*. The CO* desorption energy on Ni/ZIF-8-C is lower than that for further hydrogenation and dissociation. Comparison of Ni/ZIF-8-C with ZIF-8-C indicates that the combined effects of the highly dispersed metal or carbide and weak CO adsorption result in high CO selectivity for CO 2 hydrogenation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triptycene-Based Microporous Cyanate Resins for Adsorption/Separations of Benzene/Cyclohexane and Carbon Dioxide Gas.

PubMed

Deng, Gaoyang; Wang, Zhonggang

2017-11-29

Triptycene-based cyanate monomers 2,6,14-tricyanatotriptycene (TPC) and 2,6,14-tris(4-cyanatophenyl)triptycene (TPPC) that contain different numbers of benzene rings per molecule were synthesized, from which two microporous cyanate resins PCN-TPC and PCN-TPPC were prepared. Of interest is the observation that the two polymers have very similar porosity parameters, but PCN-TPPC uptakes considerably higher benzene (77.8 wt %) than PCN-TPC (17.6 wt %) at room temperature since the higher concentration of phenyl groups in PCN-TPPC enhances the π-π interaction with benzene molecules. Besides, the adsorption capacity of benzene in PCN-TPPC is dramatically 7 times as high as that of cyclohexane. Contrary to the adsorption of organic vapors, at 273 K and 1.0 bar, PCN-TPC with more heteroatoms in the network skeleton displays larger uptake of CO 2 and higher CO 2 /N 2 selectivity (16.4 wt %, 60) than those of PCN-TPPC (14.0 wt %, 39). The excellent and unique adsorption properties exhibit potential applications in the purification of small molecular organic hydrocarbons, e.g., separation of benzene from benzene/cyclohexane mixture as well as CO 2 capture from flue gas. Moreover, the results are helpful for deeply understanding the effect of porous and chemical structures on the adsorption properties of organic hydrocarbons and CO 2 gas.

Application of a phosphazene derivative as a flame retardant for cotton fabric using conventional method and supercritical CO2

USDA-ARS?s Scientific Manuscript database

Conventional pad-dry-cure (non-scCO2) and supercritical carbon dioxide (scCO2) application methods were investigated to study the effectiveness of a phosphazene derivative as a flame retardant on cotton fabric. 1,1',4,5-tetrahydrotrispiro[1,3,2-diazaphosphole-2,2'-[1,3,5,2,4,6]triazatriphosphinine-4...

Electro-autotrophic synthesis of higher alcohols

DOEpatents

Liao, James C.; Cho, Kwang Myung

2016-11-01

The disclosure provides a process that converts CO.sub.2 to higher alcohols (e.g. isobutanol) using electricity as the energy source. This process stores electricity (e.g. from solar energy, nuclear energy, and the like) in liquid fuels that can be used as high octane number gasoline substitutes. Instead of deriving reducing power from photosynthesis, this process derives reducing power from electrically generated mediators, either H.sub.2 or formate. H.sub.2 can be derived from electrolysis of water. Formate can be generated by electrochemical reduction of CO.sub.2. After delivering the reducing power in the cell, formate becomes CO.sub.2 and recycles back. Therefore, the biological CO.sub.2 fixation process can occur in the dark.

Electro-autotrophic synthesis of higher alcohols

DOEpatents

Liao, James C.; Cho, Kwang Myung

2015-10-06

The disclosure provides a process that converts CO.sub.2 to higher alcohols (e.g. isobutanol) using electricity as the energy source. This process stores electricity (e.g. from solar energy, nuclear energy, and the like) in liquid fuels that can be used as high octane number gasoline substitutes. Instead of deriving reducing power from photosynthesis, this process derives reducing power from electrically generated mediators, either H.sub.2 or formate. H.sub.2 can be derived from electrolysis of water. Formate can be generated by electrochemical reduction of CO.sub.2. After delivering the reducing power in the cell, formate becomes CO.sub.2 and recycles back. Therefore, the biological CO.sub.2 fixation process can occur in the dark.

Methane enhancement through co-digestion of chicken manure and thermo-oxidative cleaved wheat straw with waste activated sludge: A C/N optimization case.

PubMed

Hassan, Muhammad; Ding, Weimin; Shi, Zhendan; Zhao, Sanqin

2016-07-01

The present study emphasized the co-digestion of the thermal-H2O2 pretreated wheat straw (WS) and chicken manure (CM) with the waste activated sludge at four levels of C/N (35:1, 30:1, 25:1 and 20:1). All C/N compositions were found significant (P<0.05) to enhance methane generation and process stability during the anaerobic co-digestion of WS and CM. The experimental results revealed that the composition having C/N value of 20:1 was proved as optimum treatment with the methane enhancing capability of 85.11%, CODs removal efficiency of 48.55% and 66.83% VS removal as compared with the untreated WS. The other compositions having C/N of 25:1, 30:1 and 35:1 provided 75.85%, 63.04% and 59.96% enhanced methane respectively as compared with the control. Pretreatment of the WS reduced its C/N value up to 65%. Moreover, to optimize the most suitable C/N composition, the process stability of the co-digestion of WS and CM was deeply monitored. Copyright © 2016 Elsevier Ltd. All rights reserved.

Single-breath CO2 analysis as a predictor of lung volume in a healthy animal model during controlled ventilation.

PubMed

Stenz, R I; Grenier, B; Thompson, J E; Arnold, J H

1998-08-01

To examine the utility of single-breath CO2 analysis as a measure of lung volume. A prospective, animal cohort study comparing 21 parameters derived from single-breath CO2 analysis with lung volume measurements determined by nitrogen washout in animals during controlled ventilation. An animal laboratory in a university-affiliated medical center. Seven healthy lambs. The single-breath CO2 analysis station consists of a mainstream capnometer, a variable orifice pneumotachometer, a signal processor and computer software with capability for both on- and off-line data analysis. Twenty-one derived components of the CO2 expirogram were evaluated as predictors of lung volume. Lung volume was manipulated by 3 cm H2O incremental increases in positive end-expiratory pressure from 0 to 21 cm H2O, and ranged between 147 and 942 mL. Fifty-five measurements of lung volume were available for comparison with derived variables from the CO2 expirogam. Stepwise linear regression identified four variables that were most predictive of lung volume: a) dynamic lung compliance; b) the slope of phase 3; c) the slope of phase 2 divided by the mixed expired CO2 tension; and d) airway deadspace. The multivariate equation was highly statistically significant and explained 94% of the variance (adjusted r2 =.94, p < .0001). The bias and precision of the calculated lung volume was .00 and 51, respectively. The mean percent difference for the lung volume estimate derived from the single-breath CO2 analysis station was 0.79%. Our data indicate that analysis of the CO2 expirogram can yield accurate information about lung volume. Specifically, four variables derived from a plot of expired CO2 concentration vs. expired volume predict changes in lung volume in healthy lambs with an adjusted coefficient of determination of .94. Prospective application of this technology in the setting of lung injury and rapidly changing physiology is essential in determining the clinical usefulness of the technique.

Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper.

PubMed

Li, Christina W; Ciston, Jim; Kanan, Matthew W

2014-04-24

The electrochemical conversion of CO2 and H2O into liquid fuel is ideal for high-density renewable energy storage and could provide an incentive for CO2 capture. However, efficient electrocatalysts for reducing CO2 and its derivatives into a desirable fuel are not available at present. Although many catalysts can reduce CO2 to carbon monoxide (CO), liquid fuel synthesis requires that CO is reduced further, using H2O as a H(+) source. Copper (Cu) is the only known material with an appreciable CO electroreduction activity, but in bulk form its efficiency and selectivity for liquid fuel are far too low for practical use. In particular, H2O reduction to H2 outcompetes CO reduction on Cu electrodes unless extreme overpotentials are applied, at which point gaseous hydrocarbons are the major CO reduction products. Here we show that nanocrystalline Cu prepared from Cu2O ('oxide-derived Cu') produces multi-carbon oxygenates (ethanol, acetate and n-propanol) with up to 57% Faraday efficiency at modest potentials (-0.25 volts to -0.5 volts versus the reversible hydrogen electrode) in CO-saturated alkaline H2O. By comparison, when prepared by traditional vapour condensation, Cu nanoparticles with an average crystallite size similar to that of oxide-derived copper produce nearly exclusive H2 (96% Faraday efficiency) under identical conditions. Our results demonstrate the ability to change the intrinsic catalytic properties of Cu for this notoriously difficult reaction by growing interconnected nanocrystallites from the constrained environment of an oxide lattice. The selectivity for oxygenates, with ethanol as the major product, demonstrates the feasibility of a two-step conversion of CO2 to liquid fuel that could be powered by renewable electricity.

Stratospheric CH4 and CO2 profiles derived from SCIAMACHY solar occultation measurements

NASA Astrophysics Data System (ADS)

Noël, S.; Bramstedt, K.; Hilker, M.; Liebing, P.; Plieninger, J.; Reuter, M.; Rozanov, A.; Bovensmann, H.; Burrows, J. P.

2015-11-01

Stratospheric profiles of methane (CH4) and carbon dioxide (CO2) have been derived from solar occultation measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). The retrieval is performed using a method called "Onion Peeling DOAS" (ONPD) which combines an onion peeling approach with a weighting function DOAS (Differential Optical Absorption Spectroscopy) fit. By use of updated pointing information and optimisation of the data selection and of the retrieval approach the altitude range for reasonable CH4 could be extended to about 17 to 45 km. Furthermore, the quality of the derived CO2 has been assessed such that now the first stratospheric profiles of CO2 from SCIAMACHY are available. Comparisons with independent data sets yield an estimated accuracy of the new SCIAMACHY stratospheric profiles of about 5-10 % for CH4 and 2-3 % for CO2. The accuracy of the products is currently mainly restricted by the appearance of unexpected vertical oscillations in the derived profiles which need further investigation. Using the improved ONPD retrieval, CH4 and CO2 stratospheric data sets covering the whole SCIAMACHY time series (August 2002-April 2012) and the latitudinal range between about 50 and 70° N have been derived. Based on these time series, CH4 and CO2 trends have been estimated, which are in reasonable agreement with total column trends for these gases. This shows that the new SCIAMACHY data sets can provide valuable information about the stratosphere.

Writing System Variation and Its Consequences for Reading and Dyslexia

ERIC Educational Resources Information Center

Daniels, Peter T.; Share, David L.

2018-01-01

Most current theories of reading and dyslexia derive from a relatively narrow empirical base: research on English and a handful of other European alphabets. Furthermore, the two dominant theoretical frameworks for describing cross-script diversity--orthographic depth and psycholinguistic grain size theory--are also deeply entrenched in Anglophone…

Measuring Carbon-based Contaminant Mineralization Using Combined CO2 Flux and Radiocarbon Analyses.

PubMed

Boyd, Thomas J; Montgomery, Michael T; Cuenca, Richard H; Hagimoto, Yutaka

2016-10-21

A method is described which uses the absence of radiocarbon in industrial chemicals and fuels made from petroleum feedstocks which frequently contaminate the environment. This radiocarbon signal - or rather the absence of signal - is evenly distributed throughout a contaminant source pool (unlike an added tracer) and is not impacted by biological, chemical or physical processes (e.g., the 14 C radioactive decay rate is immutable). If the fossil-derived contaminant is fully degraded to CO2, a harmless end-product, that CO2 will contain no radiocarbon. CO2 derived from natural organic matter (NOM) degradation will reflect the NOM radiocarbon content (usually <30,000 years old). Given a known radiocarbon content for NOM (a site background), a two end-member mixing model can be used to determine the CO2 derived from a fossil source in a given soil gas or groundwater sample. Coupling the percent CO2 derived from the contaminant with the CO2 respiration rate provides an estimate for the total amount of contaminant degraded per unit time. Finally, determining a zone of influence (ZOI) representing the volume from which site CO2 is collected allows determining the contaminant degradation per unit time and volume. Along with estimates for total contaminant mass, this can ultimately be used to calculate time-to-remediate or otherwise used by site managers for decision-making.

Measuring Carbon-based Contaminant Mineralization Using Combined CO2 Flux and Radiocarbon Analyses

PubMed Central

Boyd, Thomas J.; Montgomery, Michael T.; Cuenca, Richard H.; Hagimoto, Yutaka

2016-01-01

A method is described which uses the absence of radiocarbon in industrial chemicals and fuels made from petroleum feedstocks which frequently contaminate the environment. This radiocarbon signal — or rather the absence of signal — is evenly distributed throughout a contaminant source pool (unlike an added tracer) and is not impacted by biological, chemical or physical processes (e.g., the 14C radioactive decay rate is immutable). If the fossil-derived contaminant is fully degraded to CO2, a harmless end-product, that CO2 will contain no radiocarbon. CO2 derived from natural organic matter (NOM) degradation will reflect the NOM radiocarbon content (usually <30,000 years old). Given a known radiocarbon content for NOM (a site background), a two end-member mixing model can be used to determine the CO2 derived from a fossil source in a given soil gas or groundwater sample. Coupling the percent CO2 derived from the contaminant with the CO2 respiration rate provides an estimate for the total amount of contaminant degraded per unit time. Finally, determining a zone of influence (ZOI) representing the volume from which site CO2 is collected allows determining the contaminant degradation per unit time and volume. Along with estimates for total contaminant mass, this can ultimately be used to calculate time-to-remediate or otherwise used by site managers for decision-making. PMID:27805601

The role of priming effects on the conversion of blue carbon to CO2 in the coastal zone

NASA Astrophysics Data System (ADS)

Morrison, E.; Ward, N. D.; Arellano, A. R.; Liu, Y.; Rivas-Ubach, A.; Ogram, A.; Osborne, T.; Vaughn, D.; Bianchi, T. S.

2017-12-01

Coastal ecosystems are recognized as valuable but vulnerable carbon (C) sinks, and the C stored in these systems is often referred to as blue C. These systems face many threats, particularly along low-relief coastlines such as Florida, which are susceptible to erosion and C loss as sea levels rise. Peat-derived organic matter (OM) may be degraded within downstream estuarine systems, and its degradation may be enhanced in the presence of labile algal-derived OM via microbial priming effects. To investigate the role of microbial priming effects on the degradation of peat-derived blue C, incubations were established and a suite of analyses were conducted to evaluate changes in peat-derived OM, CO2 production, metabolites, and microbial community structure (via metagenomic sequencing) over the course of the experiment. Four treatments were established: seawater with peat and algal leachate (SWPA), seawater and peat leachate (SWP), seawater and algal leachate (SWA), and seawater alone (SW). Treatments containing peat leachate (SWPA and SWP) harbored greater total DOC concentrations compared to SWA and SW treatments. Over the course of the incubation, CO2 concentrations increased in all treatments, with the highest CO2 levels in treatments with algal-derived DOM (SWA and SWPA). Both treatments with algal-derived DOM (SWA and SWPA) showed an increase in 13C-labeled CO2 over the course of the incubation, and stable isotope mass balance indicated that the conversion of peat-derived OC to CO2 occurred approximately 30% faster with the presence of algal-derived DOC. Aromaticity indices from absorption spectra were significantly lower in the SWP treatment when compared to the SWPA treatment. Dissolved organic matter molecular formulae detected by Fourier-transformed ion cyclotron resonance spectrometry indicated an increase in the degradation of peat-derived compounds when algal material was present. Overall, these findings suggest that there is an increase in microbial degradation of peat when in the presence of algal-derived DOM, which may drive the conversion of blue carbon stocks to CO2 when exported to estuarine systems.

Spatial Variations in CO2 Mixing Ratios Over a Heterogenous Landscape - Linking Airborne Measurements With Remote Sensing Derived Biophysical Parameters

NASA Astrophysics Data System (ADS)

Choi, Y.; Vadrevu, K. P.; Vay, S. A.; Woo, J.

2006-12-01

North American terrestrial ecosystems are major sources and sinks of carbon. Precise measurement of atmospheric CO2 concentrations plays an important role in the development and testing of carbon cycle models quantifying the influence of terrestrial CO2 exchange on the North American carbon budget. During the summer 2004 Intercontinental Chemical Transport Experiment North America (INTEX-NA) campaign, regional scale in-situ measurements of atmospheric CO2 were made from the NASA DC-8 affording the opportunity to explore how land surface heterogeneity relates to the airborne observations utilizing remote-sensing data products and GIS-based methods. These 1 Hz data reveal the seasonal biospheric uptake of CO2 over portions of the U.S. continent, especially east of 90°W below 2 km, compared to higher mixing ratios over water as well as within the upper troposphere where well-mixed, aged air masses were sampled. In this study, we use several remote sensing derived biophysical parameters from the LANDSAT, NOAA AVHRR, and MODIS sensors to specify spatiotemporal patterns of land use cover and vegetation characteristics for linking the airborne measurements of CO2 data with terrestrial sources of carbon. Also, CO2 flux footprint outputs from a 3-D Lagrangian atmospheric model have been integrated with satellite remote sensing data to infer CO2 variations across heterogeneous landscapes. In examining the landscape mosaic utilizing these available tools, preliminary results suggest that the lowest CO2 mixing ratios observed during INTEX-NA were over agricultural fields in Illinois dominated by corn then secondarily soybean crops. Low CO2 concentrations are attributable to sampling during the peak growing season over such C4 plants as corn having a higher photosynthetic rate via the C4-dicarboxylic acid pathway of carbon fixation compared to C3 plants such as soybeans. In addition to LANDSAT derived land cover data, results from comparisons of the airborne CO2 observations with vegetation indices of NDVI and EVI derived from MODIS data were used. Higher CO2 mixing ratios anti-correlated with the vegetation indices derived from MODIS data were observed. This is attributable to the photosynthetic uptake of CO2 by plants and convective mixing of the atmosphere. Details of satellite data characteristics related with the in-situ CO2 measurements will be presented.

Kinetic temperature of massive star-forming molecular clumps measured with formaldehyde. II. The Large Magellanic Cloud

NASA Astrophysics Data System (ADS)

Tang, X. D.; Henkel, C.; Chen, C.-H. R.; Menten, K. M.; Indebetouw, R.; Zheng, X. W.; Esimbek, J.; Zhou, J. J.; Yuan, Y.; Li, D. L.; He, Y. X.

2017-04-01

Context. The kinetic temperature of molecular clouds is a fundamental physical parameter affecting star formation and the initial mass function. The Large Magellanic Cloud (LMC) is the closest star-forming galaxy with a low metallicity and provides an ideal laboratory for studying star formation in such an environment. Aims: The classical dense molecular gas thermometer NH3 is seldom available in a low-metallicity environment because of photoionization and a lack of nitrogen atoms. Our goal is to directly measure the gas kinetic temperature with formaldehyde toward six star-forming regions in the LMC. Methods: Three rotational transitions (JKAKC = 303-202, 322-221, and 321-220) of para-H2CO near 218 GHz were observed with the Atacama Pathfinder EXperiment (APEX) 12 m telescope toward six star-forming regions in the LMC. These data are complemented by C18O 2-1 spectra. Results: Using non-local thermal equilibrium modeling with RADEX, we derive the gas kinetic temperature and spatial density, using as constraints the measured para-H2CO 321-220/303-202 and para-H2CO 303-202/C18O 2-1 ratios. Excluding the quiescent cloud N159S, where only one para-H2CO line could be detected, the gas kinetic temperatures derived from the preferred para-H2CO 321-220/303-202 line ratios range from 35 to 63 K with an average of 47 ± 5 K (errors are unweighted standard deviations of the mean). Spatial densities of the gas derived from the para-H2CO 303-202/C18O 2-1 line ratios yield 0.4-2.9 × 105 cm-3 with an average of 1.5 ± 0.4 × 105 cm-3. Temperatures derived from the para-H2CO line ratio are similar to those obtained with the same method from Galactic star-forming regions and agree with results derived from CO in the dense regions (n(H2) > 103 cm-3) of the LMC. A comparison of kinetic temperatures derived from para-H2CO with those from the dust also shows good agreement. This suggests that the dust and para-H2CO are well mixed in the studied star-forming regions. A comparison of kinetic temperatures derived from para-H2CO 321-220/303-202 and NH3(2, 2)/(1, 1) shows a drastic difference, however. In the star-forming region N159W, the gas temperature derived from the NH3(2, 2)/(1, 1) line ratio is 16 K (Ott et al. 2010, ApJ, 710, 105), which is only half the temperature derived from para-H2CO and the dust. Furthermore, ammonia shows a very low abundance in a 30'' beam. Apparently, ammonia only survives in the most shielded pockets of dense gas that are not yet irradiated by UV photons, while formaldehyde, less affected by photodissociation, is more widespread and also samples regions that are more exposed to the radiation of young massive stars. A correlation between the gas kinetic temperatures derived from para-H2CO and infrared luminosity, represented by the 250 μm flux, suggests that the kinetic temperatures traced by para-H2CO are correlated with the ongoing massive star formation in the LMC. The reduced spectra (FITS files) are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/600/A16

Kinematics of current region fragmentation in semi-inclusive deeply inelastic scattering

DOE PAGES

Boglione, M.; Collins, J.; Gamberg, L.; ...

2017-01-16

Different kinematical regions of semi-inclusive deeply inelastic scattering (SIDIS) processes correspond to different underlying partonic pictures, and it is important to understand the transition between them. We find criteria in semi-inclusive deeply inelastic scattering (SIDIS) for identifying the current fragmentation region — the kinematical region where a factorization picture with fragmentation functions is appropriate, especially for studies of transverse-momentum-dependent (TMD) functions. This region is distinguished from the central (soft) and target fragmentation regions. The basis of our argument is in the errors in approximations used in deriving factorization. As compared with previous work, we show that it is essential tomore » take account of the transverse momentum of the detected hadron, and we find a much more restricted range for genuine current fragmentation. As a result, we show that it is important to develop an extended factorization formulation to treat hadronization in the central region, as well as the current and target fragmentation regions, and to obtain a unified formalism spanning all rapidities for the detected hadron.« less

Increasing Malonyl-CoA Derived Product through Controlling the Transcription Regulators of Phospholipid Synthesis in Saccharomyces cerevisiae.

PubMed

Chen, Xiaoxu; Yang, Xiaoyu; Shen, Yu; Hou, Jin; Bao, Xiaoming

2017-05-19

Malonyl-CoA is a precursor of a variety of compounds such as polyketides and flavonoids. In Saccharomyces cerevisiae, malonyl-CoA concentration is tightly regulated and therefore maintained at a very low level, limiting the production of malonyl-CoA-derived chemicals. Here we manipulated the phospholipid synthesis transcriptional regulators to control the malonyl-CoA levels and increase the downstream product. Through manipulating different regulators including Ino2p, Ino4p, Opi1p, and a series of synthetic Ino2p variants, combining with studying the inositol and choline effect, the engineered strain achieved a 9-fold increase of the titer of malonyl-CoA-derived product 3-hydroxypropionic acid, which is among the highest improvement relative to previously reported strategies. Our study provides a new strategy to regulate malonyl-CoA availability and will contribute to the production of other highly valued malonyl-CoA-derived chemicals.

Global Kinetic Constants for Thermal Oxidative Degradation of a Cellulosic Paper

NASA Technical Reports Server (NTRS)

Kashiwagi, Takashi; Nambu, Hidesaburo

1992-01-01

Values of global kinetic constants for pyrolysis, thermal oxidative degradation, and char oxidation of a cellulosic paper were determined by a derivative thermal gravimetric study. The study was conducted at heating rates of 0.5, 1, 1.5, 3, and 5 C/min in ambient atmospheres of nitrogen, 0.28, 1.08, 5.2 percent oxygen concentrations, and air. Sample weight loss rate, concentrations of CO, CO2, and H2O in the degradation products, and oxygen consumption were continuously measured during the experiment. Values of activation energy, preexponential factor, orders of reaction, and yields of CO, CO2, H2O, total hydrocarbons, and char for each degradation reaction were derived from the results. Heat of reaction for each reaction was determined by differential scanning calorimetry. A comparison of the calculated CO, CO2, H2O, total hydrocarbons, sample weight loss rate, and oxygen consumption was made with the measured results using the derived kinetic constants, and the accuracy of the values of kinetic constants was discussed.

H-implantation in SO 2 and CO 2 ices

NASA Astrophysics Data System (ADS)

Garozzo, M.; Fulvio, D.; Gomis, O.; Palumbo, M. E.; Strazzulla, G.

2008-07-01

Ices in the solar system are observed on the surface of planets, satellites, comets and asteroids where they are continuously subordinate at particle fluxes (cosmic ions, solar wind and charged particles caught in the magnetosphere of the planets) that deeply modify their physical and structural properties. Each incoming ion destroys molecular bonds producing fragments that, by recombination, form new molecules also different from the original ones. Moreover, if the incoming ion is reactive (H +, O n+ , S n+ , etc.), it can concur to the formation of new molecules. Those effects can be studied by laboratory experiments where, with some limitation, it is possible to reproduce the astrophysical environments of planetary ices. In this work, we describe some experiments of 15-100 keV H + and He + implantation in pure sulfur dioxide (SO 2) at 16 and 80 K and carbon dioxide (CO 2) at 16 K ices aimed to search for the formation of new molecules. Among other results we confirm that carbonic acid (H 2CO 3) is formed after H-implantation in CO 2, vice versa H-implantation in SO 2 at both temperatures does not produce measurable quantity of sulfurous acid (H 2SO 3). The results are discussed in the light of their relevance to the chemistry of some solar system objects, particularly of Io, the innermost of Jupiter's Galilean satellites, that exhibits a surface very rich in frost SO 2 and it is continuously bombarded with H + ions caught in Jupiter's magnetosphere.

Stratospheric CH4 and CO2 profiles derived from SCIAMACHY solar occultation measurements

NASA Astrophysics Data System (ADS)

Noël, Stefan; Bramstedt, Klaus; Hilker, Michael; Liebing, Patricia; Plieninger, Johannes; Reuter, Max; Rozanov, Alexei; Sioris, Christopher E.; Bovensmann, Heinrich; Burrows, John P.

2016-04-01

Stratospheric profiles of methane (CH4) and carbon dioxide (CO2) have been derived from solar occultation measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). The retrieval is performed using a method called onion peeling DOAS (ONPD), which combines an onion peeling approach with a weighting function DOAS (differential optical absorption spectroscopy) fit in the spectral region between 1559 and 1671 nm. By use of updated pointing information and optimisation of the data selection as well as of the retrieval approach, the altitude range for reasonable CH4 could be broadened from 20 to 40 km to about 17 to 45 km. Furthermore, the quality of the derived CO2 has been assessed such that now the first stratospheric profiles (17-45 km) of CO2 from SCIAMACHY are available. Comparisons with independent data sets yield an estimated accuracy of the new SCIAMACHY stratospheric profiles of about 5-10 % for CH4 and 2-3 % for CO2. The accuracy of the products is currently mainly restricted by the appearance of unexpected vertical oscillations in the derived profiles which need further investigation. Using the improved ONPD retrieval, CH4 and CO2 stratospheric data sets covering the whole SCIAMACHY time series (August 2002-April 2012) and the latitudinal range between about 50 and 70° N have been derived. Based on these time series, CH4 and CO2 trends have been estimated. CH4 trends above about 20 km are not significantly different from zero and the trend at 17 km is about 3 ppbv year-1. The derived CO2 trends show a general decrease with altitude with values of about 1.9 ppmv year-1 at 21 km and about 1.3 ppmv year-1 at 39 km. These results are in reasonable agreement with total column trends for these gases. This shows that the new SCIAMACHY data sets can provide valuable information about the stratosphere.

The reactivity of plant-derived organic matter in the Amazon River and implications on aquatic carbon fluxes to the atmosphere and ocean

NASA Astrophysics Data System (ADS)

Ward, N. D.; Sawakuchi, H. O.; Keil, R. G.; da Silva, R.; Brito, D. C.; Cunha, A. C.; Gagne-Maynard, W.; de Matos, A.; Neu, V.; Bianchi, T. S.; Krusche, A. V.; Richey, J. E.

2014-12-01

The remineralization of terrestrially-derived organic carbon (OC), along with direct CO2 inputs from autochthonous plant respiration in floodplains, results in an evasive CO2 gas flux from inland waters that is an order of magnitude greater than the flux of OC to the ocean. This phenomenon is enhanced in tropical systems as a result of elevated temperatures and productivity relative to temperate and high-latitude counterparts. Likewise, this balance is suspected to be influenced by increasing global temperatures and alterations to hydrologic and land use regimes. Here, we assess the reactivity of terrestrial and aquatic plant-derived OM near the mouth of the Amazon River. The stable isotopic signature of CO2 (δ13CO2) was monitored in real-time during incubation experiments performed in a closed system gas phase equilibration chamber connected to a Picarro Cavity Ring-Down Spectrometer. Incubations were performed under natural conditions and with the injection of isotopically labeled terrestrial macromolecules (e.g. lignin) and algal fatty acids. Under natural conditions, δ13CO2 became more depleted, shifting from roughly -23‰ to -27‰ on average, suggesting that C3 terrestrial vegetation was the primary fuel for CO2 production. Upon separate injections of 13C-labeled lignin and algal fatty acids, δ13CO2 increased near instantaneously and peaked in under 12 hours. Roughly 75% of the labeled lignin was converted to CO2 at the peak in δ13CO2, whereas less than 20% of the algal fatty acids were converted to CO2 (preliminary data subject to change). The rate of labeled-OC remineralization was enhanced by the addition of a highly labile substrate (e.g. ethyl acetate). Likewise, constant measurements of O2/pCO2 along the lower river revealed anomalously high CO2 and low O2 levels near the confluence of the mainstem and large tributaries with high algal productivity. These collective results suggest that the remineralization of complex terrestrial macromolecules is a significant source of CO2 to tropical rivers, whereas algal-derived OC is primarily incorporated into the microbial loop/higher trophic levels and enhances the breakdown of more complex terrestrially-derived molecules (e.g. the "priming effect").

Eco-sustainable systems based on poly(lactic acid), diatomite and coffee grounds extract for food packaging.

PubMed

Cacciotti, Ilaria; Mori, Stefano; Cherubini, Valeria; Nanni, Francesca

2018-06-01

In the food packaging sector many efforts have been (and are) devoted to the development of new materials in order to reply to an urgent market demand for green and eco-sustainable products. Particularly a lot of attention is currently devoted both to the use of compostable and biobased polymers as innovative and promising alternative to the currently used petrochemical derived polymers, and to the re-use of waste materials coming from agriculture and food industry. In this work, multifunctional eco-sustainable systems, based on poly(lactic acid) (PLA) as biopolymeric matrix, diatomaceous earth as reinforcing filler and spent coffee grounds extract as oxygen scavenger, were produced for the first time, in order to provide a simultaneous improvement of mechanical and gas barrier properties. The influence of the diatomite and the spent coffee grounds extract on the microstructural, mechanical and oxygen barrier properties of the produced films was deeply investigated by means of X-Ray diffraction (XRD), infrared spectroscopy (FT-IR, ATR), scanning electron microscopy (SEM), uniaxial tensile tests, O 2 permeabilimetry measurements. An improvement of both mechanical and oxygen barrier properties was recorded for systems characterised by the co-presence of diatomite and coffee grounds extract, suggesting a possible synergic effect of the two additives. Copyright © 2018 Elsevier B.V. All rights reserved.

A Pilot Study to Evaluate California's Fossil Fuel CO2 Emissions Using Atmospheric Observations

NASA Astrophysics Data System (ADS)

Graven, H. D.; Fischer, M. L.; Lueker, T.; Guilderson, T.; Brophy, K. J.; Keeling, R. F.; Arnold, T.; Bambha, R.; Callahan, W.; Campbell, J. E.; Cui, X.; Frankenberg, C.; Hsu, Y.; Iraci, L. T.; Jeong, S.; Kim, J.; LaFranchi, B. W.; Lehman, S.; Manning, A.; Michelsen, H. A.; Miller, J. B.; Newman, S.; Paplawsky, B.; Parazoo, N.; Sloop, C.; Walker, S.; Whelan, M.; Wunch, D.

2016-12-01

Atmospheric CO2 concentration is influenced by human activities and by natural exchanges. Studies of CO2 fluxes using atmospheric CO2 measurements typically focus on natural exchanges and assume that CO2 emissions by fossil fuel combustion and cement production are well-known from inventory estimates. However, atmospheric observation-based or "top-down" studies could potentially provide independent methods for evaluating fossil fuel CO2 emissions, in support of policies to reduce greenhouse gas emissions and mitigate climate change. Observation-based estimates of fossil fuel-derived CO2 may also improve estimates of biospheric CO2 exchange, which could help to characterize carbon storage and climate change mitigation by terrestrial ecosystems. We have been developing a top-down framework for estimating fossil fuel CO2 emissions in California that uses atmospheric observations and modeling. California is implementing the "Global Warming Solutions Act of 2006" to reduce total greenhouse gas emissions to 1990 levels by 2020, and it has a diverse array of ecosystems that may serve as CO2 sources or sinks. We performed three month-long field campaigns in different seasons in 2014-15 to collect flask samples from a state-wide network of 10 towers. Using measurements of radiocarbon in CO2, we estimate the fossil fuel-derived CO2 present in the flask samples, relative to marine background air observed at coastal sites. Radiocarbon (14C) is not present in fossil fuel-derived CO2 because of radioactive decay over millions of years, so fossil fuel emissions cause a measurable decrease in the 14C/C ratio in atmospheric CO2. We compare the observations of fossil fuel-derived CO2 to simulations based on atmospheric modeling and published fossil fuel flux estimates, and adjust the fossil fuel flux estimates in a statistical inversion that takes account of several uncertainties. We will present the results of the top-down technique to estimate fossil fuel emissions for our field campaigns in California, and we will give an outlook for future development of the technique in California.

Transport and transformation of soil-derived CO2, CH4 and DOC sustain CO2 supersaturation in small boreal streams.

PubMed

Rasilo, Terhi; Hutchins, Ryan H S; Ruiz-González, Clara; Del Giorgio, Paul A

2017-02-01

Streams are typically supersaturated in carbon dioxide (CO 2 ) and methane (CH 4 ), and are recognized as important components of regional carbon (C) emissions in northern landscapes. Whereas there is consensus that in most of the systems the CO 2 emitted by streams represents C fixed in the terrestrial ecosystem, the pathways delivering this C to streams are still not well understood. We assessed the contribution of direct soil CO 2 injection versus the oxidation of soil-derived dissolved organic C (DOC) and CH 4 in supporting CO 2 supersaturation in boreal streams in Québec. We measured the concentrations of CO 2 , CH 4 and DOC in 43 streams and adjacent soil waters during summer base-flow period. A mass balance approach revealed that all three pathways are significant, and that the mineralization of soil-derived DOC and CH 4 accounted for most of the estimated stream CO 2 emissions (average 75% and 10%, respectively), and that these estimated contributions did not change significantly between the studied low order (≤3) streams. Whereas some of these transformations take place in the channel proper, our results suggest that they mainly occur in the hyporheic zones of the streams. Our results further show that stream CH 4 emissions can be fully explained by soil CH 4 inputs. This study confirms that these boreal streams, and in particular their hyporheic zones, are extremely active processors of soil derived DOC and CH 4 , not just vents for soil produced CO 2 . Copyright © 2016 Elsevier B.V. All rights reserved.

An analysis of geothermal and carbonic springs in the western United States sustained by deep fluid inputs.

PubMed

Colman, D R; Garcia, J R; Crossey, L J; Karlstrom, K; Jackson-Weaver, O; Takacs-Vesbach, C

2014-01-01

Hydrothermal springs harbor unique microbial communities that have provided insight into the early evolution of life, expanded known microbial diversity, and documented a deep Earth biosphere. Mesothermal (cool but above ambient temperature) continental springs, however, have largely been ignored although they may also harbor unique populations of micro-organisms influenced by deep subsurface fluid mixing with near surface fluids. We investigated the microbial communities of 28 mesothermal springs in diverse geologic provinces of the western United States that demonstrate differential mixing of deeply and shallowly circulated water. Culture-independent analysis of the communities yielded 1966 bacterial and 283 archaeal 16S rRNA gene sequences. The springs harbored diverse taxa and shared few operational taxonomic units (OTUs) across sites. The Proteobacteria phylum accounted for most of the dataset (81.2% of all 16S rRNA genes), with 31 other phyla/candidate divisions comprising the remainder. A small percentage (~6%) of bacterial 16S rRNA genes could not be classified at the phylum level, but were mostly distributed in those springs with greatest inputs of deeply sourced fluids. Archaeal diversity was limited to only four springs and was primarily composed of well-characterized Thaumarchaeota. Geochemistry across the dataset was varied, but statistical analyses suggested that greater input of deeply sourced fluids was correlated with community structure. Those with lesser input contained genera typical of surficial waters, while some of the springs with greater input may contain putatively chemolithotrophic communities. The results reported here expand our understanding of microbial diversity of continental geothermal systems and suggest that these communities are influenced by the geochemical and hydrologic characteristics arising from deeply sourced (mantle-derived) fluid mixing. The springs and communities we report here provide evidence for opportunities to understand new dimensions of continental geobiological processes where warm, highly reduced fluids are mixing with more oxidized surficial waters. © 2013 John Wiley & Sons Ltd.

A rhenium tris-carbonyl derivative as a model molecule for incorporation into phospholipid assemblies for skin applications.

PubMed

Fernández, Estibalitz; Rodríguez, Gelen; Hostachy, Sarah; Clède, Sylvain; Cócera, Mercedes; Sandt, Christophe; Lambert, François; de la Maza, Alfonso; Policar, Clotilde; López, Olga

2015-07-01

A rhenium tris-carbonyl derivative (fac-[Re(CO)3Cl(2-(1-dodecyl-1H-1,2,3,triazol-4-yl)-pyridine)]) was incorporated into phospholipid assemblies, called bicosomes, and the penetration of this molecule into skin was monitored using Fourier-transform infrared microspectroscopy (FTIR). To evaluate the capacity of bicosomes to promote the penetration of this derivative, the skin penetration of the Re(CO)3 derivative dissolved in dimethyl sulfoxide (DMSO), a typical enhancer, was also studied. Dynamic light scattering results (DLS) showed an increase in the size of the bicosomes with the incorporation of the Re(CO)3 derivative, and the FTIR microspectroscopy showed that the Re(CO)3 derivative incorporated in bicosomes penetrated deeper into the skin than when dissolved in DMSO. When this molecule was applied on the skin using the bicosomes, 60% of the Re(CO)3 derivative was retained in the stratum corneum (SC) and 40% reached the epidermis (Epi). Otherwise, the application of this molecule via DMSO resulted in 95% of the Re(CO)3 derivative being in the SC and only 5% reaching the Epi. Using a Re(CO)3 derivative with a dodecyl-chain as a model molecule, it was possible to determine the distribution of molecules with similar physicochemical characteristics in the skin using bicosomes. This fact makes these nanostructures promising vehicles for the application of lipophilic molecules inside the skin. Copyright © 2015 Elsevier B.V. All rights reserved.

Integration of metagenomic and stable carbon isotope evidence reveals the extent and mechanisms of carbon dioxide fixation in high-temperature microbial communities

DOE PAGES

Jennings, Ryan de Montmollin; Moran, James J.; Jay, Zackary J.; ...

2017-02-03

Biological fixation of CO 2 is the primary mechanism of C reduction in natural systems, and provides a diverse suite of organic compounds utilized by chemoorganoheterotrophs. The extent and mechanisms of CO 2 fixation were evaluated across a comprehensive set of high-temperature, chemotrophic microbial communities in Yellowstone National Park by combining metagenomic and stable 13C isotope analyses. Fifteen geothermal sites representing three distinct habitat types (iron-oxide mats, anoxic sulfur sediments, and filamentous ‘streamer’ communities) were investigated. Genes of the 3-hydroxypropionate/4-hydroxybutyrate, dicarboxylate/4-hydroxybutyrate, and reverse tricarboxylic acid CO 2 fixation pathways were identified in assembled genome sequence corresponding to the predominant Crenarchaeotamore » and Aquificales observed across this habitat range. Stable 13C analyses of dissolved inorganic and organic C (DIC, DOC), and possible landscape C sources were used to interpret the 13C content of microbial community samples. Isotope mixing models showed that the minimum amounts of autotrophic C in microbial biomass were > 50 % in the majority of communities analyzed, but were also dependent on the amounts of heterotrophy and/or accumulation of landscape C. Furthermore, the significance of CO 2 as a C source in these communities provides a foundation for understanding metabolic linkages among autotrophs and heterotrophs, community assembly and succession, and the likely coevolution of deeply-branching thermophiles.« less

Sensitivity of mesquite shrubland CO2 exchange to precipitation in contrasting landscape settings.

PubMed

Potts, Daniel L; Scott, Russell L; Cable, Jessica M; Huxman, Travis E; Williams, David G

2008-10-01

In semiarid ecosystems, physiography (landscape setting) may interact with woody-plant and soil microbe communities to constrain seasonal exchanges of material and energy at the ecosystem scale. In an upland and riparian shrubland, we examined the seasonally dynamic linkage between ecosystem CO2 exchange, woody-plant water status and photosynthesis, and soil respiration responses to summer rainfall. At each site, we compared tower-based measurements of net ecosystem CO2 exchange (NEE) with ecophysiological measurements among velvet mesquite (Prosopis velutina Woot.) in three size classes and soil respiration in sub-canopy and inter-canopy micro-sites. Monsoonal rainfall influenced a greater shift in the magnitude of ecosystem CO2 assimilation in the upland shrubland than in the riparian shrubland. Mesquite water status and photosynthetic gas exchange were closely linked to the onset of the North American monsoon in the upland shrubland. In contrast, the presence of shallow alluvial groundwater in the riparian shrubland caused larger size classes of mesquite to be physiologically insensitive to monsoonal rains. In both shrublands, soil respiration was greatest beneath mesquite canopies and was coupled to shallow soil moisture abundance. Physiography, through its constraint on the physiological sensitivity of deeply rooted woody plants, may interact with plant-mediated rates of soil respiration to affect the sensitivity of semiarid-ecosystem carbon exchange in response to episodic rainfall.

On the relationship between ecosystem-scale hyperspectral reflectance and CO2 exchange in European mountain grasslands

NASA Astrophysics Data System (ADS)

Balzarolo, M.; Vescovo, L.; Hammerle, A.; Gianelle, D.; Papale, D.; Tomelleri, E.; Wohlfahrt, G.

2015-05-01

In this paper we explore the skill of hyperspectral reflectance measurements and vegetation indices (VIs) derived from these in estimating carbon dioxide (CO2) fluxes of grasslands. Hyperspectral reflectance data, CO2 fluxes and biophysical parameters were measured at three grassland sites located in European mountain regions using standardized protocols. The relationships between CO2 fluxes, ecophysiological variables, traditional VIs and VIs derived using all two-band combinations of wavelengths available from the whole hyperspectral data space were analysed. We found that VIs derived from hyperspectral data generally explained a large fraction of the variability in the investigated dependent variables but differed in their ability to estimate midday and daily average CO2 fluxes and various derived ecophysiological parameters. Relationships between VIs and CO2 fluxes and ecophysiological parameters were site-specific, likely due to differences in soils, vegetation parameters and environmental conditions. Chlorophyll and water-content-related VIs explained the largest fraction of variability in most of the dependent variables. Band selection based on a combination of a genetic algorithm with random forests (GA-rF) confirmed that it is difficult to select a universal band region suitable across the investigated ecosystems. Our findings have major implications for upscaling terrestrial CO2 fluxes to larger regions and for remote- and proximal-sensing sampling and analysis strategies and call for more cross-site synthesis studies linking ground-based spectral reflectance with ecosystem-scale CO2 fluxes.

The shear modulus of metastable amorphous solids with strong central and bond-bending interactions

NASA Astrophysics Data System (ADS)

Zaccone, Alessio

2009-07-01

We derive expressions for the shear modulus of deeply quenched, glassy solids, in terms of a Cauchy-Born free energy expansion around a rigid (quenched) reference state, following the approach due to Alexander (1998 Phys. Rep. 296 65). Continuum-limit explicit expressions of the shear modulus are derived starting from the microscopic Hamiltonians of central and bond-bending interactions. The applicability of the expressions to dense covalent glasses as well as colloidal glasses involving strongly attractive or adhesive bonds is discussed.

Temperatures of dust and gas in S 140

NASA Astrophysics Data System (ADS)

Koumpia, E.; Harvey, P. M.; Ossenkopf, V.; van der Tak, F. F. S.; Mookerjea, B.; Fuente, A.; Kramer, C.

2015-08-01

Context. In dense parts of interstellar clouds (≥105 cm-3), dust and gas are expected to be in thermal equilibrium, being coupled via collisions. However, previous studies have shown that in the presence of intense radiation fields, the temperatures of the dust and gas may remain decoupled even at higher densities. Aims: The objective of this work is to study in detail the temperatures of dust and gas in the photon-dominated region S 140, especially around the deeply embedded infrared sources IRS 1-3 and at the ionization front. Methods: We derive the dust temperature and column density by combining Herschel-PACS continuum observations with SOFIA observations at 37 μm and SCUBA data at 450 μm. We model these observations using simple greybody fits and the DUSTY radiative transfer code. For the gas analysis we use RADEX to model the CO 1-0, CO 2-1, 13CO 1-0 and C18O 1-0 emission lines mapped with the IRAM-30 m telescope over a 4' field. Around IRS 1-3, we use HIFI observations of single-points and cuts in CO 9-8, 13CO 10-9 and C18O 9-8 to constrain the amount of warm gas, using the best fitting dust model derived with DUSTY as input to the non-local radiative transfer model RATRAN. The velocity information in the lines allows us to separate the quiescent component from outflows when deriving the gas temperature and column density. Results: We find that the gas temperature around the infrared sources varies between ~35 and ~55 K. In contrast to expectation, the gas is systematically warmer than the dust by ~5-15 K despite the high gas density. In addition we observe an increase of the gas temperature from 30-35 K in the surrounding up to 40-45 K towards the ionization front, most likely due to the UV radiation from the external star. Furthermore, detailed models of the temperature structure close to IRS 1 which take the known density gradient into account show that the gas is warmer and/or denser than what we model. Finally, modelling of the dust emission from the sub-mm peak SMM 1 constrains its luminosity to a few ×102L⊙. Conclusions: We conclude that the gas heating in the S 140 region is very efficient even at high densities. The most likely explanation is deep UV penetration from the embedded sources in a clumpy medium and/or oblique shocks. Based on Herschel observations. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.Final Herschel and IRAM data (cube) as FITS files are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/580/A68

Applications of several spectral techniques to characterize coordination compounds derived from 2,6-diacetylpyridine derivative

NASA Astrophysics Data System (ADS)

Chandra, Sulekh; Sharma, Amit Kumar

2009-09-01

The coordination compounds of Cr III, Mn II and Co II metal ions derived from quinquedentate 2,6-diacetylpyridine derivative have been synthesized and characterized by using the various physicochemical studies like stoichiometric, molar conductivity and magnetic, and spectral techniques like IR, NMR, mass, UV and EPR. The general stoichiometries of the complexes are found to be [Cr(H 2L)X] and [M(HL)X], where M = Mn(II) and Co(II); H 2L = dideprotonated ligand, HL = monodeprotonated ligand and X = NO 3-, Cl - and OAc -. The studies reveal that the complexes possess monomeric compositions with six coordinated octahedral geometry (Cr III and Mn II complexes) and six coordinated tetragonal geometry (Co II complexes).

Granular bamboo-derived activated carbon for high CO(2) adsorption: the dominant role of narrow micropores.

PubMed

Wei, Haoran; Deng, Shubo; Hu, Bingyin; Chen, Zhenhe; Wang, Bin; Huang, Jun; Yu, Gang

2012-12-01

Cost-effective biomass-derived activated carbons with a high CO(2) adsorption capacity are attractive for carbon capture. Bamboo was found to be a suitable precursor for activated carbon preparation through KOH activation. The bamboo size in the range of 10-200 mesh had little effect on CO(2) adsorption, whereas the KOH/C mass ratio and activation temperature had a significant impact on CO(2) adsorption. The bamboo-derived activated carbon had a high adsorption capacity and excellent selectivity for CO(2) , and also the adsorption process was highly reversible. The adsorbed amount of CO(2) on the granular activated carbon was up to 7.0 mmol g(-1) at 273 K and 1 bar, which was higher than almost all carbon materials. The pore characteristics of activated carbons responsible for high CO(2) adsorption were fully investigated. Based on the analysis of narrow micropore size distribution of several activated carbons prepared under different conditions, a more accurate micropore range contributing to CO(2) adsorption was proposed. The volume of micropores in the range of 0.33-0.82 nm had a good linear relationship with CO(2) adsorption at 273 K and 1 bar, and the narrow micropores of about 0.55 nm produced the major contribution, which could be used to evaluate CO(2) adsorption on activated carbons. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using CO2:CO Correlations to Improve Inverse Analyses of Carbon Fluxes

NASA Technical Reports Server (NTRS)

Palmer, Paul I.; Suntharalingam, Parvadha; Jones, Dylan B. A.; Jacob, Daniel J.; Streets, David G.; Fu, Qingyan; Vay, Stephanie A.; Sachse, Glen W.

2006-01-01

Observed correlations between atmospheric concentrations of CO2 and CO represent potentially powerful information for improving CO2 surface flux estimates through coupled CO2-CO inverse analyses. We explore the value of these correlations in improving estimates of regional CO2 fluxes in east Asia by using aircraft observations of CO2 and CO from the TRACE-P campaign over the NW Pacific in March 2001. Our inverse model uses regional CO2 and CO surface fluxes as the state vector, separating biospheric and combustion contributions to CO2. CO2-CO error correlation coefficients are included in the inversion as off-diagonal entries in the a priori and observation error covariance matrices. We derive error correlations in a priori combustion source estimates of CO2 and CO by propagating error estimates of fuel consumption rates and emission factors. However, we find that these correlations are weak because CO source uncertainties are mostly determined by emission factors. Observed correlations between atmospheric CO2 and CO concentrations imply corresponding error correlations in the chemical transport model used as the forward model for the inversion. These error correlations in excess of 0.7, as derived from the TRACE-P data, enable a coupled CO2-CO inversion to achieve significant improvement over a CO2-only inversion for quantifying regional fluxes of CO2.

Important role of calcium chloride in preventing carbon monoxide generation during desflurane degradation with alkali hydroxide-free carbon dioxide absorbents.

PubMed

Ando, Takahiro; Mori, Atsushi; Ito, Rie; Nishiwaki, Kimitoshi

2017-12-01

We investigated whether calcium chloride (CaCl 2 ), a supplementary additive in carbon dioxide (CO 2 ) absorbents, could affect carbon monoxide (CO) production caused by desflurane degradation, using a Japanese alkali-free CO 2 absorbent Yabashi Lime ® -f (YL-f), its CaCl 2 -free and 1% CaCl 2 -added derivatives, and other commercially available alkali-free absorbents with or without CaCl 2 . The reaction between 1 L of desflurane gas (3-10%) and 20 g of desiccated specimen was performed in an artificial closed-circuit anesthesia system for 3 min at 20 or 40 °C. The CO concentration was measured using a gas chromatograph equipped with a semiconductor sensor detector. The systems were validated by detecting dose-dependent CO production with an alkali hydroxide-containing CO 2 absorbent, Sodasorb ® . Compared with YL-f, the CaCl 2 -free derivative caused the production of significantly more CO, while the 1% CaCl 2 -added derivative caused the production of a comparable amount of CO. These phenomena were confirmed using commercially available absorbents AMSORB ® PLUS, an alkali-free absorbent with CaCl 2 , and LoFloSorb™, an alkali-free absorbent without CaCl 2 . These results suggest that CaCl 2 plays an important role in preventing CO generation caused by desflurane degradation with alkali hydroxide-free CO 2 absorbents like YL-f.

Tandem mass spectrometry measurement of the collision products of carbamate anions derived from CO2 capture sorbents: paving the way for accurate quantitation.

PubMed

Jackson, Phil; Fisher, Keith J; Attalla, Moetaz Ibrahim

2011-08-01

The reaction between CO(2) and aqueous amines to produce a charged carbamate product plays a crucial role in post-combustion capture chemistry when primary and secondary amines are used. In this paper, we report the low energy negative-ion CID results for several anionic carbamates derived from primary and secondary amines commonly used as post-combustion capture solvents. The study was performed using the modern equivalent of a triple quadrupole instrument equipped with a T-wave collision cell. Deuterium labeling of 2-aminoethanol (1,1,2,2,-d(4)-2-aminoethanol) and computations at the M06-2X/6-311++G(d,p) level were used to confirm the identity of the fragmentation products for 2-hydroxyethylcarbamate (derived from 2-aminoethanol), in particular the ions CN(-), NCO(-) and facile neutral losses of CO(2) and water; there is precedent for the latter in condensed phase isocyanate chemistry. The fragmentations of 2-hydroxyethylcarbamate were generalized for carbamate anions derived from other capture amines, including ethylenediamine, diethanolamine, and piperazine. We also report unequivocal evidence for the existence of carbamate anions derived from sterically hindered amines (Tris(2-hydroxymethyl)aminomethane and 2-methyl-2-aminopropanol). For the suite of carbamates investigated, diagnostic losses include the decarboxylation product (-CO(2), 44 mass units), loss of 46 mass units and the fragments NCO(-) (m/z 42) and CN(-) (m/z 26). We also report low energy CID results for the dicarbamate dianion ((-)O(2)CNHC(2)H(4)NHCO(2)(-)) commonly encountered in CO(2) capture solution utilizing ethylenediamine. Finally, we demonstrate a promising ion chromatography-MS based procedure for the separation and quantitation of aqueous anionic carbamates, which is based on the reported CID findings. The availability of accurate quantitation methods for ionic CO(2) capture products could lead to dynamic operational tuning of CO(2) capture-plants and, thus, cost-savings via real-time manipulation of solvent regeneration energies.

Constraining the physical structure of the inner few 100 AU scales of deeply embedded low-mass protostars

NASA Astrophysics Data System (ADS)

Persson, M. V.; Harsono, D.; Tobin, J. J.; van Dishoeck, E. F.; Jørgensen, J. K.; Murillo, N.; Lai, S.-P.

2016-05-01

Context. The physical structure of deeply embedded low-mass protostars (Class 0) on scales of less than 300 AU is still poorly constrained. While molecular line observations demonstrate the presence of disks with Keplerian rotation toward a handful of sources, others show no hint of rotation. Determining the structure on small scales (a few 100 AU) is crucial for understanding the physical and chemical evolution from cores to disks. Aims: We determine the presence and characteristics of compact, disk-like structures in deeply embedded low-mass protostars. A related goal is investigating how the derived structure affects the determination of gas-phase molecular abundances on hot-core scales. Methods: Two models of the emission, a Gaussian disk intensity distribution and a parametrized power-law disk model, are fitted to subarcsecond resolution interferometric continuum observations of five Class 0 sources, including one source with a confirmed Keplerian disk. Prior to fitting the models to the de-projected real visibilities, the estimated envelope from an independent model and any companion sources are subtracted. For reference, a spherically symmetric single power-law envelope is fitted to the larger scale emission (~1000 AU) and investigated further for one of the sources on smaller scales. Results: The radii of the fitted disk-like structures range from ~90-170 AU, and the derived masses depend on the method. Using the Gaussian disk model results in masses of 54-556 × 10-3 M⊙, and using the power-law disk model gives 9-140 × 10-3 M⊙. While the disk radii agree with previous estimates the masses are different for some of the sources studied. Assuming a typical temperature distribution (r-0.5), the fractional amount of mass in the disk above 100 K varies from 7% to 30%. Conclusions: A thin disk model can approximate the emission and physical structure in the inner few 100 AU scales of the studied deeply embedded low-mass protostars and paves the way for analysis of a larger sample with ALMA. Kinematic data are needed to determine the presence of any Keplerian disk. Using previous observations of p-H218O, we estimate the relative gas phase water abundances relative to total warm H2 to be 6.2 × 10-5 (IRAS 2A), 0.33 × 10-5 (IRAS 4A-NW), 1.8 × 10-7 (IRAS 4B), and < 2 × 10-7 (IRAS 4A-SE), roughly an order of magnitude higher than previously inferred when both warm and cold H2 were used as reference. A spherically symmetric single power-law envelope model fails to simultaneously reproduce both the small- and large-scale emission. Based on observations carried out with the IRAM Plateau de Bure Interferometer. IRAM is supported by INSU/CNRS (France), MPG (Germany) and IGN (Spain).Continuum data for the sources are available through http://dx.doi.org/10.5281/zenodo.47642 and at CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/590/A33

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2--The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates.

PubMed

Luca, Oana R; Fenwick, Aidan Q

2015-11-01

The present review covers organic transformations involved in the reduction of CO2 to chemical fuels. In particular, we focus on reactions of CO2 with organic molecules to yield carboxylic acid derivatives as a first step in CO2 reduction reaction sequences. These biomimetic initial steps create opportunities for tandem electrochemical/chemical reductions. We draw parallels between long-standing knowledge of CO2 reactivity from organic chemistry, organocatalysis, surface science and electrocatalysis. We point out some possible non-faradaic chemical reactions that may contribute to product distributions in the production of solar fuels from CO2. These reactions may be accelerated by thermal effects such as resistive heating and illumination. Copyright © 2015 Elsevier B.V. All rights reserved.

Carbonate-mediated Fe(II) oxidation in the air-cathode fuel cell: a kinetic model in terms of Fe(II) speciation.

PubMed

Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi; Sun, Min; Jiang, Yuan

2013-06-06

Due to the high redox activity of Fe(II) and its abundance in natural waters, the electro-oxidation of Fe(II) can be found in many air-cathode fuel cell systems, such as acid mine drainage fuel cells and sediment microbial fuel cells. To deeply understand these iron-related systems, it is essential to elucidate the kinetics and mechanisms involved in the electro-oxidation of Fe(II). This work aims to develop a kinetic model that adequately describes the electro-oxidation process of Fe(II) in air-cathode fuel cells. The speciation of Fe(II) is incorporated into the model, and contributions of individual Fe(II) species to the overall Fe(II) oxidation rate are quantitatively evaluated. The results show that the kinetic model can accurately predict the electro-oxidation rate of Fe(II) in air-cathode fuel cells. FeCO3, Fe(OH)2, and Fe(CO3)2(2-) are the most important species determining the electro-oxidation kinetics of Fe(II). The Fe(II) oxidation rate is primarily controlled by the oxidation of FeCO3 species at low pH, whereas at high pH Fe(OH)2 and Fe(CO3)2(2-) are the dominant species. Solution pH, carbonate concentration, and solution salinity are able to influence the electro-oxidation kinetics of Fe(II) through changing both distribution and kinetic activity of Fe(II) species.

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

The U.S. Department of Energy's (DOE) Co-Optimization of Fuels & Engines (Co-Optima) initiative is accelerating the introduction of affordable, scalable, and sustainable fuels and high-efficiency, low-emission engines with a first-of-its-kind effort to simultaneously tackle fuel and engine research and development (R&D). This report summarizes accomplishments in the first year of the project. Co-Optima is conducting concurrent research to identify the fuel properties and engine design characteristics needed to maximize vehicle performance and affordability, while deeply cutting emissions. Nine national laboratories - the National Renewable Energy Laboratory and Argonne, Idaho, Lawrence Berkeley, Lawrence Livermore, Los Alamos, Oak Ridge, Pacific Northwest, andmore » Sandia National Laboratories - are collaborating with industry and academia on this groundbreaking research.« less

Mineral precipitation in north slope aufeis

NASA Technical Reports Server (NTRS)

Hall, D. K.

1978-01-01

The Canning and Shaviovik river aufeis fields were studied on the ground and with aircraft data. Powdered calcium carbonate (CaCO3) patches, a few cm in thickness, were found in discrete locations on both aufeis fields. This is indicative of chemical weathering of limestone bedrock which is known to underlie much of the eastern arctic coastal plain of Alaska. Spring or river water which remains unfrozen throughout much of the winter carries CaCO3 in solution; as the river ice freezes more deeply the CaCO3 in solution is forced upwards through cracks in the river ice. Upon exposure to the cold air CaCO3 is excluded as the water freezes, forming successive layers during aufeis growth. In the melt season CaCO3, slush/powder accumulates in patches on top of the ice as the aufeis melts downward.

Effect of CH4 on the CO2 breakthrough pressure and permeability of partially saturated low-permeability sandstone in the Ordos Basin, China

NASA Astrophysics Data System (ADS)

Zhao, Yan; Yu, Qingchun

2018-01-01

The behavior of CO2 that coexists with CH4 and the effect of CH4 on the CO2 stream need to be deeply analyzed and studied, especially in the presence of water. Our previous studies investigated the breakthrough pressure and permeability of pure CO2 in five partially saturated low-permeability sandstone core samples from the Ordos Basin, and we concluded that rocks with a small pore size and low permeability show considerable sealing capacity even under unsaturated conditions. In this paper, we selected three of these samples for CO2-CH4 gas-mixture breakthrough experiments under various degrees of water saturation. The breakthrough experiments were performed by increasing the gas pressure step by step until breakthrough occurred. Then, the effluent gas mixture was collected for chromatographic partitioning analysis. The results indicate that CH4 significantly affects the breakthrough pressure and permeability of CO2. The presence of CH4 in the gas mixture increases the interfacial tension and, thus, the breakthrough pressure. Therefore, the injected gas mixture that contains the highest (lowest) mole fraction of CH4 results in the largest (smallest) breakthrough pressure. The permeability of the gas mixture is greater than that for pure CO2 because of CH4, and the effective permeability decreases with increased breakthrough pressure. Chromatographic partitioning of the effluent mixture gases indicates that CH4 breaks through ahead of CO2 as a result of its weaker solubility in water. Correlations are established between (1) the breakthrough pressure and water saturation, (2) the effective permeability and water saturation, (3) the breakthrough pressure and effective permeability, and (4) the mole fraction of CO2/CH4 in the effluent mixture gases and water saturation. These results deepen our understanding of the multi-phase flow behavior in the porous media under unsaturated conditions, which have implications for formulating emergency response plans for gas leakage into unsaturated zones. Finally, knowing the flow characteristic of gas mixture can guide CO2 storage, CO2-EOR and CO2-ECBM projects. Future studies should pay attention to the effects of saline water with different salt types and concentrations on the multi-phase flow behavior with applications to geological CO2 storage and energy storage using CH4.

Catalysis on Mo(CO)/sub 6/-derived supported molybdenum catalysts: CO oxidation with N/sub 2/O

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

Kazusaka, A.; Howe, R.F.

1988-05-01

The catalytic nature of Mo(CO)/sub 6/ supported on ..gamma..-Al/sub 2/O/sub 3/, KOH-doped ..gamma..-Al/sub 2/O/sub 3/, and HY-zeolite was investigated in CO oxidation with N/sub 2/O in comparison with that of a conventional partially reduced MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst. Kinetic parameters of this reaction were obtained in the range 0 to 100/sup 0/C; the rate law r = kP/sub N/sub 2/O//sup 1/P/sub CO//sup 0/ was found on all catalysts, and the activation energy was estimated to be 9.1 kcal/mol on the Mo(CO)/sub 6/-derived catalysts and 7.1 kcal/mol on the partially reduced MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst. Maximum catalytic activities weremore » obtained by activating the Mo(CO)/sub 6/-derived catalysts at 400/sup 0/C. To obtain similar activity on the MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst, it was necessary to reduce at 600/sup 0/C. The former catalysts were deactivated on repeating the reaction. On the basis of these results and those of ESR studies through the activation or deactivation process, an active site on the Mo(CO)/sub 6/-derived catalysts has been proposed. Also, clear IR absorption bands due to chemisorbed CO and N/sub 2/O species were observed on the HY-zeolite-supported catalysts. A reaction mechanism is proposed from the kinetic and IR spectroscopic results.« less

Far-ultraviolet fluorescence of carbon monoxide in the red giant Arcturus. II - Analysis of high-dispersion IUE spectra

NASA Technical Reports Server (NTRS)

Ayres, T. R.

1986-01-01

Faint, diffuse emissions near 1380 A in deeply exposed IUE spectrograms of the red giant Arcturus very likely are associated with bands of the A-X fourth-positive system of carbon monoxide, fluoresced by multiplet UV2 of neutral oxygen near 1305 A. Numerical simulations indicate that the strength of the CO bands is exceedingly sensitive, in the best available one-dimensional model of the chromosphere of Arcturus, to a delicate balance between the rapid inward attenuation of the oxygen radiation field and the rapid outward decline of the molecular absorptivity. The fortuitous character of the overlap region in the single-component model argues that one should also consider the possibility that the pumping occurs in a highly inhomogeneous chromosphere, of the type proposed in previous studies of Arcturus based on observations of the infrared absorption bands of CO.

In Situ Fabrication and Reactivation of Highly Selective and Stable Ag Catalysts for Electrochemical CO2 Conversion.

PubMed

Ma, Ming; Liu, Kai; Shen, Jie; Kas, Recep; Smith, Wilson A

2018-06-08

In this work, the highly selective and stable electrocatalytic reduction of CO 2 to CO on nanostructured Ag electrocatalysts is presented. The Ag electrocatalysts are synthesized by the electroreduction of Ag 2 CO 3 formed by in situ anodic-etching of Ag foil in a KHCO 3 electrolyte. After 3 min of this etching treatment, the Ag 2 CO 3 -derived nanostructured Ag electrocatalysts are capable of producing CO with up to 92% Faradaic efficiency at an overpotential as low as 290 mV, which surpasses all of the reported Ag catalysts at identical conditions to date. In addition, the anodic-etched Ag retained ∼90% catalytic selectivity in the electroreduction of CO 2 to CO for more than 100 h. The Ag 2 CO 3 -derived Ag is able to facilitate the activation of CO 2 via reduction of the activation energy barrier of the initial electron transfer and provide an increased number of active sites, resulting in the dramatically improved catalytic activity for the reduction of CO 2 to CO.

Search for Daemons with Nemesis

NASA Astrophysics Data System (ADS)

Bernabei, R.; Belli, P.; Cappella, F.; Cerulli, R.; D'Angelo, A.; Emiliani, F.; Incicchitti, A.

2012-03-01

The DAEMONs (DArk Electric Matter Objects) have been suggested as a possible exotic component in cosmic rays able to contribute to the Dark Matter; they belong to the wide class of the Elementary Black Holes (EBH) deeply discussed in literature. A preliminary possible DAEMONs direct detection, at ≃3σ C.L., was originally suggested by the sea-level St. Petersburg experiment (SPb); a DAEMONs flux: (1.0±0.3) DAEMONs/(days m2 sr) can be derived. Here the results obtained by the sea-level NEMESIS experiment, which has exploited the same detection approach, are presented; they restrict the DAEMONs flux to be less than 0.32 DAEMONs/(days m2 sr) at 90% C.L.

A doping technique that suppresses undesirable H2 evolution derived from overall water splitting in the highly selective photocatalytic conversion of CO2 in and by water.

PubMed

Teramura, Kentaro; Wang, Zheng; Hosokawa, Saburo; Sakata, Yoshihisa; Tanaka, Tsunehiro

2014-08-04

Photocatalytic conversion of CO2 to reduction products, such as CO, HCOOH, HCHO, CH3OH, and CH4, is one of the most attractive propositions for producing green energy by artificial photosynthesis. Herein, we found that Ga2O3 photocatalysts exhibit high conversion of CO2. Doping of Zn species into Ga2O3 suppresses the H2 evolution derived from overall water splitting and, consequently, Zn-doped, Ag-modified Ga2O3 exhibits higher selectivity toward CO evolution than bare, Ag-modified Ga2O3. We observed stoichiometric amounts of evolved O2 together with CO. Mass spectrometry clarified that the carbon source of the evolved CO is not the residual carbon species on the photocatalyst surface, but the CO2 introduced in the gas phase. Doping of the photocatalyst with Zn is expected to ease the adsorption of CO2 on the catalyst surface. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Benzoate Acid-Dependent Lattice Dimension of Co-MOFs and MOF-Derived CoS2@CNTs with Tunable Pore Diameters for Supercapacitors.

PubMed

Zou, Kang-Yu; Liu, Yi-Chen; Jiang, Yi-Fan; Yu, Cheng-Yan; Yue, Man-Li; Li, Zuo-Xi

2017-06-05

Herein three novel cobalt metal-organic frameworks (Co-MOFs) with similar ingredients, [Co(bib)(o-bdc)] ∞ (1), [Co 2 (bib) 2 (m-bdc) 2 ] ∞ (2), and {[Co(bib)(p-bdc)(H 2 O)](H 2 O) 0.5 } ∞ (3), have been synthesized from the reaction of cobalt nitrate with 1,4-bis(imidazol-1-yl)benzene (bib) and structure-related aromatic acids (1,2-benzenedicarboxylic acid = o-bdc, 1,3-benzenedicarboxylic acid = m-bdc, and 1,4-benzenedicarboxylic acid = p-bdc) by the solvothermal method. It is aimed to perform systematic research on the relationship among the conformation of benzoate acid, lattice dimension of Co-MOF, and pore diameter of MOF-derived carbon composite. Through the precursor strategy, Co-MOFs 1-3 have been utilized to synthesize porous cobalt@carbon nanotube composites (Co@CNTs). After the in situ gas-sulfurization, secondary composites CoS 2 @CNTs were successfully obtained, which kept similar morphologies of corresponding Co@CNTs without destroying previous highly dispersed structures. Co-MOFs and two series of composites (Co@CNTs and CoS 2 @CNTs) have been well characterized. Topology and Brunauer-Emmett-Teller analyses elucidate that the bdc 2- ion could control the pore diameters of MOF-derived carbon composites by adjusting the lattice dimension of Co-MOFs. The systematic studies on electrochemical properties demonstrate that (p)-CoS 2 @CNT possesses hierarchical morphology, moderate specific surface area, proper pore diameter distribution, and high graphitization, which lead to remarkable specific capacitances (839 F g -1 at 5 mV s -1 and 825 F g -1 at 0.5 A g -1 ) in 2 M potassium hydroxide solution. In addition, the (p)-CoS 2 @CNT electrode exhibits good electrochemical stability and still retains 82.9% of initial specific capacitance at the current density of 1 A g -1 after 5000 cycles.

40 CFR 98.38 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 0.138 74.49 Fossil fuel-derived fuels (solid) mmBtu/short ton kg CO2/mmBtu Municipal Solid Waste 1 9.95 90.7 Tires 26.87 85.97 Fossil fuel-derived fuels (gaseous) mmBtu/scf kg CO2/mmBtu Blast Furnace...

Human induced pluripotent stem cell (hiPSC)-derived neurons respond to convulsant drugs when co-cultured with hiPSC-derived astrocytes.

PubMed

Ishii, Misawa Niki; Yamamoto, Koji; Shoji, Masanobu; Asami, Asano; Kawamata, Yuji

2017-08-15

Accurate risk assessment for drug-induced seizure is expected to be performed before entering clinical studies because of its severity and fatal damage to drug development. Induced pluripotent stem cell (iPSC) technology has allowed the use of human neurons and glial cells in toxicology studies. Recently, several studies showed the advantage of co-culture system of human iPSC (hiPSC)-derived neurons with rodent/human primary astrocytes regarding neuronal functions. However, the application of hiPSC-derived neurons for seizure risk assessment has not yet been fully addressed, and not at all when co-cultured with hiPSC-derived astrocytes. Here, we characterized hiPSC-derived neurons co-cultured with hiPSC-derived astrocytes to discuss how hiPSC-derived neurons are useful to assess seizure risk of drugs. First, we detected the frequency of spikes and synchronized bursts hiPSC-derived neurons when co-cultured with hiPSC-derived astrocytes for 8 weeks. This synchronized burst was suppressed by the treatment with 6-cyano-7-nitroquinoxaline-2,3-dione, α-amino-3-hydroxy-5-methylisoxazole-4-propionic acid (AMPA) receptor antagonist, and D-(-)-2-amino-5-phosphonopentanoic acid, an N-Methyl-d-aspartate (NMDA) receptor antagonist. These data suggested that co-cultured hiPSC-derived neurons formed synaptic connections mediated by AMPA and NMDA receptors. We also demonstrated that co-cultured hiPSC-derived neurons showed epileptiform activity upon treatment with gabazine or kaliotoxin. Finally, we performed single-cell transcriptome analysis in hiPSC-derived neurons and found that hiPSC-derived astrocytes activated the pathways involved in the activities of AMPA and NMDA receptor functions, neuronal polarity, and axon guidance in hiPSC-derived neurons. These data suggested that hiPSC-derived astrocytes promoted the development of action potential, synaptic functions, and neuronal networks in hiPSC-derived neurons, and then these functional alterations result in the epileptiform activity in response to convulsant drugs. Our study indicates the possibility that co-culture system of hiPSC-derived neurons with hiPSC-derived astrocytes could be useful in the risk assessment of drug-induced seizure. Copyright © 2017 Elsevier B.V. All rights reserved.

Combined HQSAR, topomer CoMFA, homology modeling and docking studies on triazole derivatives as SGLT2 inhibitors.

PubMed

Yu, Shuling; Yuan, Jintao; Zhang, Yi; Gao, Shufang; Gan, Ying; Han, Meng; Chen, Yuewen; Zhou, Qiaoqiao; Shi, Jiahua

2017-06-01

Sodium-glucose cotransporter 2 (SGLT2) is a promising target for diabetes therapy. We aimed to develop computational approaches to identify structural features for more potential SGLT2 inhibitors. In this work, 46 triazole derivatives as SGLT2 inhibitors were studied using a combination of several approaches, including hologram quantitative structure-activity relationships (HQSAR), topomer comparative molecular field analysis (CoMFA), homology modeling, and molecular docking. HQSAR and topomer CoMFA were used to construct models. Molecular docking was conducted to investigate the interaction of triazole derivatives and homology modeling of SGLT2, as well as to validate the results of the HQSAR and topomer CoMFA models. The most effective HQSAR and topomer CoMFA models exhibited noncross-validated correlation coefficients of 0.928 and 0.891 for the training set, respectively. External predictions were made successfully on a test set and then compared with previously reported models. The graphical results of HQSAR and topomer CoMFA were proven to be consistent with the binding mode of the inhibitors and SGLT2 from molecular docking. The models and docking provided important insights into the design of potent inhibitors for SGLT2.

Effect of steam during Fischer–Tropsch Synthesis using biomass-derived syngas

Treesearch

Zi Wang; Khiet Mai; Nitin Kumar; Thomas Elder; Leslie H. Groom; James J. Spivey

2017-01-01

Fischer–Tropsch synthesis (FTS) with biomass- derived syngas was performed using both iron-based 100Fe/6Cu/4K/25Al catalyst and ruthenium-based 5 % Ru/SiO2 catalyst. During FTS, different concentrations of steam were co-fed with the biomass-derived syngas to promote the water gas shift reaction and increase the H2/ CO ratio...

The CO2 Abundance in Comets C2012 K1 (PanSTARRS), C2012 K5 (LINEAR), and 290P Jager as Measured with Spitzer

NASA Technical Reports Server (NTRS)

McKay, Adam J.; Kelley, Michael S.P.; Cochran, Anita L.; Bodewits, Dennis; DiSanti, Michael A.; Dello Russo, Neil; Lisse, Carey M.

2015-01-01

Carbon dioxide is one of the most abundant ices present in comets and is therefore important for understanding cometary composition and activity. We present analysis of observations of CO2 and [O I] emission in three comets to measure the CO2 abundance and evaluate the possibility of employing observations of [O I] emission in comets as a proxy for CO2. We obtained NIR imaging sensitive to CO2 of comets C/2012 K1 (PanSTARRS), C/2012 K5 (LINEAR), and 290P/Jager with the IRAC instrument on Spitzer. We acquired observations of [O I] emission in these comets with the ARCES echelle spectrometer mounted on the 3.5-m telescope at Apache Point Observatory and observations of OH with the Swift observatory (PanSTARRS) and with Keck HIRES (Jager). The CO2/H2O ratios derived from the Spitzer images are 12.6 +/- 1.3% (PanSTARRS), 28.9 +/- 3.6% (LINEAR), and 31.3 +/- 4.2% (Jager). These abundances are derived under the assumption that contamination from CO emission is negligible. The CO2 abundance for PanSTARRS is close to the average abundance measured in comets at similar heliocentric distance to date, while the abundances measured for LINEAR and Jager are significantly larger than the average abundance. From the coma morphology observed in PanSTARRS and the assumed gas expansion velocity, we derive a rotation period for the nucleus of about 9.2 h. Comparison of H2O production rates derived from ARCES and Swift data, as well as other observations, suggest the possibility of sublimation from icy grains in the inner coma. We evaluate the possibility that the [O I] emission can be employed as a proxy for CO2 by comparing CO2/H2O ratios inferred from the [O I] lines to those measured directly by Spitzer. We find that for PanSTARRS we can reproduce the observed CO2 abundance to an accuracy of approximately 20%. For LINEAR and Jager, we were only able to obtain upper limits on the CO2 abundance inferred from the [O I] lines. These upper limits are consistent with the CO2 abundances measured by Spitzer.

Delta13C values of grasses as a novel indicator of pollution by fossil-fuel-derived greenhouse gas CO2 in urban areas.

PubMed

Lichtfouse, Eric; Lichtfouse, Michel; Jaffrézic, Anne

2003-01-01

A novel fossil fuel pollution indicator based on the 13C/12C isotopic composition of plants has been designed. This bioindicator is a promising tool for future mapping of the sequestration of fossil fuel CO2 into urban vegetation. Theoretically, plants growing in fossil-fuel-CO2-contaminated areas, such as major cities, industrial centers, and highway borders, should assimilate a mixture of global atmospheric CO2 of delta13C value of -8.02 per thousand and of fossil fuel CO2 of average delta13C value of -27.28 per thousand. This isotopic difference should, thus, be recorded in plant carbon. Indeed, this study reveals that grasses growing near a major highway in Paris, France, have strikingly depleted delta13C values, averaging at -35.08 per thousand, versus rural grasses that show an average delta13C value of -30.59 per thousand. A simple mixing model was used to calculate the contributions of fossil-fuel-derived CO2 to the plant tissue. Calculation based on contaminated and noncontaminated isotopic end members shows that urban grasses assimilate up to 29.1% of fossil-fuel-CO2-derived carbon in their tissues. The 13C isotopic composition of grasses thus represents a promising new tool for the study of the impact of fossil fuel CO2 in major cities.

Disorder and Quantum Spin Ice

NASA Astrophysics Data System (ADS)

Martin, N.; Bonville, P.; Lhotel, E.; Guitteny, S.; Wildes, A.; Decorse, C.; Ciomaga Hatnean, M.; Balakrishnan, G.; Mirebeau, I.; Petit, S.

2017-10-01

We report on diffuse neutron scattering experiments providing evidence for the presence of random strains in the quantum spin-ice candidate Pr2Zr2O7 . Since Pr3 + is a non-Kramers ion, the strain deeply modifies the picture of Ising magnetic moments governing the low-temperature properties of this material. It is shown that the derived strain distribution accounts for the temperature dependence of the specific heat and of the spin-excitation spectra. Taking advantage of mean-field and spin-dynamics simulations, we argue that the randomness in Pr2Zr2O7 promotes a new state of matter, which is disordered yet characterized by short-range antiferroquadrupolar correlations, and from which emerge spin-ice-like excitations. Thus, this study gives an original research route in the field of quantum spin ice.

Significance for secure CO2 storage of earthquakes induced by fluid injection

NASA Astrophysics Data System (ADS)

Verdon, James P.

2014-05-01

The link between subsurface fluid injection and induced seismicity has gained recent significance with an increase in earthquakes associated with the disposal of oilfield waste fluids. There are obvious similarities between wastewater reinjection and proposed CO2 storage (CCS) operations. However, as well as the seismic hazard, induced seismicity during CCS operations poses additional risks, because an induced event located above the target reservoir could compromise the hydraulic integrity of the caprock. In this paper we re-examine case examples where earthquakes have been induced by wastewater injection into deep aquifers in the light of proposed future CCS operations. In particular we consider possible controls on event magnitudes, and look at the spatial distributions of events. We find that the majority of events are located below the target reservoirs. This is an encouraging observation from the perspective of caprock integrity, although it presents a challenge in terms of pre-injection characterization of deep-lying faults several kilometres below the target zone. We observe that 99% of events are found within 20 km of injection wells, suggesting a minimum radius for geomechanical characterization and monitoring. We conclude by making recommendations for modelling and monitoring strategies to be followed prior to and during commercial-scale deployment of CO2 storage projects.

Can We Monitor Ecosystem Function Using Keeling Plot Analyses of Nocturnal Cold-Air Drainage?

NASA Astrophysics Data System (ADS)

Bond, B. J.; Ocheltree, T.; Pypker, T.; Unsworth, M. H.; Mix, A. C.; William, R.

2003-12-01

The carbon isotope signature of ecosystem respiration, δ 13CR, as measured by the Keeling Plot approach, has been related to short-term variations in weather and ecosystem function in several recent studies. In order to obtain an adequate range of [CO2] and to sample a consistent vegetation type, investigators typically select sampling locations in relatively flat terrain and uniform canopy cover, but these are unusual conditions for many forested ecosystems. In a pilot study, we are collecting samples for Keeling Plot analyses in cold-air drainage systems in small (60-100 ha), deeply-incised watersheds, one covered with old-growth (ca 450-years-old) Douglas-fir/hemlock forest and one covered with young (ca 45-years-old) Douglas-fir forest. We found that the nightly range of [CO2] was typically 380-460 ppm, sufficient to develop good estimates of δ 13CR. At any point in time there was little variation in [CO2] with height through the canopy (0.5-30m), so the required range was obtained by sampling over several hours. There was no indication that samples taken from different heights or at different times of night represented sources with different isotopic signatures. The isotopic signature of respired CO2 in the older watershed averaged about 1 per mil greater than that of the young watershed, and δ 13CR of both locations correlated with modeled stomatal conductance 6 days prior to flask sampling.

FPGA Acceleration of the phylogenetic likelihood function for Bayesian MCMC inference methods.

PubMed

Zierke, Stephanie; Bakos, Jason D

2010-04-12

Likelihood (ML)-based phylogenetic inference has become a popular method for estimating the evolutionary relationships among species based on genomic sequence data. This method is used in applications such as RAxML, GARLI, MrBayes, PAML, and PAUP. The Phylogenetic Likelihood Function (PLF) is an important kernel computation for this method. The PLF consists of a loop with no conditional behavior or dependencies between iterations. As such it contains a high potential for exploiting parallelism using micro-architectural techniques. In this paper, we describe a technique for mapping the PLF and supporting logic onto a Field Programmable Gate Array (FPGA)-based co-processor. By leveraging the FPGA's on-chip DSP modules and the high-bandwidth local memory attached to the FPGA, the resultant co-processor can accelerate ML-based methods and outperform state-of-the-art multi-core processors. We use the MrBayes 3 tool as a framework for designing our co-processor. For large datasets, we estimate that our accelerated MrBayes, if run on a current-generation FPGA, achieves a 10x speedup relative to software running on a state-of-the-art server-class microprocessor. The FPGA-based implementation achieves its performance by deeply pipelining the likelihood computations, performing multiple floating-point operations in parallel, and through a natural log approximation that is chosen specifically to leverage a deeply pipelined custom architecture. Heterogeneous computing, which combines general-purpose processors with special-purpose co-processors such as FPGAs and GPUs, is a promising approach for high-performance phylogeny inference as shown by the growing body of literature in this field. FPGAs in particular are well-suited for this task because of their low power consumption as compared to many-core processors and Graphics Processor Units (GPUs).

Atmospheric carbon dioxide changes photochemical activity, soluble sugars and volatile levels in broccoli (Brassica oleracea var. italica).

PubMed

Krumbein, Angelika; Kläring, Hans-Peter; Schonhof, Ilona; Schreiner, Monika

2010-03-24

Atmospheric carbon dioxide (CO(2)) concentration is an environmental factor currently undergoing dramatic changes. The objective of the present study was to determine the effect of doubling the ambient CO(2) concentration on plant photochemistry as measured by photochemical quenching coefficient (qP), soluble sugars and volatiles in broccoli. Elevated CO(2) concentration increased qP values in leaves by up to 100% and 89% in heads, while glucose and sucrose in leaves increased by about 60%. Furthermore, in broccoli heads elevated CO(2) concentration induced approximately a 2-fold increase in concentrations of three fatty acid-derived C(7) aldehydes ((E)-2-heptenal, (E,Z)-2,4-heptadienal, (E,E)-2,4-heptadienal), two fatty acid-derived C(5) alcohols (1-penten-3-ol, (Z)-2-pentenol), and two amino acid-derived nitriles (phenyl propanenitrile, 3-methyl butanenitrile). In contrast, concentrations of the sulfur-containing compound 2-ethylthiophene and C(6) alcohol (E)-2-hexenol decreased. Finally, elevated CO(2) concentration increased soluble sugar concentrations due to enhanced photochemical activity in leaves and heads, which may account for the increased synthesis of volatiles.

TES/MLS Aura L2 Carbon Monoxide (CO) Nadir (TML2CO)

Atmospheric Science Data Center

2018-05-06

TES/MLS Aura L2 Carbon Monoxide (CO) Nadir (TML2CO) Atmospheric ... profile estimates and associated errors derived using TES & MLS spectral radiance measurements taken at nearest time and locations. ... a priori constraint vectors. News:  TES News Join TES News List Project Title:  TES ...

TES/MLS Aura L2 Carbon Monoxide (CO) Nadir (TML2CO)

Atmospheric Science Data Center

2018-05-07

TES/MLS Aura L2 Carbon Monoxide (CO) Nadir (TML2CO) ... profile estimates and associated errors derived using TES & MLS spectral radiance measurements taken at nearest time and locations. ... a priori constraint vectors. News:  TES News Join TES News List Project Title:  TES ...

Increased CO2 selectivity of asphalt-derived porous carbon through introduction of water into pore space

NASA Astrophysics Data System (ADS)

Jalilov, Almaz S.; Li, Yilun; Kittrell, Carter; Tour, James M.

2017-12-01

The development of inexpensive porous solid sorbents, such as porous carbons, that can selectively capture carbon dioxide (CO2) from natural gas wells is essential to reduce emission of CO2 to the atmosphere. However, at higher pressures, the selectivity for CO2 over that for methane (CH4) remains poor. Here we show that H2O can be imbibed within asphalt-derived porous carbon, with a surface area of 4,200 m2 g-1, to generate a hydrated powder material. While maintaining a high CO2 uptake capacity of 48 mmol g-1 (211 wt%), the molar selectivity for CO2 over CH4 increases to >200:1 and the H2O remains within the pores on repeated cycling. To mimic realistic natural gas wells, we used a 90% CH4 and 10% CO2 gas mixture and showed selective CO2 separation at 20 bar. Furthermore, in situ vibrational spectroscopy reveals the formation of an ordered matrix within the pores consisting of gas hydrates.

Control of the anisotropic shape of cobalt nanorods in the liquid phase: from experiment to theory... and back

NASA Astrophysics Data System (ADS)

Atmane, Kahina Aït; Michel, Carine; Piquemal, Jean-Yves; Sautet, Philippe; Beaunier, Patricia; Giraud, Marion; Sicard, Mickaël; Nowak, Sophie; Losno, Rémi; Viau, Guillaume

2014-02-01

The polyol process is one of the few methods allowing the preparation of metal nanoparticles in solution. Hexagonal close packed monocrystalline Co nanorods are easily obtained in basic 1,2-butanediol at 448 K after a few minutes using a Co(ii) dicarboxylate precursor. By using a combined experimental and theoretical approach, this study aims at a better understanding of the growth of anisotropic cobalt ferromagnetic nanoparticles by the polyol process. The growth of Co nanorods along the c axis of the hexagonal system was clearly evidenced by transmission electron microscopy, while the mean diameter was found to be almost constant at about 15 nm. Powder X-ray diffraction data showed that metallic cobalt was generated at the expense of a non-reduced solid lamellar intermediate phase which can be considered as a carboxylate ligand reservoir. Density functional theory calculations combined with a thermodynamic approach unambiguously showed that the main parameter governing the shape of the objects is the chemical potential of the carboxylate ligand: the crystal habit was deeply modified from rods to platelets when increasing the concentration of the ligand, i.e. its chemical potential. The approach presented in this study could be extended to a large number of particle types and growth conditions, where ligands play a key role in determining the particle shape.The polyol process is one of the few methods allowing the preparation of metal nanoparticles in solution. Hexagonal close packed monocrystalline Co nanorods are easily obtained in basic 1,2-butanediol at 448 K after a few minutes using a Co(ii) dicarboxylate precursor. By using a combined experimental and theoretical approach, this study aims at a better understanding of the growth of anisotropic cobalt ferromagnetic nanoparticles by the polyol process. The growth of Co nanorods along the c axis of the hexagonal system was clearly evidenced by transmission electron microscopy, while the mean diameter was found to be almost constant at about 15 nm. Powder X-ray diffraction data showed that metallic cobalt was generated at the expense of a non-reduced solid lamellar intermediate phase which can be considered as a carboxylate ligand reservoir. Density functional theory calculations combined with a thermodynamic approach unambiguously showed that the main parameter governing the shape of the objects is the chemical potential of the carboxylate ligand: the crystal habit was deeply modified from rods to platelets when increasing the concentration of the ligand, i.e. its chemical potential. The approach presented in this study could be extended to a large number of particle types and growth conditions, where ligands play a key role in determining the particle shape. Electronic supplementary information (ESI) available: Gas chromatograms of: (i) the as-received 1,2-butanediol solvent, (ii) the solvent treated under reflux in air after 24 h and (iii) the liquid phase after 10 min reaction at 448 K; theoretical results showing that the Co (011&cmb.macr;0) surface restructures itself into a Co (101&cmb.macr;0) surface for a 12-layer slab; adsorption modes of 1,2-butanediol on Co (101&cmb.macr;0) and (0001) surfaces. See DOI: 10.1039/c3nr03686c

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

Hlaing, Nwe Ni, E-mail: nwenihlaing76@gmail.com; Department of International Development Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo; Department of Physics, University of Yangon, 11041 Kamayut, Yangon

Recent years, CaO-based synthetic materials have been attracted attention as potential adsorbents for CO{sub 2} capture mainly due to their high CO{sub 2} adsorption capacity. In this study, micro/nanostructured aragonite CaCO{sub 3} was synthesized by a simple hydrothermal method with using polyacrylamide (PAM). The structural, morphological and thermal properties of the synthesized sample were investigated by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and thermogravimetry analysis (TG-DTA). The XRD and FESEM results showed that the obtained sample was aragonite CaCO{sub 3} with aggregated nanorods and microspheres composed of nanorods. A TG-DTA apparatus with Thermoplus 2 software was used tomore » investigate the effect of carbonation temperature on the CO{sub 2} adsorption capacity of CaO derived from aragonite CaCO{sub 3} sample. At 300 °C, the sample reached the CO{sub 2} adsorption capacity of 0.098 g-CO{sub 2}/g-adsorbent, whereas the sample achieved the highest capacity of 0.682 g-CO{sub 2}/g-adsorbent at 700 °C. The results showed that the carbonation temperature significantly influenced on the CO{sub 2} adsorption capacity of the CaO derived from aragonite CaCO{sub 3}.« less

How chemical information processing interferes with face processing: a magnetoencephalographic study.

PubMed

Walla, Peter; Mayer, Dagmar; Deecke, Lüder; Lang, Wilfried

2005-01-01

Magnetic field changes related to face encoding were recorded in 20 healthy young participants. Faces had to be deeply encoded under four kinds of simultaneous nasal chemical stimulation. Neutral room air, phenyl ethyl alcohol (PEA, rose flavor), carbon dioxide (CO2, pain), and hydrogen sulfide (H2S, rotten eggs flavor) were used as chemical stimuli. PEA and H2S represented odor stimuli, whereas CO2 was used for trigeminal stimulation (pain sensation). After the encoding of faces, the respective recognition performances were tested focusing on recognition effects related to specific chemical stimulation during encoding. The number of correctly recognized faces (hits) varied between chemical conditions. PEA stimulation during face encoding significantly increased the number of hits compared to the control condition. H2S also led to an increased mean number of hits, whereas simultaneous CO2 administration during face encoding resulted in a reduction. Analysis of the physiological data revealed two latency regions of interest. Compared to the control condition, both olfactory stimulus conditions resulted in reduced activity components peaking at about 260 ms after stimulus onset, whereas CO2 produced a strongly pronounced enhanced activity component peaking at about 700 ms after stimulus onset. Both olfactory conditions elicited only weak enhanced activities at about 700 ms, and CO2 did not show any difference activity at 260 ms after stimulus onset compared to the control condition. It is concluded that the early activity differences represent subconscious olfactory information processing leading to enhanced memory performances irrespective of the hedonic value, at least if they are only subconsciously processed. The later activity is suggested to reflect conscious CO2 perception negatively affecting face encoding and therefore leading to reduced subsequent face recognition. We interpret that conscious processing of nasal chemical stimulation competes with deep face encoding with respect to cortical resources, whereas subconscious processing of nasal chemical stimulation does not.

Biofuel Production from Jatropha Bio-Oil Derived Fast Pyrolysis: Effect and Mechanism of CoMoS Supported on Al2O3

NASA Astrophysics Data System (ADS)

Rodseanglung, T.; Ratana, T.; Phongaksorn, M.; Tungkamani, S.

2018-03-01

The aims of this research was to understand the CoMo/Al2O3 sulfide catalyst effect to remove oxygen-containing and nitrogen-containing molecules from Jatropha bio-oil derived fast pyrolysis converted to biofuels via hydrotreating process. The activity and selectivity of CoMo/γ-Al2O3 sulfided catalysts in hydrodeoxygenation (HDO) of Jatropha bio-oil derived fast pyrolysis was evaluated in a Parr batch reactor under 50 bar of H2 atmosphere for 2 h at 300 320 and 340 °C. It appeared that the CoMo/Al2O3 sulfide catalyst have high performance in activity for promoting the fatty acid, fatty ester, fatty amide and fatty nitrile compounds were converted to paraffin/olefin (Diesel range), this could be the CUS site on supported Al2O3 catalyst. The difference in selectivity products allowed us to propose a reaction scheme.

Chemistry of the oxophosphinidene ligand. 2. Reactivity of the anionic complexes [MCp{P(O)R*}(CO)(2)](-) (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3)) toward electrophiles based on elements different from carbon.

PubMed

Alonso, María; Alvarez, M Angeles; García, M Esther; Ruiz, Miguel A; Hamidov, Hayrullo; Jeffery, John C

2010-12-20

The anionic oxophosphinidene complexes (H-DBU)[MCp{P(O)R*}(CO)(2)] (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3); Cp = η(5)-C(5)H(5), DBU = 1,8-diazabicyclo [5.4.0] undec-7-ene) displayed multisite reactivity when faced with different electrophilic reagents. The reactions with the group 14 organochloride compounds ER(4-x)Cl(x) (E = Si, Ge, Sn, Pb) led to either phosphide-like, oxophosphinidene-bridged derivatives [MCp{P(OE')R*}(CO)(2)] (E' = SiMe(3), SiPh(3), GePh(3), GeMe(2)Cl) or to terminal oxophosphinidene complexes [MCp{P(O)R*}(CO)(2)(E')] (E' = SnPh(3), SnPh(2)Cl, PbPh(3); Mo-Pb = 2.8845(4) Å for the MoPb compound). A particular situation was found in the reaction with SnMe(3)Cl, this giving a product existing in both tautomeric forms, with the phosphide-like complex [MCp{P(OSnMe(3))R*}(CO)(2)] prevailing at room temperature and the tautomer [MCp{P(O)R*}(CO)(2)(SnMe(3))] being the unique species present below 203 K in dichloromethane solution. The title anions also showed a multisite behavior when reacting with transition-metal based electrophiles. Thus, the reactions with the complexes [M'Cp(2)Cl(2)] (M' = Ti, Zr) gave phosphide-like derivatives [MCp{P(OM')R*}(CO)(2)] (M = Mo, M' = TiCp(2)Cl, ZrCp(2)Cl; M = W, M' = ZrCp(2)Cl), displaying a bridging κ(1),κ(1)-P,O- oxophosphinidene ligand connecting MCp(CO)(2) and M'Cp(2)Cl metal fragments (W-P = 2.233(1) Å, O-Zr = 2.016(4) Å for the WZr compound]. In contrast, the reactions with the complex [AuCl{P(p-tol)(3)}] gave the metal-metal bonded derivatives trans-[MCp{P(O)R*}(CO)(2){AuP(p-tol)(3)}] (M = Mo, W; Mo-Au = 2.7071(7) Å). From all the above results it was concluded that the terminal oxophosphinidene complexes are preferentially formed under conditions of orbital control, while charge-controlled reactions tend to give derivatives with the electrophilic fragment bound to the oxygen atom of the oxophosphinidene ligand (phosphide-like, oxophosphinidene-bridged derivatives).

The scavenging reactions of nitrogen dioxide radical and carbonate radical by tea polyphenol derivatives: a pulse radiolysis study

NASA Astrophysics Data System (ADS)

Miao, Jin-Ling; Wang, Wen-Feng; Pan, Jing-Xi; Lu, Chang-Yuan; Li, Rong-Qun; Yao, Si-De

2001-02-01

The reactions of tea polyphenol derivatives, including epicatechin (EC) and epigallocatechin gallate (EGCG), with nitrogen dioxide radical (NO 2rad ) and carbonate radical (CO 3rad - ) have been studied in detail using time-resolved pulse radiolysis technique. In all the cases, the corresponding phenoxyl radical was formed through electron transfer reaction. From the build-up kinetics of the phenoxyl radicals and the decay kinetics of CO 3rad - radical, the reaction rate constants of EC, EGCG with NO 2rad and CO 3rad - were determined to be 9.0×10 7, 1.2×10 8 and 5.6×10 8, 6.6×10 8 dm 3 mol -1 s -1, respectively. Therefore, tea polyphenol derivatives proved to be efficient scavengers of NO 2rad and CO 3rad - radicals.

Large divergence of satellite and Earth system model estimates of global terrestrial CO2 fertilization

USGS Publications Warehouse

Smith, W. Kolby; Reed, Sasha C.; Cleveland, Cory C.; Ballantyne, Ashley P; Anderegg, William R. L.; Wieder, William R.; Liu, Yi Y; Running, Steven W.

2015-01-01

Atmospheric mass balance analyses suggest that terrestrial carbon (C) storage is increasing, partially abating the atmospheric [CO2] growth rate, although the continued strength of this important ecosystem service remains uncertain. Some evidence suggests that these increases will persist owing to positive responses of vegetation growth (net primary productivity; NPP) to rising atmospheric [CO2] (that is, ‘CO2 fertilization’). Here, we present a new satellite-derived global terrestrial NPP data set, which shows a significant increase in NPP from 1982 to 2011. However, comparison against Earth system model (ESM) NPP estimates reveals a significant divergence, with satellite-derived increases (2.8 ± 1.50%) less than half of ESM-derived increases (7.6  ±  1.67%) over the 30-year period. By isolating the CO2 fertilization effect in each NPP time series and comparing it against a synthesis of available free-air CO2 enrichment data, we provide evidence that much of the discrepancy may be due to an over-sensitivity of ESMs to atmospheric [CO2], potentially reflecting an under-representation of climatic feedbacks and/or a lack of representation of nutrient constraints. Our understanding of CO2 fertilization effects on NPP needs rapid improvement to enable more accurate projections of future C cycle–climate feedbacks; we contend that better integration of modelling, satellite and experimental approaches offers a promising way forward.

Polyisoprenoid epoxides stimulate the biosynthesis of coenzyme Q and inhibit cholesterol synthesis.

PubMed

Bentinger, Magnus; Tekle, Michael; Brismar, Kerstin; Chojnacki, Tadeusz; Swiezewska, Ewa; Dallner, Gustav

2008-05-23

In our search for compounds that up-regulate the biosynthesis of coenzyme Q (CoQ), we discovered that irradiation of CoQ with ultraviolet light results in the formation of a number of compounds that influence the synthesis of mevalonate pathway lipids by HepG2 cells. Among the compounds that potently stimulated CoQ synthesis while inhibiting cholesterol synthesis, derivatives of CoQ containing 1-4 epoxide moieties in their polyisoprenoid side chains were identified. Subsequently, chemical epoxidation of all-trans-polyprenols of different lengths revealed that the shorter farnesol and geranylgeraniol derivatives were without effect, whereas the longer derivatives of solanesol enhanced CoQ and markedly reduced cholesterol biosynthesis. In contrast, none of the modified trans-trans-poly-cis-polyprenols exerted noticeable effects. Tocotrienol epoxides were especially potent in our system; those with one epoxide moiety in the side-chain generally up-regulated CoQ biosynthesis by 200-300%, whereas those with two such moieties also decreased cholesterol synthesis by 50-90%. Prolonged treatment of HepG2 cells with tocotrienol epoxides for 26 days elevated their content of CoQ by 30%. In addition, the levels of mRNA encoding enzymes involved in CoQ biosynthesis were also elevated by the tocotrienol epoxides. The site of inhibition of cholesterol synthesis was shown to be oxidosqualene cyclase. In conclusion, epoxide derivatives of certain all-trans-polyisoprenoids cause pronounced stimulation of CoQ synthesis and, in some cases, simultaneous reduction of cholesterol biosynthesis by HepG2 cells.

CO2 Biofixation of Actinobacillus succinogenes Through Novel Amine-Functionalized Polystyrene Microsphere Materials.

PubMed

Zhu, Wenhao; Li, Qiang; Dai, Ning

2017-02-01

CO 2 -derived succinate production was enhanced by Actinobacillus succinogenes through polystyrene (PSt) microsphere materials for CO 2 adsorption in bioreactor, and the adhesion forces between A. succinogenes bacteria and PSt materials were characterized. Synthesized uniformly sized and highly cross-linked PSt microspheres had high specific surface areas. After modification with amine functional groups, the novel amine-functionalized PSt microspheres exhibited a high adsorption capacity of 25.3 mg CO 2 /g materials. After addition with the functionalized microspheres into the culture broth, CO 2 supply to the cells increased. Succinate production by A. succinogenes can be enhanced from 29.6 to 48.1 g L -1 . Moreover, the characterization of interaction forces between A. succinogenes cells and the microspheres indicated that the maximal adhesive force was about 250 pN. The amine-functionalized PSt microspheres can adsorb a large amount of CO 2 and be employed for A. succinogenes anaerobic cultivation in bioreactor for high-efficiency production of CO 2 -derived succinate.

Constraining Ecosystem Gross Primary Production and Transpiration with Measurements of Photosynthetic 13CO2 Discrimination

NASA Astrophysics Data System (ADS)

Blonquist, J. M.; Wingate, L.; Ogeé, J.; Bowling, D. R.

2011-12-01

The stable carbon isotope composition of atmospheric CO2 (δ13Ca) can provide useful information on water use efficiency (WUE) dynamics of terrestrial ecosystems and potentially constrain models of CO2 and water fluxes at the land surface. This is due to the leaf-level relationship between photosynthetic 13CO2 discrimination (Δ), which influences δ13Ca, and the ratio of leaf intercellular to atmospheric CO2 mole fractions (Ci / Ca), which is related to WUE and is determined by the balance between C assimilation (CO2 demand) and stomatal conductance (CO2 supply). We used branch-scale Δ derived from tunable diode laser absorption spectroscopy measurements collected in a Maritime pine forest to estimate Ci / Ca variations over an entire growing season. We combined Ci / Ca estimates with rates of gross primary production (GPP) derived from eddy covariance (EC) to estimate canopy-scale stomatal conductance (Gs) and transpiration (T). Estimates of T were highly correlated to T estimates derived from sapflow data (y = 1.22x + 0.08; r2 = 0.61; slope P < 0.001) and T predictions from an ecosystem model (MuSICA) (y = 0.88x - 0.05; r2 = 0.64; slope P < 0.001). As an alternative to estimating T, Δ measurements can be used to estimate GPP by combining Ci / Ca estimates with Gs estimates from sapflow data. Estimates of GPP were determined in this fashion and were highly correlated to GPP values derived from EC (y = 0.82 + 0.07; r2 = 0.61; slope P < 0.001) and GPP predictions from MuSICA (y = 1.10 + 0.42; r2 = 0.50; slope P < 0.001). Results demonstrate that the leaf-level relationship between Δ and Ci / Ca can be extended to the canopy-scale and that Δ measurements have utility for partitioning ecosystem-scale CO2 and water fluxes.

Feedbacks among O2 and CO2 in deep soil gas, oxidation of ferrous minerals, and fractures: A hypothesis for steady-state regolith thickness

NASA Astrophysics Data System (ADS)

Kim, Hyojin; Stinchcomb, Gary; Brantley, Susan L.

2017-02-01

O2 and CO2, the two essential reactants in weathering along with water and minerals, are important in deep regolith development because they diffuse to weathering fronts at depth. We monitored the dynamics of these gas concentrations in the hand-augerable zone on three ridgetops-one on granite and two on diabase-in Virginia (VA) and Pennsylvania (PA), U.S.A. and related the gas chemistry to regolith development. The VA granite and the PA diabase protoliths were more deeply weathered than the VA diabase. We attribute this to high protolith fracture density. The pO2 and pCO2 measurements of these more fractured sites displayed the characteristics of aerobic respiration year round. In contrast, the relation of pO2 versus pCO2 on the more massive VA diabase is consistent with seasonal changes in the dominant electron acceptor from O2 to Fe(III), likely regulated by the expansion/contraction of nontronite in the soil BC horizon. These observations suggest that the fracture density is a first order control on deep regolith gas chemistry. However, fractures can be present in protolith but also can be caused by oxidation of ferrous minerals. We propose that subsurface pO2 and weathering-induced fracturing can create positive feedbacks in some lithologies that cause regolith to thicken while nonetheless maintaining aerobic respiration at depth. In contrast, in the absence of weathering-induced fracturing and depletion of pO2, a negative feedback that may be modulated by soil micro-biota ultimately results in thin regolith. These feedbacks may have been important in weathering systems over much of earth's history.

Interaction of peridotite with Ca-rich carbonatite melt at 3.1 and 6.5 GPa: Implication for merwinite formation in upper mantle, and for the metasomatic origin of sublithospheric diamonds with Ca-rich suite of inclusions

NASA Astrophysics Data System (ADS)

Sharygin, Igor S.; Shatskiy, Anton; Litasov, Konstantin D.; Golovin, Alexander V.; Ohtani, Eiji; Pokhilenko, Nikolay P.

2018-03-01

We performed an experimental study, designed to reproduce the formation of an unusual merwinite + olivine-bearing mantle assemblage recently described as a part of a Ca-rich suite of inclusions in sublithospheric diamonds, through the interaction of peridotite with an alkali-rich Ca-carbonatite melt, derived from deeply subducted oceanic crust. In the first set of experiments, we studied the reaction between powdered Mg-silicates, olivine and orthopyroxene, and a model Ca-carbonate melt (molar Na:K:Ca = 1:1:2), in a homogeneous mixture, at 3.1 and 6.5 GPa. In these equilibration experiments, we observed the formation of a merwinite + olivine-bearing assemblage at 3.1 GPa and 1200 °C and at 6.5 GPa and 1300-1400 °C. The melts coexisting with this assemblage have a low Si and high Ca content (Ca# = molar 100 × Ca/(Ca + Mg) > 0.57). In the second set of experiments, we investigated reaction rims produced by interaction of the same Ca-carbonate melt (molar Na:K:Ca = 1:1:2) with Mg-silicate, olivine and orthopyroxene, single crystals at 3.1 GPa and 1300 °C and at 6.5 GPa and 1400 °C. The interaction of the Ca-carbonate melt with olivine leads to merwinite formation through the expected reaction: 2Mg2SiO4 (olivine) + 6CaCO3 (liquid) = Ca3MgSi2O8 (merwinite) + 3CaMg(CO3)2 (liquid). Thus, our experiments confirm the idea that merwinite in the upper mantle may originate via interaction of peridotite with Ca-rich carbonatite melt, and that diamonds hosting merwinite may have a metasomatic origin. It is remarkable that the interaction of the Ca-carbonate melt with orthopyroxene crystals does not produce merwinite both at 3.1 and 6.5 GPa. This indicates that olivine grain boundaries are preferable for merwinite formation in the upper mantle.

Comparative docking and CoMFA analysis of curcumine derivatives as HIV-1 integrase inhibitors.

PubMed

Gupta, Pawan; Garg, Prabha; Roy, Nilanjan

2011-08-01

The docking studies and comparative molecular field analysis (CoMFA) were performed on highly active molecules of curcumine derivatives against 3' processing activity of HIV-1 integrase (IN) enzyme. The optimum CoMFA model was selected with statistically significant cross-validated r(2) value of 0.815 and non-cross validated r (2) value of 0.99. The common pharmacophore of highly active molecules was used for screening of HIV-1 IN inhibitors. The high contribution of polar interactions in pharmacophore mapping is well supported by docking and CoMFA results. The results of docking, CoMFA, and pharmacophore mapping give structural insights as well as important binding features of curcumine derivatives as HIV-1 IN inhibitors which can provide guidance for the rational design of novel HIV-1 IN inhibitors.

Chiral and achiral phosphine derivatives of alkylidyne tricobalt carbonyl clusters as catalyst precursors for (asymmetric) inter- and intramolecular Pauson-Khand reactions.

PubMed

Moberg, Viktor; Mottalib, M Abdul; Sauer, Désirée; Poplavskaya, Yulia; Craig, Donald C; Colbran, Stephen B; Deeming, Antony J; Nordlander, Ebbe

2008-05-14

Phosphine derivatives of alkylidyne tricobalt carbonyl clusters have been tested as catalysts/catalyst precursors in intermolecular and (asymmetric) intramolecular Pauson-Khand reactions. A number of new phosphine derivatives of the tricobalt alkylidyne clusters [Co3(micro3-CR)(CO)9] (R = H, CO2Et) were prepared and characterised. The clusters [Co3(micro3-CR)(CO)9-x(PR'3)x] (PR'3 = achiral or chiral monodentate phosphine, x = 1-3) and [Co3(micro3-CR)(CO)7)(P-P)] (P-P = chiral diphosphine; 1,1'- and 1,2-structural isomers) were assayed as catalysts for intermolecular and (asymmetric) intramolecular Pauson-Khand reactions. The phosphine-substituted tricobalt clusters proved to be viable catalysts/catalyst precursors that gave moderate to very good product yields (up to approximately 90%), but the enantiomeric excesses were too low for the clusters to be of practical use in the asymmetric reactions.

Rapid Removal of Atmospheric CO2 by Urban Soils.

PubMed

Washbourne, Carla-Leanne; Lopez-Capel, Elisa; Renforth, Phil; Ascough, Philippa L; Manning, David A C

2015-05-05

The measured calcium carbonate content of soils to a depth of 100 mm at a large urban development site has increased over 18 months at a rate that corresponds to the sequestration of 85 t of CO2/ha (8.5 kg of CO2 m(-2)) annually. This is a consequence of rapid weathering of calcium silicate and hydroxide minerals derived from the demolition of concrete structures, which releases Ca that combines with CO2 ultimately derived from the atmosphere, precipitating as calcite. Stable isotope data confirm an atmospheric origin for carbonate carbon, and 14C dating indicates the predominance of modern carbon in the pedogenic calcite. Trial pits show that carbonation extends to depths of ≥1 m. Work at other sites shows that the occurrence of pedogenic carbonates is widespread in artificially created urban soils containing Ca and Mg silicate minerals. Appropriate management of fewer than 12000 ha of urban land to maximize calcite precipitation has the potential to remove 1 million t of CO2 from the atmosphere annually. The maximal global potential is estimated to be approximately 700-1200 Mt of CO2 per year (representing 2.0-3.7% of total emissions from fossil fuel combustion) based on current rates of production of industry-derived Ca- and Mg-bearing materials.

Redox Heterogenity in MORB

NASA Astrophysics Data System (ADS)

Cottrell, E.; Kelley, K. A.

2012-12-01

Mantle oxygen fugacity (fO2) has a first-order effect on the petrogenesis of mantle-derived melts and the speciation of mantle fluids. Current debate centers on the spatial uniformity of upper mantle fO2 and its constancy through geologic time. We use iron K-edge X-ray absorption near-edge structure (μXANES) spectroscopy to provide Fe3+ /ΣFe ratios of submarine mantle-derived basalts from mid-ocean ridges (MORB) as a proxy for fO2. A global survey of primitive (>8.75 wt% MgO) MORB glasses at spreading centers, unaffected by plumes, reveals a decrease in Fe3+ /ΣFe ratio of 12% relative with indices of mantle enrichment such as 87/86Sr, 208/204Pb, Ba/La, and Rb/Sr ratios. The strong negative correlation between upper mantle fO2 and enrichment recorded by MORB glasses contrasts with the positive relationship hinted at by abyssal peridotite oxybarometry (e.g. Ballhaus, CMP, 1993) and the general prediction of a positive correlation born of the expectation that Fe3+ can be treated as more incompatible than Fe2+ during mantle melting. These data unequivocally link upper mantle oxidation state to mantle source enrichment. EMORB generation is commonly attributed to subduction-related processes. That EMORB is more reduced than NMORB implies that deeply subducted and recycled lithologies, such as anoxic sediment, may be more reduced than ambient mantle. Negative correlations between traditional tracers of recycled sediment (e.g. +Nb anomaly, high 87/86Sr, high LILE/LREE) and redox support this hypothesis. Preservation of redox signatures on plate-recycling timescales of hundreds of millions to billions of years would require the mantle to be very poorly buffered. Alternatively, MORB Fe3+ /ΣFe ratios may be generated in situ beneath ridges as a function of variable carbon content. The shallow MORB source is too oxidized to stabilize graphite (Cottrell and Kelley, EPSL, 2011) and carbon exists as oxides. Decreasing fO2 with increasing depth eventually stabilizes reduced carbon species (diamond, carbides, alloys), however, and aCO2 may buffer mantle assemblages. Upon ascent, reduced carbon in upwelling mantle must oxidize, reducing Fe in the process such that more carbon-rich mantle would arrive at the surface with a lower Fe3+ /ΣFe ratio. We cannot directly correlate Fe3+ /ΣFe ratios with CO2 concentrations because submarine basalts have variably degassed CO2; however, the unequivocally carbon-rich sample 2πD43 (popping rock) does record a low Fe3+ /ΣFe ratio. CO2 variations on the order of 80 ppm in the mantle source would explain the range of MORB/EMORB Fe3+ /ΣFe ratios we observe, indicating a possible range of carbon concentrations in subduction-related lithologies. The relationships between MORB Fe3+ /ΣFe ratios, trace elements, and isotopes are consistent with modeled mixtures of depleted melts and low-degree carbonatitic melts of ancient subducted igneous crust plus 5-15% sediment (Stracke et al., G3, 2001) using the near-solidus carbonatitic partition coefficients of Dasgupta et al., Chem Geol, (2009). It may be that low degree carbonatitic melts even act through geologic time to scavenge and fractionate trace elements, creating enriched high-carbon reservoirs. Low Fe3+ /ΣFe ratios, and even EMORB itself, may therefore herald greater carbon concentrations, and the influence of low-degree carbonatitic melts, in Earth's mantle.

Directed amination of non-acidic arene C-H bonds by a copper-silver catalytic system.

PubMed

Tran, Ly Dieu; Roane, James; Daugulis, Olafs

2013-06-03

Amine meets arene: A method for direct amination of β-C(sp(2))-H bonds of benzoic acid derivatives and γ-C(sp(2))-H bonds of benzylamine derivatives has been developed. The reaction is catalyzed by Cu(OAc)2 and a Ag2CO3 cocatalyst, and shows high generality and functional-group tolerance, as well as providing a straightforward means for the preparation of ortho-aminobenzoic acid derivatives. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Comparative Data-Based Modeling Study on Respiratory CO2 Gas Exchange during Mechanical Ventilation

PubMed Central

Kim, Chang-Sei; Ansermino, J. Mark; Hahn, Jin-Oh

2016-01-01

The goal of this study is to derive a minimally complex but credible model of respiratory CO2 gas exchange that may be used in systematic design and pilot testing of closed-loop end-tidal CO2 controllers in mechanical ventilation. We first derived a candidate model that captures the essential mechanisms involved in the respiratory CO2 gas exchange process. Then, we simplified the candidate model to derive two lower-order candidate models. We compared these candidate models for predictive capability and reliability using experimental data collected from 25 pediatric subjects undergoing dynamically varying mechanical ventilation during surgical procedures. A two-compartment model equipped with transport delay to account for CO2 delivery between the lungs and the tissues showed modest but statistically significant improvement in predictive capability over the same model without transport delay. Aggregating the lungs and the tissues into a single compartment further degraded the predictive fidelity of the model. In addition, the model equipped with transport delay demonstrated superior reliability to the one without transport delay. Further, the respiratory parameters derived from the model equipped with transport delay, but not the one without transport delay, were physiologically plausible. The results suggest that gas transport between the lungs and the tissues must be taken into account to accurately reproduce the respiratory CO2 gas exchange process under conditions of wide-ranging and dynamically varying mechanical ventilation conditions. PMID:26870728

Visualization and Classification of Deeply Seated Collateral Networks in Moyamoya Angiopathy with 7T MRI.

PubMed

Matsushige, T; Kraemer, M; Sato, T; Berlit, P; Forsting, M; Ladd, M E; Jabbarli, R; Sure, U; Khan, N; Schlamann, M; Wrede, K H

2018-06-07

Collateral networks in Moyamoya angiopathy have a complex angioarchitecture difficult to comprehend on conventional examinations. This study aimed to evaluate morphologic patterns and the delineation of deeply seated collateral networks using ultra-high-field MRA in comparison with conventional DSA. Fifteen white patients with Moyamoya angiopathy were investigated in this prospective trial. Sequences acquired at 7T were TOF-MRA with 0.22 × 0.22 × 0.41 mm 3 resolution and MPRAGE with 0.7 × 0.7 × 0.7 mm 3 resolution. Four raters evaluated the presence of deeply seated collateral networks and image quality in a consensus reading of DSA, TOF-MRA, and MPRAGE using a 5-point scale in axial source images and maximum intensity projections. Delineation of deeply seated collateral networks by different imaging modalities was compared by means of the McNemar test, whereas image quality was compared using the Wilcoxon signed-rank test. The relevant deeply seated collateral networks were classified into 2 categories and 6 pathways. A total of 100 collateral networks were detected on DSA; 106, on TOF-MRA; and 73, on MPRAGE. Delineation of deeply seated collateral networks was comparable between TOF-MRA and DSA ( P = .25); however, both were better than MPRAGE ( P < .001). This study demonstrates excellent delineation of 6 distinct deeply seated collateral network pathways in Moyamoya angiopathy in white adults using 7T TOF-MRA, comparable to DSA. © 2018 by American Journal of Neuroradiology.

Heat flow vs. atmospheric greenhouse on early Mars

NASA Technical Reports Server (NTRS)

Fanale, F. P.; Postawko, S. E.

1991-01-01

Researchers derived a quantitative relationship between the effectiveness of an atmospheric greenhouse and internal heat flow in producing the morphological differences between earlier and later Martian terrains. The derivation is based on relationships previously derived by other researchers. The reasoning may be stated as follows: the CO2 mean residence time in the Martian atmosphere is almost certainly much shorter than the total time span over which early climate differences are thought to have been sustained. Therefore, recycling of previously degassed CO2 quickly becomes more important than the ongoing supply of juvenile CO2. If so, then the atmospheric CO2 pressure, and thereby the surface temperature, may be approximated mathematically as a function of the total degassed CO2 in the atmosphere plus buried material and the ratio of the atmospheric and regolith mean residence times. The latter ratio can also be expressed as a function of heat flow. Hence, it follows that the surface temperature may be expressed as a function of heat flow and the total amount of available CO2. However, the depth to the water table can simultaneously be expressed as a function of heat flow and the surface temperature (the boundary condition). Therefore, for any given values of total available CO2 and regolith conductivity, there exist coupled independent equations which relate heat flow, surface temperature, and the depth to the water table. This means we can now derive simultaneous values of surface temperature and the depth of the water table for any value of the heat flow. The derived relationship is used to evaluate the relative importance of the atmospheric greenhouse effect and the internal regolith thermal gradient in producing morphological changes for any value of the heat flow, and to assess the absolute importance of each of the values of the heat flow which are thought to be reasonable on independent geophysical grounds.

MUFITS Code for Modeling Geological Storage of Carbon Dioxide at Sub- and Supercritical Conditions

NASA Astrophysics Data System (ADS)

Afanasyev, A.

2012-12-01

Two-phase models are widely used for simulation of CO2 storage in saline aquifers. These models support gaseous phase mainly saturated with CO2 and liquid phase mainly saturated with H2O (e.g. TOUGH2 code). The models can be applied to analysis of CO2 storage only in relatively deeply-buried reservoirs where pressure exceeds CO2 critical pressure. At these supercritical reservoir conditions only one supercritical CO2-rich phase appears in aquifer due to CO2 injection. In shallow aquifers where reservoir pressure is less than the critical pressure CO2 can split in two different liquid-like and gas-like phases (e.g. Spycher et al., 2003). Thus a region of three-phase flow of water, liquid and gaseous CO2 can appear near the CO2 injection point. Today there is no widely used and generally accepted numerical model capable of the three-phase flows with two CO2-rich phases. In this work we propose a new hydrodynamic simulator MUFITS (Multiphase Filtration Transport Simulator) for multiphase compositional modeling of CO2-H2O mixture flows in porous media at conditions of interest for carbon sequestration. The simulator is effective both for supercritical flows in a wide range of pressure and temperature and for subcritical three-phase flows of water, liquid CO2 and gaseous CO2 in shallow reservoirs. The distinctive feature of the proposed code lies in the methodology for mixture properties determination. Transport equations and Darcy correlation are solved together with calculation of the entropy maximum that is reached in thermodynamic equilibrium and determines the mixture composition. To define and solve the problem only one function - mixture thermodynamic potential - is required. The potential is determined using a three-parametric generalization of Peng-Robinson equation of state fitted to experimental data (Todheide, Takenouchi, Altunin etc.). We apply MUFITS to simple 1D and 2D test problems of CO2 injection in shallow reservoirs subjected to phase changes between liquid and gaseous CO2. We consider CO2 injection into highly heterogeneous the 10th SPE reservoir. We provide analysis of physical phenomena that have control temperature distribution in the reservoir. The distribution is non-monotonic with regions of high and low temperature. The main phenomena responsible for considerable temperature decline around CO2 injection point is the liquid CO2 evaporation process. We also apply the code to real-scale 3D simulations of CO2 geological storage at supercritical conditions in Sleipner field and Johansen formation (Fig). The work is supported financially by the Russian Foundation for Basic Research (12-01-31117) and grant for leading scientific schools (NSh 1303.2012.1). CO2 phase saturation in Johansen formation after 50 years of injection and 1000 years of rest period

Injection of Compact Torus into the HIST spherical torus plasmas

NASA Astrophysics Data System (ADS)

Sugawara, M.; Katsumoto, S.; Kikuchi, Y.; Fukumoto, N.; Nagata, M.

2006-10-01

The three-dimensional interaction of a spheromak-like compact torus (CT) plasma with spherical torus (ST) plasmas has been experimentally studied to understand magnetic reconnection, helicity current drive, particle fuelling and Alfvén wave excitation [1]. We have examined how the sign of helicity (Co-HI and Counter-HI) of the injected CT influences on the ST plasmas on HIST [2]. The dynamics of the CT have been identified to be significantly different between the both injection cases. Time-frequency analysis shows that the fluctuation induced in the co-HI case has the maximum spectral amplitude at around 300 -- 400 kHz that may indicate the magnetic reconnection. In this case, the CT particle is released quickly at a periphery region, but on the other hand, for the counter-HI case, the CT could penetrate deeply into the core region as accompanied by Alfvén wave due to no magnetic reconnection. [1] M. Nagata, et al., Nucl. Fusion 45, 1056 (2005) [2] M. Nagata, et al., Physics of Plasmas 10, 2932 (2003)

Synthesis, spectroscopic, DFT studies and biological activity of some ruthenium carbonyl derivatives of bis-(salicylaldehyde)phenylenediimine Schiff base ligand

NASA Astrophysics Data System (ADS)

Ramadan, Ramadan M.; Abu Al-Nasr, Ahmad K.; Ali, Omayma A. M.

2018-06-01

Bis-(salicylaldehyde)phenylenediimine Schiff base (H2salphen) reacted oxidatively with the triruthenium dodecacarbonyl complex, [Ru3(CO)12] to give the dicarbonyl derivative [Ru(CO)2(salphen)], 1. In presence of a secondary ligand L (L = pyridine, triphenyl phosphine, 2-aminobenzimidazole or thiourea), the monocarbonyl derivatives [Ru(CO)(salphen)L], 2-5, were isolated. When the bipyridine (bpy) ligand was used as a secondary ligand, the dicarbonyl complex [Ru(CO)2(Hsalphen)(bpy)], 6, was obtained. In complexes 1-5, the Schiff base ligand acted as a tetradentate, while it coordinated as a bidentate in complex 6. The structure and stoichiometry of the complexes were investigated by the conventional analytical and spectroscopic techniques, which revealed that they have several structural arrangements. The structures of ligand and complexes were verified by theoretical calculations based on accurate DFT approximations. The relative reactivities were estimated using chemical descriptors analysis. Biological activities of the complexes against the Escherchia coli and Staphylococcus aureus bacteria were screened.

Genome Sequence of the Verrucomicrobium Opitutus terrae PB90-1, an Abundant Inhabitant of Rice Paddy Soil Ecosystems▿

PubMed Central

van Passel, Mark W. J.; Kant, Ravi; Palva, Airi; Copeland, Alex; Lucas, Susan; Lapidus, Alla; Glavina del Rio, Tijana; Pitluck, Sam; Goltsman, Eugene; Clum, Alicia; Sun, Hui; Schmutz, Jeremy; Larimer, Frank W.; Land, Miriam L.; Hauser, Loren; Kyrpides, Nikolaos; Mikhailova, Natalia; Richardson, P. Paul; Janssen, Peter H.; de Vos, Willem M.; Smidt, Hauke

2011-01-01

Bacteria of the deeply branching phylum Verrucomicrobia are rarely cultured yet commonly detected in metagenomic libraries from aquatic, terrestrial, and intestinal environments. We have sequenced the genome of Opitutus terrae PB90-1, a fermentative anaerobe within this phylum, isolated from rice paddy soil and capable of propionate production from plant-derived polysaccharides. PMID:21398538

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.

Experimental and simulation studies of iron oxides for geochemical fixation of CO2-SO2 gas mixtures

USGS Publications Warehouse

Garcia, Susana; Rosenbauer, Robert J.; Palandri, James; Maroto-Valer, M. Mercedes

2011-01-01

Iron-bearing minerals are reactive phases of the subsurface environment and could potentially trap CO2–SO2gas mixtures derived from fossil fuel combustion processes by their conversion to siderite (FeCO3) and dissolved sulfate. Changes in fluid and mineral compositions resulting from reactions, involving the co-injection of SO2 with CO2 were observed both theoretically and experimentally. Experiments were conducted with a natural hematite (α-Fe2O3) sample. A high pressure-high temperature apparatus was used to simulate conditions in geologic formations deeper than 800 m, where CO2 is in the supercritical state. Solid samples were allowed to react with a NaCl–NaOH brine and SO2-bearing CO2-dominated gas mixtures. The predicted equilibrium mineral assemblage at 100 °C and 250 bar became hematite, dawsonite (NaAl(OH)2CO3), siderite (FeCO3) and quartz (SiO2). Experimentally, siderite and dawsonite, derived from the presence of kaolinite (Al2Si2O5(OH)4) in the parent material, were present in residual solids at longer reaction time intervals, which agreed well with results from the modelling work.

Deeply Virtual Exclusive Processes and Generalized Parton Distributions

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

,

2011-06-01

The goal of the comprehensive program in Deeply Virtual Exclusive Scattering at Jefferson Laboratory is to create transverse spatial images of quarks and gluons as a function of their longitudinal momentum fraction in the proton, the neutron, and in nuclei. These functions are the Generalized Parton Distributions (GPDs) of the target nucleus. Cross section measurements of the Deeply Virtual Compton Scattering (DVCS) reaction ep {yields} ep{gamma} in Hall A support the QCD factorization of the scattering amplitude for Q^2 {>=} 2 GeV^2. Quasi-free neutron-DVCS measurements on the Deuteron indicate sensitivity to the quark angular momentum sum rule. Fully exclusive H(e,more » e'p{gamma} ) measurements have been made in a wide kinematic range in CLAS with polarized beam, and with both unpolarized and longitudinally polarized targets. Existing models are qualitatively consistent with the JLab data, but there is a clear need for less constrained models. Deeply virtual vector meson production is studied in CLAS. The 12 GeV upgrade will be essential for for these channels. The {rho} and {omega} channels reactions offer the prospect of flavor sensitivity to the quark GPDs, while the {phi}-production channel is dominated by the gluon distribution.« less

Macrophage-derived microvesicles promote proliferation and migration of Schwann cell on peripheral nerve repair

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

Zhan, Chuan, E-mail: zhchuansy@163.com; Ma, Cheng-bin; Yuan, Hong-mou

Background: Macrophages have been implicated in peripheral nerve regeneration. However, whether macrophages-derived microvesicles (MVs) are involved in this process remains unknown. In the present study, the effects of macrophages-derived MVs on proliferation and migration of Schwann cells (SCs) were evaluated in both in vitro and in vivo. Methods: Human monocytic leukaemia cell line (THP-1) was successfully driven to M1 and M2 phenotypes by delivery of either IFN-γ or IL-4, respectively. SCs incubated with M1 or M2 macrophages-derived MVs, the cell migration and proliferation were assessed, and expression levels of nerve growth factor (NGF) and Laminin were measured. A rat model of sciaticmore » nerve was established and the effects of macrophages-derived MVs on nerve regeneration were investigated. Results: M2-derived MVs elevated migration, proliferation, NFG and Laminin protein levels of SCs compared with M1-or M0-derived MVs. The relative expression levels of miR-223 were also increased in M2 macrophages and M2-derived MVs. Transfected M2 macrophages with miR-223 inhibitor then co-incubated with SCs, an inhibition of cell migration and proliferation and a down-regulated levels of NFG and Laminin protein expression were observed. In vivo, M2-derived MVs significantly increased the infiltration and axon number of SCs. Conclusion: M2-derived MVs promoted proliferation and migration of SCs in vitro and in vivo, which provided a therapeutic strategy for nerve regeneration. - Highlights: • M2 macrophages-derived MVs elevated migration and proliferation of SCs. • M2 macrophages-derived MVs up-regulated NFG and Laminin expression of SCs. • MiR-223 expression was increased in M2 macrophages-derived MVs. • MiR-223 inhibitor reduced migration and proliferation of SCs co-incubated with MVs. • MiR-223 inhibitor down-regulated NFG and Laminin levels of SCs co-incubated with MVs.« less

ATLASGAL-selected massive clumps in the inner Galaxy. VI. Kinetic temperature and spatial density measured with formaldehyde

NASA Astrophysics Data System (ADS)

Tang, X. D.; Henkel, C.; Wyrowski, F.; Giannetti, A.; Menten, K. M.; Csengeri, T.; Leurini, S.; Urquhart, J. S.; König, C.; Güsten, R.; Lin, Y. X.; Zheng, X. W.; Esimbek, J.; Zhou, J. J.

2018-03-01

Context. Formaldehyde (H2CO) is a reliable tracer to accurately measure the physical parameters of dense gas in star-forming regions. Aim. We aim to determine directly the kinetic temperature and spatial density with formaldehyde for the 100 brightest ATLASGAL-selected clumps (the TOP100 sample) at 870 μm representing various evolutionary stages of high-mass star formation. Methods: Ten transitions (J = 3-2 and 4-3) of ortho- and para-H2CO near 211, 218, 225, and 291 GHz were observed with the Atacama Pathfinder EXperiment (APEX) 12 m telescope. Results: Using non-LTE models with RADEX, we derived the gas kinetic temperature and spatial density with the measured para-H2CO 321-220/303-202, 422-321/404-303, and 404-303/303-202 ratios. The gas kinetic temperatures derived from the para-H2CO 321-220/303-202 and 422-321/404-303 line ratios are high, ranging from 43 to >300 K with an unweighted average of 91 ± 4 K. Deduced Tkin values from the J = 3-2 and 4-3 transitions are similar. Spatial densities of the gas derived from the para-H2CO 404-303/303-202 line ratios yield 0.6-8.3 × 106 cm-3 with an unweighted average of 1.5 (±0.1) × 106 cm-3. A comparison of kinetic temperatures derived from para-H2CO, NH3, and dust emission indicates that para-H2CO traces a distinctly higher temperature than the NH3 (2, 2)/(1, 1) transitions and the dust, tracing heated gas more directly associated with the star formation process. The H2CO line widths are found to be correlated with bolometric luminosity and increase with the evolutionary stage of the clumps, which suggests that higher luminosities tend to be associated with a more turbulent molecular medium. It seems that the spatial densities measured with H2CO do not vary significantly with the evolutionary stage of the clumps. However, averaged gas kinetic temperatures derived from H2CO increase with time through the evolution of the clumps. The high temperature of the gas traced by H2CO may be mainly caused by radiation from embedded young massive stars and the interaction of outflows with the ambient medium. For Lbol/Mclump ≳ 10 L⊙/M⊙, we find a rough correlation between gas kinetic temperature and this ratio, which is indicative of the evolutionary stage of the individual clumps. The strong relationship between H2CO line luminosities and clump masses is apparently linear during the late evolutionary stages of the clumps, indicating that LH_2CO does reliably trace the mass of warm dense molecular gas. In our massive clumps H2CO line luminosities are approximately linearly correlated with bolometric luminosities over about four orders of magnitude in Lbol, which suggests that the mass of dense molecular gas traced by the H2CO line luminosity is well correlated with star formation. Source and H2CO parameters (Tables A.1-A.7) are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/611/A6

Structural properties of a family of hydrogen-bonded co-crystals formed between gemfibrozil and hydroxy derivatives of t-butylamine, determined directly from powder X-ray diffraction data

NASA Astrophysics Data System (ADS)

Cheung, Eugene Y.; David, Sarah E.; Harris, Kenneth D. M.; Conway, Barbara R.; Timmins, Peter

2007-03-01

We report the formation and structural properties of co-crystals containing gemfibrozil and hydroxy derivatives of t-butylamine H 2NC(CH 3) 3-n(CH 2OH) n, with n=0, 1, 2 and 3. In each case, a 1:1 co-crystal is formed, with transfer of a proton from the carboxylic acid group of gemfibrozil to the amino group of the t-butylamine derivative. All of the co-crystal materials prepared are polycrystalline powders, and do not contain single crystals of suitable size and/or quality for single crystal X-ray diffraction studies. Structure determination of these materials has been carried out directly from powder X-ray diffraction data, using the direct-space Genetic Algorithm technique for structure solution followed by Rietveld refinement. The structural chemistry of this series of co-crystal materials reveals well-defined structural trends within the first three members of the family ( n=0, 1, 2), but significantly contrasting structural properties for the member with n=3.

Effect of simulated coal-derived gas composition on H{sub 2}S poisoning behavior evaluated using a disaggregation scheme

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

Li, T.S.; Miao, H.; Chen, T.

2009-07-01

H{sub 2}S poisoning is an important issue for solid oxide fuel cells (SOFCs) operated with syngas. The effect of simulated coal-derived gas composition on H{sub 2}S poisoning behavior was evaluated using a disaggregation scheme where the influence of H{sub 2} content was determined separately using a typical anode-supported SOFC operated with a N2/H{sub 2} mixture gas, while the effect of other compositions (CO, CO{sub 2}, and H{sub 2}O) was investigated with simulated coal-derived gas having constant H{sub 2} and CO flow rates balanced by a H{sub 2}/N2 mixture gas (83% H{sub 2} and 17% N2). The results indicated that themore » extent of H{sub 2}S poisoning was not pertinent to H{sub 2} content when the cell was tested galvanostatically with a current density of 0.3 A/cm{sup 2} at 800{sup o}C using a N2/H{sub 2} mixture gas containing 10 ppm H{sub 2}S, and the H{sub 2}S poisoning impact can be completely removed by switching to sulfur-free gas. The CO, CO{sub 2}, and high water vapor content aggravated the H{sub 2}S poisoning effect, and the performance was almost irrecoverable when the cell was tested with a 35% H{sub 2}-46% CO-16% N2-3% H{sub 2}O mixture gas containing 12.5 ppm H{sub 2}S. However, the introduction of 10% CO{sub 2} and an increase in H{sub 2}O content from 3 to 10% in the mixture gas can promote the performance recoverability to a larger extent.« less

DFT and 3D-QSAR Studies of Anti-Cancer Agents m-(4-Morpholinoquinazolin-2-yl) Benzamide Derivatives for Novel Compounds Design

NASA Astrophysics Data System (ADS)

Zhao, Siqi; Zhang, Guanglong; Xia, Shuwei; Yu, Liangmin

2018-06-01

As a group of diversified frameworks, quinazolin derivatives displayed a broad field of biological functions, especially as anticancer. To investigate the quantitative structure-activity relationship, 3D-QSAR models were generated with 24 quinazolin scaffold molecules. The experimental and predicted pIC50 values for both training and test set compounds showed good correlation, which proved the robustness and reliability of the generated QSAR models. The most effective CoMFA and CoMSIA were obtained with correlation coefficient r 2 ncv of 1.00 (both) and leave-one-out coefficient q 2 of 0.61 and 0.59, respectively. The predictive abilities of CoMFA and CoMSIA were quite good with the predictive correlation coefficients ( r 2 pred ) of 0.97 and 0.91. In addition, the statistic results of CoMFA and CoMSIA were used to design new quinazolin molecules.

Partitioning of atmospheric carbon dioxide over Central Europe: insights from combined measurements of CO2 mixing ratios and their carbon isotope composition.

PubMed

Zimnoch, Miroslaw; Jelen, Dorota; Galkowski, Michal; Kuc, Tadeusz; Necki, Jaroslaw; Chmura, Lukasz; Gorczyca, Zbigniew; Jasek, Alina; Rozanski, Kazimierz

2012-09-01

Regular measurements of atmospheric CO (2) mixing ratios and their carbon isotope composition ((13)C/(12)C and (14)C/(12)C ratios) performed between 2005 and 2009 at two sites of contrasting characteristics (Krakow and the remote mountain site Kasprowy Wierch) located in southern Poland were used to derive fossil fuel-related and biogenic contributions to the total CO (2) load measured at both sites. Carbon dioxide present in the atmosphere, not coming from fossil fuel and biogenic sources, was considered 'background' CO (2). In Krakow, the average contribution of fossil fuel CO (2) was approximately 3.4%. The biogenic component was of the same magnitude. Both components revealed a distinct seasonality, with the fossil fuel component reaching maximum values during winter months and the biogenic component shifted in phase by approximately 6 months. The partitioning of the local CO (2) budget for the Kasprowy Wierch site revealed large differences in the derived components: the fossil fuel component was approximately five times lower than that derived for Krakow, whereas the biogenic component was negative in summer, pointing to the importance of photosynthetic sink associated with extensive forests in the neighbourhood of the station. While the presented study has demonstrated the strength of combined measurements of CO (2) mixing ratios and their carbon isotope signature as efficient tools for elucidating the partitioning of local atmospheric CO (2) loads, it also showed the important role of the land cover and the presence of the soil in the footprint of the measurement location, which control the net biogenic surface CO (2) fluxes.

Carbon Dioxide - rock interaction: from molecular observations to theorised interactions in fluid-rock systems

NASA Astrophysics Data System (ADS)

Calcara, Massimo; Borgia, Andrea

2013-04-01

Current global warming theories have produced some benefits: among them, detailed studies on CO2 and its properties, possible applications and perspectives. Starting from its use as a "green solvent" (for instance in decaffeination process), to enhance system in oil recovery, to capture and storage enough amount of CO2 in geological horizon. So, a great debate is centred around this molecule. One More useful research in natural horizon studies is its theorised use in Enhanced Geothermal Systems with CO2 as the only working fluid. In any case, the CO2 characteristics should be deeply understood, before injecting a molecule prone to change easily its aggregation state at relatively shallow depth. CO2 Rock interaction becomes therefore a focal point in approaching research sectors linked in some manner to natural or induced presence of carbon dioxide in geological horizons. Possible chemical interactions between fluids and solids have always been a central topic in defining evolution of the system as a whole in terms of dissolutions, reactions, secondary mineral formation and, in case of whichever plant, scaling. Questions arise in case of presence of CO2 with host rocks. Chemical and molecular properties are strategic. CO2 Rock interactions are based on eventual solubility capability of pure liquid and supercritical CO2 seeking and eventually quantifying its polar and/or ionic solvent capabilities. Single molecule at STP condition is linear, with central carbon atom and oxygen atoms at opposite site on a straight line with a planar angle. It has a quadrupolar moment due to the electronegativity difference between carbon and oxygen. As soon as CO2 forms bond with water, it deforms even at atmospheric pressure, assuming an induced dipole moment with a value around 0.02 Debye. Hydrated CO2 forms a hydrophilic bond; it deforms with an angle of 178 degrees. Pure CO2 forms self aggregates. In the simplest case a dimer, with two molecules of CO2 exerting mutual attraction and forming at a first impact a structure defined parallel or slipped parallel or a more stable T shaped. As soon as pressure is applied, density changes and appears a stable (induced) dipole moment 0.22 Debye: phase changes and CO2 dipole moment reaches 0.85 Debye dipole moment. Pure CO2, here the only liquid phase, assumes Lewis acid/base properties. Polar solvent properties seem to be real, and some experiments have observed this characteristics. This stated, present work try to show computer aided simulation in chemical and physical evolution of a portion of rock with liquid and supercritical CO2, with and without water, in granite and oceanic basalt formations.

Amazon rainforest responses to elevated CO2: Deriving model-based hypotheses for the AmazonFACE experiment

NASA Astrophysics Data System (ADS)

Rammig, A.; Fleischer, K.; Lapola, D.; Holm, J.; Hoosbeek, M.

2017-12-01

Increasing atmospheric CO2 concentration is assumed to have a stimulating effect ("CO2 fertilization effect") on forest growth and resilience. Empirical evidence, however, for the existence and strength of such a tropical CO2 fertilization effect is scarce and thus a major impediment for constraining the uncertainties in Earth System Model projections. The implications of the tropical CO2 effect are far-reaching, as it strongly influences the global carbon and water cycle, and hence future global climate. In the scope of the Amazon Free Air CO2 Enrichment (FACE) experiment, we addressed these uncertainties by assessing the CO2 fertilization effect at ecosystem scale. AmazonFACE is the first FACE experiment in an old-growth, highly diverse tropical rainforest. Here, we present a priori model-based hypotheses for the experiment derived from a set of 12 ecosystem models. Model simulations identified key uncertainties in our understanding of limiting processes and derived model-based hypotheses of expected ecosystem responses to elevated CO2 that can directly be tested during the experiment. Ambient model simulations compared satisfactorily with in-situ measurements of ecosystem carbon fluxes, as well as carbon, nitrogen, and phosphorus stocks. Models consistently predicted an increase in photosynthesis with elevated CO2, which declined over time due to developing limitations. The conversion of enhanced photosynthesis into biomass, and hence ecosystem carbon sequestration, varied strongly among the models due to different assumptions on nutrient limitation. Models with flexible allocation schemes consistently predicted an increased investment in belowground structures to alleviate nutrient limitation, in turn accelerating turnover rates of soil organic matter. The models diverged on the prediction for carbon accumulation after 10 years of elevated CO2, mainly due to contrasting assumptions in their phosphorus cycle representation. These differences define the expected response ratio to elevated CO2 at the AmazonFACE site and identify priorities for experimental work and model development.

Crystal engineering: co-crystals of cinnamic acid derivatives with a pyridyl derivative co-crystallizer.

PubMed

Lorenzo, Daniel A; Forrest, Sebastian J K; Sparkes, Hazel A

2016-02-01

A number of hydrogen-bonded co-crystals, consisting of a cinnamic acid derivative and a pyridyl co-crystallizer, have been synthesized and their properties investigated by X-ray diffraction. Samples were prepared by recrystallization or solvent drop grinding of trans-cinnamic acid (1), 4-methylcinnamic acid (2), 4-methoxy cinnamic acid (3) or 3,4-methoxy cinnamic acid (4), with 4,4-dipyridyl (A), iso-nicotinamide (B) or nicotinamide (C). The X-ray single-crystal structures of seven novel co-crystals, obtained through recrystallization, are examined and the hydrogen-bonding interactions discussed. Consistent hydrogen-bonding motifs were observed for samples prepared when using 4,4-dipyridyl (A) or iso-nicotinamide (B) as the co-crystallizing agent. Powder X-ray diffraction analysis of the samples prepared by solvent drop grinding suggests the formation of ten co-crystals.

CaO-Based CO2 Sorbents Effectively Stabilized by Metal Oxides.

PubMed

Naeem, Muhammad Awais; Armutlulu, Andac; Imtiaz, Qasim; Müller, Christoph R

2017-11-17

Calcium looping (i.e., CO 2 capture by CaO) is a promising second-generation CO 2 capture technology. CaO, derived from naturally occurring limestone, offers an inexpensive solution, but due to the harsh operating conditions of the process, limestone-derived sorbents undergo a rapid capacity decay induced by the sintering of CaCO 3 . Here, we report a Pechini method to synthesize cyclically stable, CaO-based CO 2 sorbents with a high CO 2 uptake capacity. The sorbents synthesized feature compositional homogeneity in combination with a nanostructured and highly porous morphology. The presence of a single (Al 2 O 3 or Y 2 O 3 ) or bimetal oxide (Al 2 O 3 -Y 2 O 3 ) provides cyclic stability, except for MgO which undergoes a significant increase in its particle size with the cycle number. We also demonstrate a direct relationship between the CO 2 uptake and the morphology of the synthesized sorbents. After 30 cycles of calcination and carbonation, the best performing sorbent, containing an equimolar mixture of Al 2 O 3 and Y 2 O 3 , exhibits a CO 2 uptake capacity of 8.7 mmol CO 2  g -1 sorbent, which is approximately 360 % higher than that of the reference limestone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Effect of CO2 on Partial Reactive Crystallization of MORB-Eclogite-derived Basaltic Andesite in Peridotite and Generation of Silica-Undersaturated Basalts

NASA Astrophysics Data System (ADS)

Mallik, A.; Dasgupta, R.

2012-12-01

Recycled oceanic crust (MORB-eclogite) is considered to be the dominant heterogeneity in Earth's mantle. Because MORB-eclogite is more fusible than peridotite, siliceous partial melt derived from it must react with peridotite while the latter is still in the subsolidus state. Thus, studying such reactive process is important in understanding melting dynamics of the Earth's mantle. Reaction of MORB-eclogite-derived andesitic partial melt with peridotite can produce alkalic melts by partial reactive crystallization but these melts are not as silica-undersaturated as many natural basanites, nephelinites or melititites [1]. In this study, we constrain how dissolved CO2 in a siliceous MORB-eclogite-derived partial melt affects the reaction phase equilibria involving peridotite and can produce nephelinitic melts. Here we compare experiments on CO2-free [1] and 2.6 wt.% CO2 bearing andesitic melt+lherzolite mixtures conducted at 1375 °C and 3 GPa with added melt fraction of 8-50 wt.%. In both CO2-free and CO2-bearing experiments, melt and olivine are consumed and opx and garnet are produced, with the extent of modal change for a given melt-rock ratio being greater for the CO2-bearing experiments. While the residue evolves to a garnet websterite by adding 40% of CO2-bearing melt, the residue becomes olivine-free by adding 50% of the CO2-free melt. Opx mode increases from 12 to ~55 wt.% for 0 to 40% melt addition in CO2-bearing system and 12 to ~43 wt.% for 0 to 50% melt addition in CO2-free system. Garnet mode, for a similar range of melt-rock ratio, increases from ~10 to ~15 wt.% for CO2 bearing system and to ~11 wt.% for CO2-free system. Reacted melts from 25-33% of CO2-bearing melt-added runs contain ~39 wt.% SiO2 , ~11-13 wt.% TiO2, ~9 wt.% Al2O3, ~11 wt.% FeO*, 16 wt.% MgO, 10-11 wt.% CaO, and 3 wt.% Na2O whereas experiments with a similar melt-rock ratio in a CO2-free system yield melts with 44-45 wt.% SiO2, 6-7 wt.% TiO2, 13-14 wt.% Al2O3, 10-11 wt.% FeO*, 12-13 wt.% MgO, ~8 wt.% CaO, and ~4 wt.% Na2O. Our study shows that with only 2.6 wt.% CO2, andesites, owing to partial reactive crystallization in a peridotite matrix, can evolve to nephelinites (as opposed to basanites for CO2-free runs) that match with silica-undersaturated oceanic basalts better than reacted melts from CO2-free conditions. The effects of CO2 on the partial reactive crystallization of andesite in a fertile peridotite matrix thus are: a) lowered melt- SiO2 owing to increased stability of opx at the liquidus of basalt, b) lowered Al2O3 content of basalts owing to increased crystallization of garnet. Experiments with 1 and 5 wt.% CO2-bearing andesite-peridotite mixture are underway and will be presented. [1] Mallik and Dasgupta (2012), EPSL, 329-330, 97-108.

Maize and prairie root contributions to soil CO2 emissions in the field

USDA-ARS?s Scientific Manuscript database

Background and aims: A major hurdle in closing carbon budgets is partitioning soil-surface CO2 fluxes by source. This study aims to estimate CO2 resulting from root growth (RG) in the field. Methods: We used periodic 48-hour shading over two seasons to estimate and compare RG-derived CO2 in one annu...

Investigation of Oxygen Reduction Activity of Catalysts Derived from Co and Co/Zn Methyl-Imidazolate Frameworks in Proton Exchange Membrane Fuel Cells

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

Chong, Lina; Goenaga, Gabriel A.; Williams, Kia

We demonstrated that the oxygen reduction reaction (ORR) activity over the catalysts derived from pyrolyzed cobalt zeolitic imidazolate frameworks depends strongly on the imidazole ligand structure and cobalt content. The activity and durability of these catalysts were tested in the proton exchange membrane fuel cell for the first time. The membrane electrode assembly containing a catalyst derived from Co/Zn bimetallic ZIF at cathode achieved an open circuit voltage of 0.93 V, a current density of 28 mA cm-2 at 0.8 ViR-free and a peak power density of 374 mW cm-2.

In silico prediction of inhibitory effects of pyrazol-5-one and indazole derivatives on GSK3β kinase enzyme

NASA Astrophysics Data System (ADS)

Wang, Fangfang; Liu, Mengmeng; Liu, Jianling

2012-09-01

Glycogen synthase kinase-3 beta (GSK3β) plays an important role in a diverse number of regulatory pathways by phosphorylation of several different cellular targets and its inhibitors have been evaluated as promising drug candidates. In this work, 192 3-aryl-4-(arylhydrazono)-1H-pyrazol-5-one analogs (AHP) and indazoles (ID) derivatives possessing selective binding affinity for GSK3β kinase were studied using the 3D-QSAR/CoMFA/CoMSIA methodologies. The obtained CoMFA/CoMSIA models exhibit both good internal and external predictive abilities, i.e., Rcv2=0.551,Rpred2=0.698 for AHP derivatives and Rcv2=0.511,Rpred2=0.791 for ID analogs. Of paramount interest is the observation derived from the combination of molecular dynamics and molecular docking studies that Val135 and Asp133 are responsible for the binding recognition for AHP molecules, while residues Val135 and Pro136 are mainly involved in the specific ligand-kinase interactions for ID analogs. The developed models are seeking to be helpful for the rational design of novel potent GSK3β inhibitors.

Τhe observational and empirical thermospheric CO2 and NO power do not exhibit power-law behavior; an indication of their reliability

NASA Astrophysics Data System (ADS)

Varotsos, C. A.; Efstathiou, M. N.

2018-03-01

In this paper we investigate the evolution of the energy emitted by CO2 and NO from the Earth's thermosphere on a global scale using both observational and empirically derived data. In the beginning, we analyze the daily power observations of CO2 and NO received from the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) equipment on the NASA Thermosphere-Ionosphere-Mesosphere Energetics and Dynamics (TIMED) satellite for the entire period 2002-2016. We then perform the same analysis on the empirical daily power emitted by CO2 and NO that were derived recently from the infrared energy budget of the thermosphere during 1947-2016. The tool used for the analysis of the observational and empirical datasets is the detrended fluctuation analysis, in order to investigate whether the power emitted by CO2 and by NO from the thermosphere exhibits power-law behavior. The results obtained from both observational and empirical data do not support the establishment of the power-law behavior. This conclusion reveals that the empirically derived data are characterized by the same intrinsic properties as those of the observational ones, thus enhancing the validity of their reliability.

Study of CO2 cyclic absorption stability of CaO-based sorbents derived from lime mud purified by sucrose method.

PubMed

Ma, AiHua; Jia, QingMing; Su, HongYing; Zhi, YunFei; Tian, Na; Wu, Jing; Shan, ShaoYun

2016-02-01

Using lime mud (LM) purified by sucrose method, derived from paper-making industry, as calcium precursor, and using mineral rejects-bauxite-tailings (BTs) from aluminum production as dopant, the CaO-based sorbents for high-temperature CO2 capture were prepared. Effects of BTs content, precalcining time, and temperature on CO2 cyclic absorption stability were illustrated. The cyclic carbonation behavior was investigated in a thermogravimetric analyzer (TGA). Phase composition and morphologies were analyzed by XRD and SEM. The results reflected that the as-synthesized CaO-based sorbent doped with 10 wt% BTs showed a superior CO2 cyclic absorption-desorption conversion during multiple cycles, with conversion being >38 % after 50 cycles. Occurrence of Ca12Al14O33 phase during precalcination was probably responsible for the excellent CO2 cyclic stability.

Insights into the relationship between CO₂ switchability and basicity: examples of melamine and its derivatives.

PubMed

Yin, Hongyao; Feng, Yujun; Liu, Hanbin; Mu, Meng; Fei, Chenhong

2014-08-26

Owing to its wide availability, nontoxicity, and low cost, CO2 working as a trigger to reversibly switch material properties, including polarity, ionic strength, hydrophilicity, viscosity, surface charge, and degree of polymerization or cross-linking, has attracted an increasing attention in recent years. However, a quantitative correlation between basicity of these materials and their CO2 switchability has been less documented though it is of great importance for fabricating switchable system. In this work, the "switch-on" and "switch-off" abilities of melamine and its amino-substituted derivatives by introducing and removing CO2 are studied, and then their quantitative relationship with basicity is established, so that performances of other organobases can be quantitatively predicted. These findings are beneficial for forecasting the CO2 stimuli-responsive behavior of other organobases and the design of CO2-switchable materials.

Overcoming the positive-capture strategy in young children: learning about indeterminacy.

PubMed

Klahr, David; Chen, Zhe

2003-01-01

Two experiments were conducted to examine whether and how 4- and 5-year-olds learn to distinguish determinate from indeterminate evidence. Children were asked to decide whether various patterns of evidence were sufficient to reach unambiguous conclusions. This study replicated the finding that young children tend to use a strategy that, although generally successful, fails on evidence patterns in which a single positive instance co-occurs with an unexplored source of evidence. Experiment 1 demonstrated that this positive-capture strategy is deeply entrenched, even in a meaningful, pragmatic context. With a microgenetic design, Experiment 2 revealed that young children are capable of replacing the positive-capture strategy with a correct strategy when they are exposed to various analogous tasks in several training sessions.

Comparative analysis of geological features and seasonal processes in "Inca City" and "Pityusa Patera" regions on Mars

NASA Astrophysics Data System (ADS)

Manrubia, S. C.; Prieto Ballesteros, O.; González Kessler, C.; Fernández Remolar, D.; Córdoba-Jabonero, C.; Selsis, F.; Bérczi, S.; Gánti, T.; Horváth, A.; Sik, A.; Szathmáry, E.

2004-03-01

We carry out a comparative analysis of the morphological and seasonal features of two regions in the Martian Southern Polar Region: the Inca City (82S 65W) and the Pityusa Patera zone (66S 37E). These two sites are representative of a large number of areas which are subjected to dynamical, seasonal processes that deeply modify the local conditions of those regions. Due to varitions in sunlight, seasonal CO2 accumulates during autumn and winter and starts defrosting in spring. By mid summer the seasonal ice has disappeared. Despite a number of relevant differences in the morphology of the seasonal features observed, they seem to result from similar processes.

Fractional calculus in hydrologic modeling: A numerical perspective

PubMed Central

Benson, David A.; Meerschaert, Mark M.; Revielle, Jordan

2013-01-01

Fractional derivatives can be viewed either as handy extensions of classical calculus or, more deeply, as mathematical operators defined by natural phenomena. This follows the view that the diffusion equation is defined as the governing equation of a Brownian motion. In this paper, we emphasize that fractional derivatives come from the governing equations of stable Lévy motion, and that fractional integration is the corresponding inverse operator. Fractional integration, and its multi-dimensional extensions derived in this way, are intimately tied to fractional Brownian (and Lévy) motions and noises. By following these general principles, we discuss the Eulerian and Lagrangian numerical solutions to fractional partial differential equations, and Eulerian methods for stochastic integrals. These numerical approximations illuminate the essential nature of the fractional calculus. PMID:23524449

North American CO2 fluxes for 2007-2015 from NOAA's CarbonTracker-Lagrange Regional Inverse Modeling Framework

NASA Astrophysics Data System (ADS)

Andrews, A. E.; Hu, L.; Thoning, K. W.; Nehrkorn, T.; Mountain, M. E.; Jacobson, A. R.; Michalak, A.; Dlugokencky, E. J.; Sweeney, C.; Worthy, D. E. J.; Miller, J. B.; Fischer, M. L.; Biraud, S.; van der Velde, I. R.; Basu, S.; Tans, P. P.

2017-12-01

CarbonTracker-Lagrange (CT-L) is a new high-resolution regional inverse modeling system for improved estimation of North American CO2 fluxes. CT-L uses footprints from the Stochastic Time-Inverted Lagrangian Transport (STILT) model driven by high-resolution (10 to 30 km) meteorological fields from the Weather Research and Forecasting (WRF) model. We performed a suite of synthetic-data experiments to evaluate a variety of inversion configurations, including (1) solving for scaling factors to an a priori flux versus additive corrections, (2) solving for fluxes at 3-hrly resolution versus at coarser temporal resolution, (3) solving for fluxes at 1o × 1o resolution versus at large eco-regional scales. Our framework explicitly and objectively solves for the optimal solution with a full error covariance matrix with maximum likelihood estimation, thereby enabling rigorous uncertainty estimates for the derived fluxes. In the synthetic-data inversions, we find that solving for weekly scaling factors of a priori Net Ecosystem Exchange (NEE) at 1o × 1o resolution with optimization of diurnal cycles of CO2 fluxes yields faithful retrieval of the specified "true" fluxes as those solved at 3-hrly resolution. In contrast, a scheme that does not allow for optimization of diurnal cycles of CO2 fluxes suffered from larger aggregation errors. We then applied the optimal inversion setup to estimate North American fluxes for 2007-2015 using real atmospheric CO2 observations, multiple prior estimates of NEE, and multiple boundary values estimated from the NOAA's global Eulerian CarbonTracker (CarbonTracker) and from an empirical approach. Our derived North American land CO2 fluxes show larger seasonal amplitude than those estimated from the CarbonTracker, removing seasonal biases in the CarbonTracker's simulated CO2 mole fractions. Independent evaluations using in-situ CO2 eddy covariance flux measurements and independent aircraft profiles also suggest an improved estimation on North American CO2 fluxes from CT-L. Furthermore, our derived CO2 flux anomalies over North America corresponding to the 2012 North American drought and the 2015 El Niño are larger than derived by the CarbonTracker. They also indicate different responses of ecosystems to those anomalous climatic events.

Relationship between clinical signs and pulmonary function estimated by the single breath diagram for CO(2) (SBD-CO(2)) in horses with chronic obstructive pulmonary disease.

PubMed

Herholz, C; Straub, R; Gerber, V; Wampfler, B; Lüthi, S; Imhof, A; Moens, Y; Busato, A

2002-03-01

The pulmonary health of 66 horses was assessed by a clinical examination and simple supplementary diagnostic methods. Single breath diagrams for CO(2) (SBD-CO(2)) and derived lung function indices were used to determine pulmonary function. The clinical signs in different groups were related to the results of the lung function indices derived from the SBD-CO(2). In horses with moderate to severe chronic obstructive pulmonary disease (COPD), a significant relationship was found between the respiratory frequency and the ratio of Bohr's dead space to the tidal volume (VD(Bohr)/VT), and between the physiological dead space/tidal volume ratio (VD(phys)/VT) and the ratio of the alveolar dead space to the alveolar tidal volume (VD(alv)/VT(alv)), but no significant associations were found between the arterial oxygen tension (P(a)O(2)) and lung function indices derived from the SBD-CO(2). The occurrence of cough, the viscosity of tracheobronchial mucus and the amount of polynuclear neutrophils in tracheobronchial aspirates were significantly related to the expiratory tidal volume (VT), the total expired volume of CO(2) (VCO(2)), VD(Bohr)/VT, VD(phys)/VT and VD(alv)/VT(alv). We conclude that abnormal findings in these clinical parameters indicate a measurable ventilation and perfusion (V(A)/Q) mismatch which is reflected by increases in dead space, VD(Bohr)/VT and VD(phys)/VT as well as VD(alv)/VT(alv). Copyright 2002 Elsevier Science Ltd. All rights reserved.

Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts

DOE PAGES

Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P.; ...

2015-07-30

CO electroreduction activity on oxide-derived Cu (OD-Cu) was found to correlate with metastable surface features that bind CO strongly. OD-Cu electrodes prepared by H 2 reduction of Cu 2O precursors reduce CO to acetate and ethanol with nearly 50% Faradaic efficiency at moderate overpotential. Temperature-programmed desorption of CO on OD-Cu revealed the presence of surface sites with strong CO binding that are distinct from the terraces and stepped sites found on polycrystalline Cu foil. After annealing at 350 °C, the surface-area corrected current density for CO reduction is 44-fold lower and the Faradaic efficiency is less than 5%. These changesmore » are accompanied by a reduction in the proportion of strong CO binding sites. Here, we propose that the active sites for CO reduction on OD-Cu surfaces are strong CO binding sites that are supported by grain boundaries. Uncovering these sites is a first step toward understanding the surface chemistry necessary for efficient CO electroreduction.« less

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

M. Mercedes Maroto-Valer; John M. Andresen; Yinzhi Zhang

This research program focused on the development of fly ash derived sorbents to capture CO{sub 2} from power plant flue gas emissions. The fly ash derived sorbents developed represent an affordable alternative to existing methods using specialized activated carbons and molecular sieves, that tend to be very expensive and hinder the viability of the CO{sub 2} sorption process due to economic constraints. Under Task 1 'Procurement and characterization of a suite of fly ashes', 10 fly ash samples, named FAS-1 to -10, were collected from different combustors with different feedstocks, including bituminous coal, PRB coal and biomass. These samples presentedmore » a wide range of LOI value from 0.66-84.0%, and different burn-off profiles. The samples also spanned a wide range of total specific surface area and pore volume. These variations reflect the difference in the feedstock, types of combustors, collection hopper, and the beneficiation technologies the different fly ashes underwent. Under Task 2 'Preparation of fly ash derived sorbents', the fly ash samples were activated by steam. Nitrogen adsorption isotherms were used to characterize the resultant activated samples. The cost-saving one-step activation process applied was successfully used to increase the surface area and pore volume of all the fly ash samples. The activated samples present very different surface areas and pore volumes due to the range in physical and chemical properties of their precursors. Furthermore, one activated fly ash sample, FAS-4, was loaded with amine-containing chemicals (MEA, DEA, AMP, and MDEA). The impregnation significantly decreased the surface area and pore volume of the parent activated fly ash sample. Under Task 3 'Capture of CO{sub 2} by fly ash derived sorbents', sample FAS-10 and its deashed counterpart before and after impregnation of chemical PEI were used for the CO{sub 2} adsorption at different temperatures. The sample FAS-10 exhibited a CO{sub 2} adsorption capacity of 17.5mg/g at 30 C, and decreases to 10.25mg/g at 75 C, while those for de-ashed counterpart are 43.5mg/g and 22.0 mg/g at 30 C and 75 C, respectively. After loading PEI, the CO{sub 2} adsorption capacity increased to 93.6 mg/g at 75 C for de-ashed sample and 62.1 mg/g at 75 C for raw fly ash sample. The activated fly ash, FAS-4, and its chemical loaded counterparts were tested for CO{sub 2} capture capacity. The activated carbon exhibited a CO{sub 2} adsorption capacity of 40.3mg/g at 30 C that decreased to 18.5mg/g at 70 C and 7.7mg/g at 120 C. The CO{sub 2} adsorption capacity profiles changed significantly after impregnation. For the MEA loaded sample the capacity increased to 68.6mg/g at 30 C. The loading of MDEA and DEA initially decreased the CO{sub 2} adsorption capacity at 30 C compared to the parent sample but increased to 40.6 and 37.1mg/g, respectively, when the temperature increased to 70 C. The loading of AMP decrease the CO{sub 2} adsorption capacity compared to the parent sample under all the studied temperatures. Under Task 4 'Comparison of the CO{sub 2} capture by fly ash derived sorbents with commercial sorbents', the CO{sub 2} adsorption capacities of selected activated fly ash carbons were compared to commercial activated carbons. The CO{sub 2} adsorption capacity of fly ash derived activated carbon, FAS-4, and its chemical loaded counterpart presented CO{sub 2} capture capacities close to 7 wt%, which are comparable to, and even better than, the published values of 3-4%.« less

Charge-Transfer Analysis of 2p3d Resonant Inelastic X-ray Scattering of Cobalt Sulfide and Halides

PubMed Central

2017-01-01

We show that with 2p3d resonant inelastic X-ray scattering (RIXS) we can accurately determine the charge-transfer parameters of CoF2, CoCl2, CoBr2, and CoS. The 160 meV resolution RIXS results are compared with charge-transfer multiplet calculations. The improved resolution and the direct observation of the crystal field and charge-transfer excitations allow the determination of more accurate parameters than could be derived from X-ray absorption and X-ray photoemission, both limited in resolution by their lifetime broadening. We derive the crystal field and charge-transfer parameters of the Co2+ ions, which provides the nature of the ground state of the Co2+ ions with respect to symmetry and hybridization. In addition, the increased spectral resolution allows the more accurate determination of the atomic Slater integrals. The results show that the crystal field energy decreases with increasing ligand covalency. The L2 edge RIXS spectra show that the intensity of the (Coster–Kronig induced) nonresonant X-ray emission is a measure of ligand covalency. PMID:29170686

Rational construction of a stable Zn4O-based MOF for highly efficient CO2 capture and conversion.

PubMed

Zhou, Hui-Fang; Liu, Bo; Hou, Lei; Zhang, Wen-Yan; Wang, Yao-Yu

2018-01-11

By employing a carboxylate ligand derived from benzene-1,4-dicarboxylate, a chemically stable Zn 4 O-based self-penetrating metal-organic framework has been rationally synthesized, which exhibits high CO 2 adsorption and efficient catalytic conversion for CO 2 cycloaddition.

Measuring priming using 14C of respired CO2: effects on respiration source pools and interactions with warming

NASA Astrophysics Data System (ADS)

Hopkins, F. M.; Trumbore, S.

2011-12-01

The role of substrate availability on soil carbon turnover is a critical unknown in predicting future soil carbon stocks. Substrate composition and availability can be altered by land cover change, warming, and nitrogen deposition, which can in turn affect soil carbon stocks through the priming effect. In particular, little is understood about the interaction between warming and changing substrate concentration. We examined the interactions between global change factors and the priming effect using sucrose addition to incubations of soils from two forest Free Air CO2 Enrichment (FACE) sites (Duke and Aspen). In addition to the in situ global change manipulations conducted at these sites, the CO2 fertilization procedure over the decade-long experiment labeled soil carbon pools with fossil-derived carbon (depleted in 14C relative to the background isotope content of soil carbon), allowing us to determine the effect of priming on respiration of soil carbon substrates of different ages. Thus, we used the carbon-13 signature of sucrose-derived CO2 to account for losses of substrate C, and the carbon-14 signature to partition fluxes of soil-derived CO2 between pre-FACE (> 10 y) and FACE derived (< 10 y) carbon sources. At both sites, we observed a positive priming effect-an increase in the rate of soil carbon derived respiration due to sucrose addition. However, the effect of substrate addition on respiratory source pools, as measured by 14C of respiration, varied greatly. At Duke FACE, we observed an increase in 14C content of CO2 of primed soil carbon, whereas at Aspen, we observed no difference. The amount of CO2 released by priming increased with temperature, but was proportionally similar to the amount of increase in basal respiration rates (no differences in Q10). At Duke, both warming and priming served to increase the 14C of respiration, whereas only warming changed 14C of respiration at Aspen. Despite similar overall carbon stocks, differences in the source of the priming effect between the two sites may be due to inherent differences in the relative role of stabilization factors within the soil carbon stock.

Extraordinary GU-rich single-strand RNA identified from SARS coronavirus contributes an excessive innate immune response.

PubMed

Li, Yan; Chen, Ming; Cao, Hongwei; Zhu, Yuanfeng; Zheng, Jiang; Zhou, Hong

2013-02-01

A dangerous cytokine storm occurs in the SARS involving in immune disorder, but many aspects of the pathogenetic mechanism remain obscure since its outbreak. To deeply reveal the interaction of host and SARS-CoV, based on the basic structural feature of pathogen-associated molecular pattern, we created a new bioinformatics method for searching potential pathogenic molecules and identified a set of SARS-CoV specific GU-rich ssRNA fragments with a high-density distribution in the genome. In vitro experiments, the result showed the representative SARS-CoV ssRNAs had powerful immunostimulatory activities to induce considerable level of pro-inflammatory cytokine TNF-a, IL-6 and IL-12 release via the TLR7 and TLR8, almost 2-fold higher than the strong stimulatory ssRNA40 that was found previously from other virus. Moreover, SARS-CoV ssRNA was able to cause acute lung injury in mice with a high mortality rate in vivo experiment. It suggests that SARS-CoV specific GU-rich ssRNA plays a very important role in the cytokine storm associated with a dysregulation of the innate immunity. This study not only presents new evidence about the immunopathologic damage caused by overactive inflammation during the SARS-CoV infection, but also provides a useful clue for a new therapeutic strategy. Copyright © 2012 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

3D-QSAR and docking studies of 3-Pyridine heterocyclic derivatives as potent PI3K/mTOR inhibitors

NASA Astrophysics Data System (ADS)

Yang, Wenjuan; Shu, Mao; Wang, Yuanqiang; Wang, Rui; Hu, Yong; Meng, Lingxin; Lin, Zhihua

2013-12-01

Phosphoinosmde-3-kinase/ mammalian target of rapamycin (PI3K/mTOR) dual inhibitors have attracted a great deal of interest as antitumor drugs research. In order to design and optimize these dual inhibitors, two types of 3D-quantitative structure-activity relationship (3D-QSAR) studies based on the ligand alignment and receptor alignment were applied using the comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA). In the study based on ligands alignment, models of PI3K (CoMFA with r2, 0.770; q2, 0.622; CoMSIA with r2, 0.945; q2, 0.748) and mTOR (CoMFA with r2, 0.850; q2, 0.654; CoMSIA with r2, 0.983; q2, 0.676) have good predictability. And in the study based on receptor alignment, models of PI3K (CoMFA with r2, 0.745; q2, 0.538; CoMSIA with r2, 0.938; q2, 0.630) and mTOR (CoMFA with r2, 0.977; q2, 0.825; CoMSIA with r2, 0.985; q2, 0.728) also have good predictability. 3D contour maps and docking results suggested different groups on the core parts of the compounds could enhance the biological activities. Finally, ten derivatives as potential candidates of PI3K/mTOR inhibitors with good predicted activities were designed.

Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO 2 Reduction

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

Lum, Yanwei; Yue, Binbin; Lobaccaro, Peter

Here, copper electrodes, prepared by reduction of oxidized metallic copper, have been reported to exhibit higher activity for the electrochemical reduction of CO 2 and better selectivity toward C 2 and C 3 (C 2+) products than metallic copper that has not been preoxidized. We report here an investigation of the effects of four different preparations of oxide-derived electrocatalysts on their activity and selectivity for CO 2 reduction, with particular attention given to the selectivity to C 2+ products. All catalysts were tested for CO 2 reduction in 0.1 M KHCO 3 and 0.1 M CsHCO 3 at applied voltagesmore » in the range from –0.7 to –1.0 V vs RHE. The best performing oxide-derived catalysts show up to ~70% selectivity to C 2+ products and only ~3% selectivity to C 1 products at –1.0 V vs RHE when CsHCO 3 is used as the electrolyte. In contrast, the selectivity to C 2+ products decreases to ~56% for the same catalysts tested in KHCO 3. By studying all catalysts under identical conditions, the key factors affecting product selectivity could be discerned. These efforts reveal that the surface area of the oxide-derived layer is a critical parameter affecting selectivity. A high selectivity to C 2+ products is attained at an overpotential of –1 V vs RHE by operating at a current density sufficiently high to achieve a moderately high pH near the catalyst surface but not so high as to cause a significant reduction in the local concentration of CO 2. On the basis of recent theoretical studies, a high pH suppresses the formation of C 1 relative to C 2+ products. At the same time, however, a high local CO 2 concentration is necessary for the formation of C 2+ products.« less

Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO 2 Reduction

DOE PAGES

Lum, Yanwei; Yue, Binbin; Lobaccaro, Peter; ...

2017-07-06

Here, copper electrodes, prepared by reduction of oxidized metallic copper, have been reported to exhibit higher activity for the electrochemical reduction of CO 2 and better selectivity toward C 2 and C 3 (C 2+) products than metallic copper that has not been preoxidized. We report here an investigation of the effects of four different preparations of oxide-derived electrocatalysts on their activity and selectivity for CO 2 reduction, with particular attention given to the selectivity to C 2+ products. All catalysts were tested for CO 2 reduction in 0.1 M KHCO 3 and 0.1 M CsHCO 3 at applied voltagesmore » in the range from –0.7 to –1.0 V vs RHE. The best performing oxide-derived catalysts show up to ~70% selectivity to C 2+ products and only ~3% selectivity to C 1 products at –1.0 V vs RHE when CsHCO 3 is used as the electrolyte. In contrast, the selectivity to C 2+ products decreases to ~56% for the same catalysts tested in KHCO 3. By studying all catalysts under identical conditions, the key factors affecting product selectivity could be discerned. These efforts reveal that the surface area of the oxide-derived layer is a critical parameter affecting selectivity. A high selectivity to C 2+ products is attained at an overpotential of –1 V vs RHE by operating at a current density sufficiently high to achieve a moderately high pH near the catalyst surface but not so high as to cause a significant reduction in the local concentration of CO 2. On the basis of recent theoretical studies, a high pH suppresses the formation of C 1 relative to C 2+ products. At the same time, however, a high local CO 2 concentration is necessary for the formation of C 2+ products.« less

Interstitial solutions and diagenesis in deeply buried marine sediments: results from the Deep Sea Drilling Project

USGS Publications Warehouse

Sayles, F.L.; Manheim, F.T.

1975-01-01

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments. Pelagic clays and slowly deposited (<1 cm/103yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters. In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/103 yr the changes chiefly involve gains of Ca2+ and Sr2+ and losses of Mg2+ which balance the Ca2+ enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr2+ may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg2+ for Ca2+ during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca2+ and Sr2+ enrichment is again characteristic, but Mg2+ losses exceed Ca2+ gains with the excess being balanced by SO4post staggered2- losses. The data indicate that the reactions are similar to those noted above, except that the Ca2+ released is not kept in solution but is precipitated by the HCO3post staggered- produced in SO4post staggered2- reduction. In both these types of pore waters Na+ is usually conservative, but K+ depletions are frequent. In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na+, Si and CO2, and slight enhancement in Cl-. The changes are attributed to exchange of Na+ for Ca2+ in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity. Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO4post staggered2-, strong HCO3post staggered- enrichment, formation of NH4post staggered+, and methane synthesis from H2 and CO2 once SO4post staggered2- is eliminated. K+ and often Na+ (slightly) are depleted in the interstitial waters. Ca2+ depletion may occur owing to precipitation of CaCO3. In most cases interstitial Cl- remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl- are observed in some sediments adjacent to continents. ?? 1975.

Radiocarbon-depleted CO2 evidence for fuel biodegradation at the Naval Air Station North Island (USA) fuel farm site.

PubMed

Boyd, Thomas J; Pound, Michael J; Lohr, Daniel; Coffin, Richard B

2013-05-01

Dissolved CO(2) radiocarbon and stable carbon isotope ratios were measured in groundwater from a fuel contaminated site at the North Island Naval Air Station in San Diego, CA (USA). A background groundwater sampling well and 16 wells in the underground fuel contamination zone were evaluated. For each sample, a two end-member isotopic mixing model was used to determine the fraction of CO(2) derived from fossil fuel. The CO(2) fraction from fossil sources ranged from 8 to 93% at the fuel contaminated site, while stable carbon isotope values ranged from -14 to +5‰VPDB. Wells associated with highest historical and contemporary fuel contamination showed the highest fraction of CO(2) derived from petroleum (fossil) sources. Stable carbon isotope ratios indicated sub-regions on-site with recycled CO(2) (δ(13)CO(2) as high as +5‰VPDB) - most likely resulting from methanogenesis. Ancillary measurements (pH and cations) were used to determine that no fossil CaCO(3), for instance limestone, biased the analytical conclusions. Radiocarbon analysis is verified as a viable and definitive technique for confirming fossil hydrocarbon conversion to CO(2) (complete oxidation) at hydrocarbon-contaminated groundwater sites. The technique should also be very useful for assessing the efficacy of engineered remediation efforts and by using CO(2) production rates, contaminant mass conversion over time and per unit volume.

Critical evaluation of 13C natural abundance techniques to partition soil-surface CO2 efflux

NASA Astrophysics Data System (ADS)

Snell, H.; Midwood, A. J.; Robinson, D.

2013-12-01

Soil is the largest terrestrial store of carbon and the flux of CO2 from soils to the atmosphere is estimated at around 98 Pg (98 billion tonnes) of carbon per year. The CO2 efflux from the soil surface is derived from plant root and rhizosphere respiration (autotrophically fuelled) and microbial degradation of soil organic matter (heterotrophic respiration). Heterotrophic respiration is a key determinant of an ecosystem's long-term C balance, but one that is difficult to measure in the field. One approach involves partitioning the total soil-surface CO2 efflux between heterotrophic and autotrophic components; this can be done using differences in the natural abundance stable isotope ratios (δ13C) of autotrophic and heterotrophic CO2 as the end-members of a simple mixing model. In most natural, temperate ecosystems, current and historical vegetation cover (and therefore also plant-derived soil organic matter) is produced from C3 photosynthesis so the difference in δ13C between the autotrophic and heterotrophic CO2 sources is small. Successful partitioning therefore requires accurate and precise measurements of the δ13CO2 of the autotrophic and heterotrophic end-members (obtained by measuring the δ13CO2 of soil-free roots and root-free soil) and of total soil CO2 efflux. There is currently little consensus on the optimum measurement protocols. Here we systematically tested some of the most commonly used techniques to identify and minimise methodological errors. Using soil-surface chambers to sample total CO2 efflux and a cavity ring-down spectrometer to measure δ13CO2 in a partitioning study on a Scottish moorland, we found that: using soil-penetrating collars leads to a more depleted chamber measurement of total soil δ13CO2 as a result of severing roots and fungal hyphae or equilibrating with δ13CO2 at depth or both; root incubations provide an accurate estimate of in-situ root respired δ13CO2 provided they are sampled within one hour; the δ13CO2 from root-free soil changes rapidly during incubation and even CO2 sampled very soon after excavation is unlikely to give an accurate estimate of the heterotrophic isotope end-member, to solve this we applied non-linear regressions to the change in δ13CO2 with time to derive the heterotrophic end-member in undisturbed soil.

Properties of the plant- and manure-derived biochars and their sorption of dibutyl phthalate and phenanthrene

NASA Astrophysics Data System (ADS)

Qiu, Mengyi; Sun, Ke; Jin, Jie; Gao, Bo; Yan, Yu; Han, Lanfang; Wu, Fengchang; Xing, Baoshan

2014-06-01

The properties of plant residue-derived biochars (PLABs) and animal waste-derived biochars (ANIBs) obtained at low and high heating treatment temperatures (300 and 450°C) as well as their sorption of dibutyl phthalate (DBP) and phenanthrene (PHE) were investigated in this study. The higher C content of PLABs could explain that CO2-surface area (CO2-SA) of PLABs was remarkably high relative to ANIBs. OC and aromatic C were two key factors influencing the CO2-SA of the biochars. Much higher surface C content of the ANIBs than bulk C likely explained that the ANIBs exhibited higher sorption of DBP and PHE compared to the PLABs. H-bonding should govern the adsorption of DBP by most of the tested biochars and π-π interaction play an important role in the adsorption of PHE by biochars. High CO2-SA (>200 m2 g-1) demonstrated that abundant nanopores of OC existed within the biochars obtained 450°C (HTBs), which likely result in high and nonlinear sorption of PHE by HTBs.

Plant polyketide synthases: a chalcone synthase-type enzyme which performs a condensation reaction with methylmalonyl-CoA in the biosynthesis of C-methylated chalcones.

PubMed

Schröder, J; Raiber, S; Berger, T; Schmidt, A; Schmidt, J; Soares-Sello, A M; Bardshiri, E; Strack, D; Simpson, T J; Veit, M; Schröder, G

1998-06-09

Heterologous screening of a cDNA library from Pinusstrobus seedlings identified clones for two chalcone synthase (CHS) related proteins (PStrCHS1 and PStrCHS2, 87.6% identity). Heterologous expression in Escherichia coli showed that PStrCHS1 performed the typical CHS reaction, that it used starter CoA-esters from the phenylpropanoid pathway, and that it performed three condensation reactions with malonyl-CoA, followed by the ring closure to the chalcone. PstrCHS2 was completely inactive with these starters and also with linear CoA-esters. Activity was detected only with a diketide derivative (N-acetylcysteamine thioester of 3-oxo-5-phenylpent-4-enoic acid) that corresponded to the CHS reaction intermediate postulated after the first condensation reaction. PstrCHS2 performed only one condensation, with 6-styryl-4-hydroxy-2-pyrone derivatives as release products. The enzyme preferred methylmalonyl-CoA against malonyl-CoA, if only methylmalonyl-CoA was available. These properties and a comparison with the CHS from Pinus sylvestris suggested for PstrCHS2 a special function in the biosynthesis of secondary products. In contrast to P. sylvestris, P. strobus contains C-methylated chalcone derivatives, and the methyl group is at the position predicted from a chain extension with methylmalonyl-CoA in the second condensation of the biosynthetic reaction sequence. We propose that PstrCHS2 specifically contributes the condensing reaction with methylmalonyl-CoA to yield a methylated triketide intermediate. We discuss a model that the biosynthesis of C-methylated chalcones represents the simplest example of a modular polyketide synthase.

Evolution of CO lines in time-dependent models of protostellar disk formation

NASA Astrophysics Data System (ADS)

Harsono, D.; Visser, R.; Bruderer, S.; van Dishoeck, E. F.; Kristensen, L. E.

2013-07-01

Context. Star and planet formation theories predict an evolution in the density, temperature, and velocity structure as the envelope collapses and forms an accretion disk. While continuum emission can trace the dust evolution, spectrally resolved molecular lines are needed to determine the physical structure and collapse dynamics. Aims: The aim of this work is to model the evolution of the molecular excitation, line profiles, and related observables during low-mass star formation. Specifically, the signatures of disks during the deeply embedded stage (Menv > M⋆) are investigated. Methods: The semi-analytic 2D axisymmetric model of Visser and collaborators has been used to describe the evolution of the density, stellar mass, and luminosity from the pre-stellar to the T-Tauri phase. A full radiative transfer calculation is carried out to accurately determine the time-dependent dust temperatures. The time-dependent CO abundance is obtained from the adsorption and thermal desorption chemistry. Non-LTE near-IR (NIR), far-IR (FIR), and submm lines of CO have been simulated at a number of time steps. Results: In single dish (10-20'' beams), the dynamics during the collapse are best probed through highly excited 13CO and C18O lines, which are significantly broadened by the infall process. In contrast to the dust temperature, the CO excitation temperature derived from submm/FIR data does not vary during the protostellar evolution, consistent with C18O observations obtained with Herschel and from ground-based telescopes. The NIR spectra provide complementary information to the submm lines by probing not only the cold outer envelope but also the warm inner region. The NIR high-J (≥8) absorption lines are particularly sensitive to the physical structure of the inner few AU, which does show evolution. The models indicate that observations of 13CO and C18O low-J submm lines within a ≤1″ (at 140 pc) beam are well suited to probe embedded disks in Stage I (Menv < M⋆) sources, consistent with recent interferometric observations. High signal-to-noise ratio subarcsec resolution data with ALMA are needed to detect the presence of small rotationally supported disks during the Stage 0 phase and various diagnostics are discussed. The combination of spatially and spectrally resolved lines with ALMA and at NIR is a powerful method to probe the inner envelope and disk formation process during the embedded phase. Appendices are available in electronic form at http://www.aanda.org

CO2 and soil water potential as regulators of the growth and N fraction derived from fixation of a legume in tallgrass prairie communities

USDA-ARS?s Scientific Manuscript database

CO2 enrichment may increase N input to ecosystems by increasing N2 fixation, but the fixation-CO2 response depends on factors such as soil water availability that are influenced by both CO2 and soil properties. We used the d15N natural abundance method to determine N2 fixation by the legume Desmant...

Formate production through biocatalysis

PubMed Central

Alissandratos, Apostolos; Kim, Hye-Kyung; Easton, Christopher J

2013-01-01

The generation of formate from CO2 provides a method for sequestration of this greenhouse gas as well as the production of a valuable commodity chemical and stabilized form of hydrogen fuel. Formate dehydrogenases are enzymes with the potential to catalyze this reaction; however they generally favor the reverse process, i.e., formate oxidation. By contrast, the formate dehydrogenase of the acetogen Clostridium carboxidivorans has been found to preferentially catalyze the reduction of CO2. This is in accord with its natural role to introduce CO2 as a carbon source in the Wood-Ljungdahl pathway. The direction of catalysis derives from the enzyme’s low affinity for formate. This enzyme is therefore an excellent candidate for biotechnological applications aimed at producing formic acid and derivative chemicals from CO2. PMID:23841981

Spectroscopic evaluation of Co(II), Ni(II) and Cu(II) complexes derived from thiosemicarbazone and semicarbazone

NASA Astrophysics Data System (ADS)

Chandra, Sulekh; Kumar, Anil

2007-12-01

Co(II), Ni(II) and Cu(II) complexes were synthesized with thiosemicarbazone (L 1) and semicarbazone (L 2) derived from 2-acetyl furan. These complexes were characterized by elemental analysis, molar conductance, magnetic moment, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non-electrolytic nature. All the complexes are of high-spin type. On the basis of different spectral studies six coordinated geometry may be assigned for all the complexes except Co(L) 2(SO 4) and Cu(L) 2(SO 4) [where L = L 1 and L 2] which are of five coordinated square pyramidal geometry.

Effect of bicarbonate on iron-mediated oxidation of low-density lipoprotein

NASA Astrophysics Data System (ADS)

Arai, Hirofumi; Berlett, Barbara S.; Chock, P. Boon; Stadtman, Earl R.

2005-07-01

Oxidation of low-density lipoprotein (LDL) may play an important role in atherosclerosis. We studied the effects of bicarbonate/CO2 and phosphate buffer systems on metal ion-catalyzed oxidation of LDL to malondialdehyde (MDA) and to protein carbonyl and MetO derivatives. Our results revealed that LDL oxidation in mixtures containing free iron or heme derivatives was much greater in bicarbonate/CO2 compared with phosphate buffer. However, when copper was substituted for iron in these mixtures, the rate of LDL oxidation in both buffers was similar. Iron-catalyzed oxidation of LDL was highly sensitive to inhibition by phosphate. Presence of 0.3-0.5 mM phosphate, characteristic of human serum, led to 30-40% inhibition of LDL oxidation in bicarbonate/CO2 buffer. Iron-catalyzed oxidation of LDL to MDA in phosphate buffer was inhibited by increasing concentrations of albumin (10-200 μM), whereas MDA formation in bicarbonate/CO2 buffer was stimulated by 10-50 μM albumin but inhibited by higher concentrations. However, albumin stimulated the oxidation of LDL proteins to carbonyl derivatives at all concentrations examined in both buffers. Conversion of LDL to MDA in bicarbonate/CO2 buffer was greatly stimulated by ADP, ATP, and EDTA but only when EDTA was added at a concentration equal to that of iron. At higher than stoichiometric concentrations, EDTA prevented oxidation of LDL. Results of these studies suggest that interactions between bicarbonate and iron or heme derivatives leads to complexes with redox potentials that favor the generation of reactive oxygen species and/or to the generation of highly reactive CO2 anion or bicarbonate radical that facilitates LDL oxidation. Freely available online through the PNAS open access option.Abbreviations: LDL, low-density lipoprotein; MDA, malondialdehyde; MetO, methionine sulfoxide.

CO2 Separation and Capture Properties of Porous Carbonaceous Materials from Leather Residues

PubMed Central

Bermúdez, José M.; Dominguez, Pablo Haro; Arenillas, Ana; Cot, Jaume; Weber, Jens; Luque, Rafael

2013-01-01

Carbonaceous porous materials derived from leather skin residues have been found to have excellent CO2 adsorption properties, with interestingly high gas selectivities for CO2 (α > 200 at a gas composition of 15% CO2/85% N2, 273K, 1 bar) and capacities (>2 mmol·g−1 at 273 K). Both CO2 isotherms and the high heat of adsorption pointed to the presence of strong binding sites for CO2 which may be correlated with both: N content in the leather residues and ultrasmall pore sizes. PMID:28788352

Interactive Effects of Climate Change and Decomposer Communities on the Stabilization of Wood-Derived Carbon Pools: Catalyst for a New Study

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

Resh, Sigrid C.

Globally, forest soils store ~two-thirds as much carbon (C) as the atmosphere. Although wood makes up the majority of forest biomass, the importance of wood contributions to soil C pools is unknown. Even with recent advances in the mechanistic understanding of soil processes, integrative studies tracing C input pathways and biological fluxes within and from soils are lacking. Therefore, our research objectives were to assess the impact of different fungal decay pathways (i.e., white-rot versus brown-rot)—in interaction with wood quality, soil temperature, wood location (i.e., soil surface and buried in mineral soil), and soil texture—on the transformation of woody materialmore » into soil CO 2 efflux, dissolved organic carbon (DOC), and soil C pools. The use of 13C-depleted woody biomass harvested from the Rhinelander, WI free-air carbon dioxide enrichment (Aspen-FACE) experiment affords the unique opportunity to distinguish the wood-derived C from other soil C fluxes and pools. We established 168 treatment plots across six field sites (three sand and three loam textured soil). Treatment plots consisted of full-factorial design with the following treatments: 1. Wood chips from elevated CO 2, elevated CO 2 + O 3, or ambient atmosphere AspenFACE treatments; 2. Inoculated with white rot (Bjerkandera adusta) or brown rot (Gloeophyllum sepiarium) pure fungal cultures, or the original suite of endemic microbial community on the logs; and 3. Buried (15cm in soil as a proxy for coarse roots) or surface applied wood chips. We also created a warming treatment using open-topped, passive warming chambers on a subset of the above treatments. Control plots with no added wood (“no chip control”) were incorporated into the research design. Soils were sampled for initial δ 13C values, CN concentrations, and bulk density. A subset of plots were instrumented with lysimeters for sampling soil water and temperature data loggers for measuring soil temperatures. To determine the early pathways of decomposition, we measured soil surface CO 2 efflux, dissolved organic C (DOC), and DO 13C approximately monthly over two growing seasons from a subsample of the research plots. To determine the portion of soil surface CO 2 efflux attributable to wood-derived C, we used Keeling plot techniques to estimate the associated δ 13C values of the soil CO 2 efflux. We measured the δ 13CO 2 once during the peak of each growing season. Initial values for soil δ 13C values and CN concentrations averaged across the six sites were -26.8‰ (standard error = 0.04), 2.46% (se = 0.11), and 0.15% (se = 0.01), respectively. The labeled wood chips from the Aspen FACE treatments had an average δ13C value of -39.5‰ (se 0.10). The >12 ‰ isotopic difference between the soil and wood chip δ 13C values provides the basis for tracking the wood-derived C through the early stages of decomposition and subsequent storage in the soil. Across our six research sites, average soil surface CO 2 efflux ranged from 1.04 to 2.00 g CO 2 m -2 h -1 for the first two growing seasons. No wood chip controls had an average soil surface CO 2 efflux of 0.67 g CO 2 m -2 h -1 or about half of that of the wood chip treatment plots. Wood-derived CO 2 efflux was higher for loam textured soils relative to sands (0.70 and 0.54 g CO 2 m -2 h -1, respectively; p = 0.045)), for surface relative to buried wood chip treatments (0.92 and 0.39 g CO 2 m -2 h -1, respectively; p < 0.001), for warmed relative to ambient temperature treatments (0.99 and 0.78 g CO 2 m -2 h -1, respectively; 0.004), and for natural rot relative to brown and white rots (0.93, 0.82, and 0.78 g CO 2 m -2 h -1, respectively; p = 0.068). Our first two growing seasons of soil surface CO 2 efflux data show that wood chip location (i.e., surface vs. buried chip application) is very important, with surface chips loosing twice the wood-derived CO 2. The DOC data support this trend for greater loss of ecosystem C from surface chips. This has strong implications for the importance of root and buried wood for ecosystem C retention. This strong chip location effect on wood-derived C loss was significantly modified by soil texture, soil temperature, decomposer communities, and wood quality as effected by potential future CO 2 and O 3 levels.« less

CO from enhanced HO activity or from CORM-2 inhibits both O2- and NO production and downregulates HO-1 expression in LPS-stimulated macrophages.

PubMed

Srisook, Klaokwan; Han, Shan-Shu; Choi, Hyung-Sim; Li, Mei-Hua; Ueda, Hideo; Kim, Chaekyun; Cha, Young-Nam

2006-01-12

Carbon monoxide (CO) arising from heme degradation, catalyzed particularly by the stress-inducible heme oxygenase-1 (HO-1), has recently been demonstrated to provide cytoprotection against cell death in macrophages stimulated with bacterial lipopolysaccharide (LPS). In the present study, we determined the effects of CO on the production of reactive oxygen species (ROS) and nitric oxide (NO) by the LPS-stimulated RAW 264.7 macrophages. In addition, effect of CO-exposure on the production of superoxide (O(2)(-)) in the phorbol myristate acetate (PMA)-stimulated PLB-985 neutrophils was determined. Production of ROS by the LPS-stimulated macrophages pretreated with 50microM [Ru(CO)(3)Cl(2)](2), a CO-releasing molecule (CORM-2), was abolished and the production of O(2)(-) by the PMA-stimulated neutrophils pretreated with the CORM-2 was decreased markedly. The CORM-2 (50microM) was not cytotoxic to both the unstimulated and LPS-stimulated macrophages when determined by employing mitochondrial reductase function test (MTT assay). In macrophages pretreated with increasing doses of CORM-2, both the LPS-derived upregulations of iNOS (NO production) and HO-1 expression (CO production) were suppressed in a dose-dependent manner. Alternatively, when the macrophages were treated with LPS and CO-donor together, the LPS-derived increase in NO production was decreased. Conversely, when the control and LPS-stimulated macrophages were treated with zinc protoporphyrin IX (ZnPP) to inhibit the HO activity blocking endogenous production of CO (basal and enhanced), macrophages died extensively. Interestingly, production of NO in the LPS-stimulated macrophages increased significantly following the ZnPP treatment. Addition of CORM-2 to the LPS-treated cells that were being treated additionally with ZnPP did not prevent the cell death. However, endogenous overproduction of CO by super-induction of HO-1 (obtained by pretreatment of macrophages with either buthionine sulfoximine or hemin) decreased the LPS-derived iNOS expression without affecting cell survival. Combined, these results indicated that enhanced HO activity is essential for the survival of LPS-stimulated macrophages. Thus, upregulation of HO-1 and overproduction of CO may allow the survival of LPS-stimulated macrophages; first, by eliminating the free heme to prevent Fenton reaction, second, by limiting the availability of free heme required for induction of NO-producing heme enzyme (i.e., iNOS), third, by limiting additional production of O(2)(-) and NO via CO-derived inhibition on the activities of heme enzymes like NADPH oxidase and iNOS, respectively. CO may allow the LPS-activated macrophages to return back to the normal quiet state insensitive to additional stimuli causing oxidative stress.

Electrochemical and solid-state NMR studies on LiCoO 2 coated with Al 2O 3 derived from carboxylate-alumoxane

NASA Astrophysics Data System (ADS)

Fey, George T. K.; Kao, H. M.; Muralidharan, P.; Kumar, T. P.; Cho, Y. D.

The surface of LiCoO 2 cathodes was coated with various wt.% of Al 2O 3 derived from methoxyethoxy acetate-alumoxane (MEA-alumoxane) by a mechano-thermal coating procedure, followed by calcination at 723 K in air for 10 h. The structure and morphology of the surface modified LiCoO 2 samples have been characterized with XRD, SEM, EDS, TEM, BET, XPS/ESCA and solid-state 27Al magic angle spinning (MAS) NMR techniques. The Al 2O 3 coating forms a thin layer on the surface of the core material with an average thickness of 20 nm. The corresponding 27Al MAS NMR spectrum basically exhibited the same characteristics as the spectrum for pristine Al 2O 3 derived from MEA-alumoxane, indicating that the local environment of aluminum atoms was not significantly changed at coating levels below 1 wt.%. This provides direct evidence that Al 2O 3 was on the surface of the core materials. The LiCoO 2 coated with 1 wt.% Al 2O 3 sustained continuous cycle stability 13 times longer than pristine LiCoO 2. A comparison of the electrochemical impedance behavior of the pristine and coated materials revealed that the failure of pristine cathode performance is associated with an increase in the particle-particle resistance upon continuous cycling. Coating improved the cathode performance by suppressing the characteristic structural phase transitions (hexagonal to monoclinic to hexagonal) that occur in pristine LiCoO 2 during the charge-discharge processes.

Solubility correlation of anthraquinone derivatives in supercritical carbon dioxide

NASA Astrophysics Data System (ADS)

Alwi, Ratna Surya; Tamura, Kazuhiro; Tanaka, Tatsuro; Shimizu, Keisuke

2017-05-01

In this work, solubilites of anthraquinone dyestuffs in supercritical carbon dioxide (sc-CO2) were correlated by semiempirical models, expressed in terms of CO2 density. All solubility data used, experimentally measured by us, and were described in details elsewhere; namely, 1,4-diaminoanthraquinone and 1,4-bis(ethylamino)anthraquinone [J. Chem. Thermo-dyn. 74, 119-125 (2014)]; 1-amino-4-hydroxyanthraquinone and 1-hydroxy-4-nitroanthraquionone [Dyes Pigm.113, 351-356 (2015)]; 1,4-diamino-2,3-dichloroanthraquinone and 1,8-dihydroxy-4,5-dinitroanthraquinone [J. Chem. Eng. Data 60, 3046-3052 (2015)], and 1-aminoanthraquinone and 1-nitroanthraquinone [J. Chem. Thermodyn. 104, 162-168 (2017)]. It was found that 1-aminoanthraquinone shows the highest solubility at 383,15 K and pressure of 25 MPa, and the solubility of anthraquinone derivatives in sc-CO2 changed by the substituent groups. Satisfactory agreement between the experimental data used and calculated solubilities of the anthraquinone derivatives was obtained.

Kinetic Temperature and Carbon Dioxide from Broadband Infrared Limb Emission Measurements Taken from the TIMED/SABER Instrument

NASA Technical Reports Server (NTRS)

Mertens, Christopher J.; Russell III, James M.; Mlynczak, Martin G.; She, Chiao-Yao; Schmidlin, Francis J.; Goldberg, Richard A.; Lopez-Puertas, Manuel; Wintersteiner, Peter P.; Picard, Richard H.; Winick, Jeremy R.;

Employing CO2 as reaction medium for in-situ suppression of the formation of benzene derivatives and polycyclic aromatic hydrocarbons during pyrolysis of simulated municipal solid waste.

PubMed

Lee, Jechan; Choi, Dongho; Tsang, Yiu Fai; Oh, Jeong-Ik; Kwon, Eilhann E

2017-05-01

This study proposes a strategic principle to enhance the thermal efficiency of pyrolysis of municipal solid waste (MSW). An environmentally sound energy recovery platform was established by suppressing the formation of harmful organic compounds evolved from pyrolysis of MSW. Using CO 2 as reaction medium/feedstock, CO generation was enhanced through the following: 1) expediting the thermal cracking of volatile organic carbons (VOCs) evolved from the thermal degradation of the MSWs and 2) directly reacting VOCs with CO 2 . This particular influence of CO 2 on pyrolysis of the MSWs also led to the in-situ mitigation of harmful organic compounds (e.g., benzene derivatives and polycyclic aromatic hydrocarbons (PAHs)) considering that CO 2 acted as a carbon scavenger to block reaction pathways toward benzenes and PAHs in pyrolysis. To understand the fundamental influence of CO 2 , simulated MSWs (i.e., various ratios of biomass to polymer) were used to avoid any complexities arising from the heterogeneous matrix of MSW. All experimental findings in this study suggested the foreseeable environmental application of CO 2 to energy recovery from MSW together with disposal of MSW. Copyright © 2017 Elsevier Ltd. All rights reserved.

CO abundance variations in the Orion Molecular Cloud

NASA Astrophysics Data System (ADS)

Ripple, F.; Heyer, M. H.; Gutermuth, R.; Snell, R. L.; Brunt, C. M.

2013-05-01

Infrared stellar photometry from the Two Micron All-Sky Survey (2MASS) and spectral line imaging observations of 12CO and 13CO J = 1-0 line emission from the Five College Radio Astronomy Observatory (FCRAO) 14-m telescope are analysed to assess the variation of the CO abundance with physical conditions throughout the Orion A and Orion B molecular clouds. Three distinct Av regimes are identified in which the ratio between the 13CO column density and visual extinction changes corresponding to the photon-dominated envelope, the strongly self-shielded interior, and the cold, dense volumes of the clouds. Within the strongly self-shielded interior of the Orion A cloud, the 13CO abundance varies by 100 per cent with a peak value located near regions of enhanced star formation activity. The effect of CO depletion on to the ice mantles of dust grains is limited to regions with Av > 10 mag and gas temperatures less than ˜20 K as predicted by chemical models that consider thermal evaporation to desorb molecules from grain surfaces. Values of the molecular mass of each cloud are independently derived from the distributions of Av and 13CO column densities with a constant 13CO-to-H2 abundance over various extinction ranges. Within the strongly self-shielded interior of the cloud (Av> 3 mag), 13CO provides a reliable tracer of H2 mass with the exception of the cold, dense volumes where depletion is important. However, owing to its reduced abundance, 13CO does not trace the H2 mass that resides in the extended cloud envelope, which comprises 40-50 per cent of the molecular mass of each cloud. The implied CO luminosity to mass ratios, M/LCO, are 3.2 and 2.9 for Orion A and Orion B, respectively, which are comparable to the value (2.9), derived from γ-ray observations of the Orion region. Our results emphasize the need to consider local conditions when applying CO observations to derive H2 column densities.

CO 2 Saline Storage Demonstration in Colorado Sedimentary Basins. Applied Studies in Reservoir Assessment and Dynamic Processes Affecting Industrial Operations

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

Nummedal, Dag; Doran, Kevin; Sitchler, Alexis

2012-09-30

This multitask research project was conducted in anticipation of a possible future increase in industrial efforts at CO 2 storage in Colorado sedimentary basins. Colorado is already the home to the oldest Rocky Mountain CO 2 storage site, the Rangely Oil Field, where CO 2-EOR has been underway since the 1980s. The Colorado Geological Survey has evaluated storage options statewide, and as part of the SW Carbon Sequestration Partnership the Survey, is deeply engaged in and committed to suitable underground CO 2 storage. As a more sustainable energy industry is becoming a global priority, it is imperative to explore themore » range of technical options available to reduce emissions from fossil fuels. One such option is to store at least some emitted CO 2 underground. In this NETL-sponsored CO 2 sequestration project, the Colorado School of Mines and our partners at the University of Colorado have focused on a set of the major fundamental science and engineering issues surrounding geomechanics, mineralogy, geochemistry and reservoir architecture of possible CO 2 storage sites (not limited to Colorado). Those are the central themes of this final report and reported below in Tasks 2, 3, 4, and 6. Closely related to these reservoir geoscience issues are also legal, environmental and public acceptance concerns about pore space accessibility—as a precondition for CO 2 storage. These are addressed in Tasks 1, 5 and 7. Some debates about the future course of the energy industry can become acrimonius. It is true that the physics of combustion of hydrocarbons makes it impossible for fossil energy to attain a carbon footprint anywhere nearly as low as that of renewables. However, there are many offsetting benefits, not the least that fossil energy is still plentiful, it has a global and highly advanced distribution system in place, and the footprint that the fossil energy infrastructure occupies is orders of magnitude smaller than renewable energy facilities with equivalent energy capacity. Finally, inexpensive natural gas here in North America is pushing coal for electricity generation off the market, thus reducing US CO 2 emissions faster than any other large industrialized nation. These two big factors argue for renewed efforts to find technology solutions to reduce the carbon footprint (carbon dioxide as well as methane and trace gases) of conventional and unconventional oil and gas. One major such technology component is likely to be carbon capture, utilization and storage.« less

Importance of Micropore-Mesopore Interfaces in Carbon Dioxide Capture by Carbon-Based Materials.

PubMed

Durá, Gema; Budarin, Vitaliy L; Castro-Osma, José A; Shuttleworth, Peter S; Quek, Sophie C Z; Clark, James H; North, Michael

2016-08-01

Mesoporous carbonaceous materials (Starbons®) derived from low-value/waste bio-resources separate CO2 from CO2 /N2 mixtures. Compared to Norit activated charcoal (AC), Starbons® have much lower microporosities (8-32 % versus 73 %) yet adsorb up to 65 % more CO2 . The presence of interconnected micropores and mesopores is responsible for the enhanced CO2 adsorption. The Starbons® also showed three-four times higher selectivity for CO2 adsorption rather than N2 adsorption compared to AC. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Forest response to elevated CO2 is conserved across a broad range of productivity

Treesearch

R. Norby; E. DeLucia; B. Gielen; C. Calfapietra; C. Giardina; J. King; J. Ledford; H. McCarthy; D. Moore; R. Ceulemans; P. De Angelis; A. C. Finzi; D. F. Karnosky; M. E. Kubiske; M. Lukac; K. S. Pregitzer; G. E. Scarascia-Mugnozza; W. Schlesinger and R. Oren.

2005-01-01

Climate change predictions derived from coupled carbon-climate models are highly dependent on assumptions about feedbacks between the biosphere and atmosphere. One critical feedback occurs if C uptake by the biosphere increases in response to the fossil-fuel driven increase in atmospheric [CO2] ("CO2 fertilization...

Molecular Modeling Studies of 4,5-Dihydro-1H-pyrazolo[4,3-h] quinazoline Derivatives as Potent CDK2/Cyclin A Inhibitors Using 3D-QSAR and Docking

PubMed Central

Ai, Yong; Wang, Shao-Teng; Sun, Ping-Hua; Song, Fa-Jun

2010-01-01

CDK2/cyclin A has appeared as an attractive drug targets over the years with diverse therapeutic potentials. A computational strategy based on comparative molecular fields analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) followed by molecular docking studies were performed on a series of 4,5-dihydro-1H-pyrazolo[4,3-h]quinazoline derivatives as potent CDK2/cyclin A inhibitors. The CoMFA and CoMSIA models, using 38 molecules in the training set, gave r2cv values of 0.747 and 0.518 and r2 values of 0.970 and 0.934, respectively. 3D contour maps generated by the CoMFA and CoMSIA models were used to identify the key structural requirements responsible for the biological activity. Molecular docking was applied to explore the binding mode between the ligands and the receptor. The information obtained from molecular modeling studies may be helpful to design novel inhibitors of CDK2/cyclin A with desired activity. PMID:21152296

Molecular modeling studies of 4,5-dihydro-1H-pyrazolo[4,3-h] quinazoline derivatives as potent CDK2/Cyclin a inhibitors using 3D-QSAR and docking.

PubMed

Ai, Yong; Wang, Shao-Teng; Sun, Ping-Hua; Song, Fa-Jun

2010-09-28

CDK2/cyclin A has appeared as an attractive drug targets over the years with diverse therapeutic potentials. A computational strategy based on comparative molecular fields analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) followed by molecular docking studies were performed on a series of 4,5-dihydro-1H-pyrazolo[4,3-h]quinazoline derivatives as potent CDK2/cyclin A inhibitors. The CoMFA and CoMSIA models, using 38 molecules in the training set, gave r(2) (cv) values of 0.747 and 0.518 and r(2) values of 0.970 and 0.934, respectively. 3D contour maps generated by the CoMFA and CoMSIA models were used to identify the key structural requirements responsible for the biological activity. Molecular docking was applied to explore the binding mode between the ligands and the receptor. The information obtained from molecular modeling studies may be helpful to design novel inhibitors of CDK2/cyclin A with desired activity.

Comprehensive analysis of coding-lncRNA gene co-expression network uncovers conserved functional lncRNAs in zebrafish.

PubMed

Chen, Wen; Zhang, Xuan; Li, Jing; Huang, Shulan; Xiang, Shuanglin; Hu, Xiang; Liu, Changning

2018-05-09

Zebrafish is a full-developed model system for studying development processes and human disease. Recent studies of deep sequencing had discovered a large number of long non-coding RNAs (lncRNAs) in zebrafish. However, only few of them had been functionally characterized. Therefore, how to take advantage of the mature zebrafish system to deeply investigate the lncRNAs' function and conservation is really intriguing. We systematically collected and analyzed a series of zebrafish RNA-seq data, then combined them with resources from known database and literatures. As a result, we obtained by far the most complete dataset of zebrafish lncRNAs, containing 13,604 lncRNA genes (21,128 transcripts) in total. Based on that, a co-expression network upon zebrafish coding and lncRNA genes was constructed and analyzed, and used to predict the Gene Ontology (GO) and the KEGG annotation of lncRNA. Meanwhile, we made a conservation analysis on zebrafish lncRNA, identifying 1828 conserved zebrafish lncRNA genes (1890 transcripts) that have their putative mammalian orthologs. We also found that zebrafish lncRNAs play important roles in regulation of the development and function of nervous system; these conserved lncRNAs present a significant sequential and functional conservation, with their mammalian counterparts. By integrative data analysis and construction of coding-lncRNA gene co-expression network, we gained the most comprehensive dataset of zebrafish lncRNAs up to present, as well as their systematic annotations and comprehensive analyses on function and conservation. Our study provides a reliable zebrafish-based platform to deeply explore lncRNA function and mechanism, as well as the lncRNA commonality between zebrafish and human.

Room temperature solid-state synthesis of a conductive polymer for applications in stable I₂-free dye-sensitized solar cells.

PubMed

Kim, Byeonggwan; Koh, Jong Kwan; Kim, Jeonghun; Chi, Won Seok; Kim, Jong Hak; Kim, Eunkyoung

2012-11-01

A solid-state polymerizable monomer, 2,5-dibromo-3,4-propylenedioxythiophene (DBProDOT), was synthesized at 25 °C to produce a conducting polymer, poly(3,4-propylenedioxythiophene) (PProDOT). Crystallographic studies revealed a short interplane distance between DBProDOT molecules, which was responsible for polymerization at low temperature with a lower activation energy and higher exothermic reaction than 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) or its derivatives. Upon solid-state polymerization (SSP) of DBProDOT at 25 °C, PProDOT was obtained in a self-doped state with tribromide ions and an electrical conductivity of 0.05 S cm⁻¹, which is considerably higher than that of chemically-polymerized PProDOT (2×10⁻⁶ S cm⁻¹). Solid-state ¹³C NMR spectroscopy and DFT calculations revealed polarons in PProDOT and a strong perturbation of carbon nuclei in thiophenes as a result of paramagnetic broadening. DBProDOT molecules deeply penetrated and polymerized to fill nanocrystalline TiO₂ pores with PProDOT, which functioned as a hole-transporting material (HTM) for I₂-free solid-state dye-sensitized solar cells (ssDSSCs). With the introduction of an organized mesoporous TiO₂ (OM-TiO₂) layer, the energy conversion efficiency reached 3.5 % at 100 mW cm⁻², which was quite stable up to at least 1500 h. The cell performance and stability was attributed to the high stability of PProDOT, with the high conductivity and improved interfacial contact of the electrode/HTM resulting in reduced interfacial resistance and enhanced electron lifetime. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and reactivity of mononuclear iron models of [Fe]-hydrogenase that contain an acylmethylpyridinol ligand.

PubMed

Hu, Bowen; Chen, Dafa; Hu, Xile

2014-02-03

[Fe]-hydrogenase has a single iron-containing active site that features an acylmethylpyridinol ligand. This unique ligand environment had yet to be reproduced in synthetic models; however the synthesis and reactivity of a new class of small molecule mimics of [Fe]-hydrogenase in which a mono-iron center is ligated by an acylmethylpyridinol ligand has now been achieved. Key to the preparation of these model compounds is the successful C-O cleavage of an alkyl ether moiety to form the desired pyridinol ligand. Reaction of solvated complex [(2-CH2CO-6-HOC5H3N)Fe(CO)2(CH3CN)2](+)(BF4)(-) with thiols or thiophenols in the presence of NEt3 yielded 5-coordinate iron thiolate complexes. Further derivation produced complexes [(2-CH2CO-6-HOC5H3N)Fe(CO)2(SCH2CH2OH)] and [(2-CH2CO-6-HOC5H3N)Fe(CO)2(CH3COO)], which can be regarded as models of FeGP cofactors of [Fe]-hydrogenase extracted by 2-mercaptoethanol and acetic acid, respectively. When the derivative complexes were treated with HBF4 ⋅Et2O, the solvated complex was regenerated by protonation of the thiolate ligands. The reactivity of several models with CO, isocyanide, cyanide, and H2 was also investigated. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparing Methods for Cardiac Output: Intraoperatively Doppler-Derived Cardiac Output Measured With 3-Dimensional Echocardiography Is Not Interchangeable With Cardiac Output by Pulmonary Catheter Thermodilution.

PubMed

Graeser, Karin; Zemtsovski, Mikhail; Kofoed, Klaus F; Winther-Jensen, Matilde; Nilsson, Jens C; Kjaergaard, Jesper; Møller-Sørensen, Hasse

2018-01-09

Estimation of cardiac output (CO) is essential in the treatment of circulatory unstable patients. CO measured by pulmonary artery catheter thermodilution is considered the gold standard but carries a small risk of severe complications. Stroke volume and CO can be measured by transesophageal echocardiography (TEE), which is widely used during cardiac surgery. We hypothesized that Doppler-derived CO by 3-dimensional (3D) TEE would agree well with CO measured with pulmonary artery catheter thermodilution as a reference method based on accurate measurements of the cross-sectional area of the left ventricular outflow tract. The primary aim was a systematic comparison of CO with Doppler-derived 3D TEE and CO by thermodilution in a broad population of patients undergoing cardiac surgery. A subanalysis was performed comparing cross-sectional area by TEE with cardiac computed tomography (CT) angiography. Sixty-two patients, scheduled for elective heart surgery, were included; 1 was subsequently excluded for logistic reasons. Inclusion criteria were coronary artery bypass surgery (N = 42) and aortic valve replacement (N = 19). Exclusion criteria were chronic atrial fibrillation, left ventricular ejection fraction below 0.40 and intracardiac shunts. Nineteen randomly selected patients had a cardiac CT the day before surgery. All images were stored for blinded post hoc analyses, and Bland-Altman plots were used to assess agreement between measurement methods, defined as the bias (mean difference between methods), limits of agreement (equal to bias ± 2 standard deviations of the bias), and percentage error (limits of agreement divided by the mean of the 2 methods). Precision was determined for the individual methods (equal to 2 standard deviations of the bias between replicate measurements) to determine the acceptable limits of agreement. We found a good precision for Doppler-derived CO measured by 3D TEE, but although the bias for Doppler-derived CO by 3D compared to thermodilution was only 0.3 L/min (confidence interval, 0.04-0.58), there were wide limits of agreement (-1.8 to 2.5 L/min) with a percentage error of 55%. Measurements of cross-sectional area by 3D TEE had low bias of -0.27 cm (confidence interval, -0.45 to -0.08) and a percentage error of 18% compared to cardiac CT angiography. Despite low bias, the wide limits of agreement of Doppler-derived CO by 3D TEE compared to CO by thermodilution will limit clinical application and can therefore not be considered interchangeable with CO obtained by thermodilution. The lack of agreement is not explained by lack of agreement of the 3D technique.

Brain-Derived Neurotrophic Factor (BDNF) and Traumatic Brain Injury (Head and Spinal)

DTIC Science & Technology

1999-01-01

surface area. J Microscopy 150: 117-136. Osterman-Latif C, Mader M, Felgenhauer K (1993) An efficient sandwich-ELISA for the determination of choline ...anesthesia and surgery but were not injured (sham injury). After the appropriate survival times, the rats were deeply anesthetized with an overdose of...post-injury (Hicks et al., 1997b, 1998). Tissue Processing Following deep anesthesia with an overdose of sodium pentobarbital, the animals ".vere

Does Miscanthus cultivation on organic soils compensate for carbon loss from peat oxidation? A dual label study

NASA Astrophysics Data System (ADS)

Bader, Cédric; Leifeld, Jens; Müller, Moritz; Schulin, Rainer

2016-04-01

Agricultural use of organic soils requires drainage and thereby changes conditions in these soils from anoxic to oxic. As a consequence, organic carbon that had been accumulated over millennia is rapidly mineralized, so that these soils are converted from a CO2 sink to a source. The peat mineralization rate depends mainly on drainage depth, but also on crop type. Various studies show that Miscanthus, a C4 bioenergy plant, shows potential for carbon sequestration in mineral soils because of its high productivity, its dense root system, absence of tillage and high preharvest litterfall. If Miscanthus cropping would have a similar effect in organic soils, peat consumption and thus CO2 emissions might be reduced. For our study we compared two adjacent fields, on which organic soil is cultivated with Miscanthus (since 20 years) and perennial grass (since 6 years). Both sites are located in the Bernese Seeland, the largest former peatland area of Switzerland. To determine wether Miscanthus-derived carbon accumulated in the organic soil, we compared the stable carbon isotopic signatures of the experimental soil with those of an organic soil without any C4-plant cultivation history. To analyze the effect of C4-C accumulation on peat degradability we compared the CO2 emissions by incubating 90 soil samples of the two fields for more than one year. Additionally, we analysed the isotopic CO2 composition (13C, 14C) during the first 25 days of incubation after trapping the emitted CO2 in NaOH and precipitating it as BaCO3. The ∂13C values of the soil imply, that the highest share of C4-C of around 30% is situated at a depth of 10-20 cm. Corn that used to be cultivated on the grassland field before 2009 still accounts for 8% of SOC. O/C and H/C ratios of the peat samples indicate a stronger microbial imprint of organic matter under Miscanthus cultivation. The amount of CO2 emitted was not affected by the cultivation type. On average 57% of the CO2 was C4 derived in the Miscanthus field, whereas 38% was C4-derived in the Grassland field. According to our radiocarbon data, 38% of the CO2 must have originated from peat-derived OM on the Miscanthus field, whereas 57% of the CO2 was derived from peat in the grassland. Although peat minerlaization seems to be smaller and a significant amount of C4-C accumulated under Miscanthus, peat mineralization nonetheless contributed substantially to soil respiration. Together, our data do not support the hypothesis that Miscanthus cultivation can fully compensate for organic matter loss in drained peatlands.

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes.

PubMed

Li, Yulong; Rauchfuss, Thomas B

2016-06-22

Virtually all organosulfur compounds react with Fe(0) carbonyls to give the title complexes. These reactions are reviewed in light of major advances over the past few decades, spurred by interest in Fe2(μ-SR)2(CO)x centers at the active sites of the [FeFe]-hydrogenase enzymes. The most useful synthetic route to Fe2(μ-SR)2(CO)6 involves the reaction of thiols with Fe2(CO)9 and Fe3(CO)12. Such reactions can proceed via mono-, di-, and triiron intermediates. The reactivity of Fe(0) carbonyls toward thiols is highly chemoselective, and the resulting dithiolato complexes are fairly rugged. Thus, many complexes tolerate further synthetic elaboration directed at the organic substituents. A second major route involves alkylation of Fe2(μ-S2)(CO)6, Fe2(μ-SH)2(CO)6, and Li2Fe2(μ-S)2(CO)6. This approach is especially useful for azadithiolates Fe2[(μ-SCH2)2NR](CO)6. Elaborate complexes arise via addition of the FeSH group to electrophilic alkenes, alkynes, and carbonyls. Although the first example of Fe2(μ-SR)2(CO)6 was prepared from ferrous reagents, ferrous compounds are infrequently used, although the Fe(II)(SR)2 + Fe(0) condensation reaction is promising. Almost invariably low-yielding, the reaction of Fe3(CO)12, S8, and a variety of unsaturated substrates results in C-H activation, affording otherwise inaccessible derivatives. Thiones and related C═S-containing reagents are highly reactive toward Fe(0), often giving complexes derived from substituted methanedithiolates and C-H activation.

Drivers of pCO2 variability in two contrasting coral reef lagoons: The influence of submarine groundwater discharge

NASA Astrophysics Data System (ADS)

Cyronak, Tyler; Santos, Isaac R.; Erler, Dirk V.; Maher, Damien T.; Eyre, Bradley D.

2014-04-01

The impact of groundwater on pCO2 variability was assessed in two coral reef lagoons with distinct drivers of submarine groundwater discharge (SGD). Diel variability of pCO2 in the two ecosystems was explained by a combination of biological drivers and SGD inputs. In Rarotonga, a South Pacific volcanic island, 222Rn-derived SGD was driven primarily by a steep terrestrial hydraulic gradient, and the water column was influenced by the high pCO2 (5501 µatm) of the fresh groundwater. In Heron Island, a Great Barrier Reef coral cay, SGD was dominated by seawater recirculation through the sediments (i.e., tidal pumping), and pCO2 was mainly impacted through the stimulation of biological processes. The Rarotonga water column had a higher average pCO2 (549 µatm) than Heron Island (471 µatm). However, pCO2 exhibited a greater diel range in Heron Island (778 µatm) than in Rarotonga (507 µatm). The Rarotonga water column received 29.0 ± 8.2 mmol free-CO2 m-2 d-1 from SGD, while the Heron Island water column received 12.1 ± 4.2 mmol free-CO2 m-2 d-1. Over the course of this study, both systems were sources of CO2 to the atmosphere with SGD-derived free-CO2 most likely contributing a large portion to the air-sea CO2 flux. Studies measuring the carbon chemistry of coral reefs (e.g., metabolism and calcification rates) may need to consider the effects of groundwater inputs on water column carbonate chemistry. Local drivers of coral reef carbonate chemistry such as SGD may offer more approachable management solutions to mitigating the effects of ocean acidification on coral reefs.

Macrocyclic triamine derived glucose analogues for 99m Tc(CO)3 labeling: synthesis and biological evaluation as potential tumor-imaging agents.

PubMed

Liu, Teli; Gan, Qianqian; Zhang, Junbo

2017-02-01

[ 99m Tc(CO) 3 (H 2 O) 3 ] + has attracted great attention among 99m Tc-labeling techniques, due to its ease of preparation, readily substituted water molecules of the precursor fac-[ 99m Tc(CO) 3 (H 2 O) 3 ] + by a variety of functional groups, small size and inertness. Bifunctional chelator based on a macrocyclic polyamine framework shows easy complexation with [ 99m Tc(CO) 3 (H 2 O) 3 ] + to produce stable complex. In this study, two novel 1, 5, 9-triazacyclododecane derivatives containing a glucose group (6 and 7) were successfully synthesized by reacting different glucose-azides with alkyne-[12]aneN 3 via the so-called click chemistry and radiolabeled with [ 99m Tc(CO) 3 (H 2 O) 3 ] + to form 99m Tc(CO) 3 -6 (C-1-substituted complex) and 99m Tc(CO) 3 -7 (C-2-substituted complex) in high yields. The complexes were stable in vitro over 6 h when incubated in saline at room temperature and in mouse serum at 37 °C. The partition coefficient results showed that they were hydrophilic. The biodistribution studies in Kunming mice bearing S 180 tumor showed both complexes showed accumulation in the tumor. Between them, 99m Tc(CO) 3 -7 had the advantages of much higher tumor uptake and tumor/muscle ratio. Compared with other reported 99m Tc-radiolabeled glucose derivatives, 99m Tc(CO) 3 -7 also showed a higher tumor uptake and tumor/muscle ratio, suggesting it would be a potential candidate for further development as a tumor-imaging agent. © 2017 John Wiley & Sons A/S.

Maui Gravity and Soil Gas Surveys

DOE Data Explorer

John Akerley

2010-04-01

Contains a ground-based gravity survey of South Maui and a series of soil CO2 flux and temperature surveys encompassing Maui and the Big Island. The gravity survey was collected from approximately 284 km2 and consisted of 400 gravity stations with 400 m spacing. Locations were derived with full DGPS. Station and line location, Complete Bouger Anomaly, first vertical derivative and horizontal gradient maps were calculated and produced. The soil CO2 flux and temperature surveys were conducted on the islands of Hawaii and Maui in April and July 2010. Average soil temperatures were measured over 10 cm depth using a hand-held thermocouple. Soil CO2 fluxes were measured using a portable accumulation chamber instrument.

Photoassisted Synthesis of Mixed-Metal Clusters;(PPN)(CoOs3(CO)13), H2RuOs3(CO13, and H2FeOs3(CO)13.

DTIC Science & Technology

1980-05-30

8 -1 Photoassisted Synthesis of Mixed-Metal Clusters: Interim echnicalfe 0M [PPN][ Cofs (CO) H OP]CC andF F ’ " 13 2 136. PERFORMING ORG. REPORT NUMBER...the reaction conditions.2 A low yield of the unstable protonated derivative HCoOs3 (CO)13 was obtained in a single experiment in which K[Co(CO)4] was...data.1 Apparently [V(CO)6]" is a sufficiently strong reducing agent to reduce both of these trimers to their respective anions, although the 6 proton

Design, synthesis, pharmacological evaluation and in silico ADMET prediction of novel substituted benzimidazole derivatives as angiotensin II-AT1 receptor antagonists based on predictive 3D QSAR models.

PubMed

Vyas, V K; Gupta, N; Ghate, M; Patel, S

2014-01-01

In this study we designed novel substituted benzimidazole derivatives and predicted their absorption, distribution, metabolism, excretion and toxicity (ADMET) properties, based on a predictive 3D QSAR study on 132 substituted benzimidazoles as AngII-AT1 receptor antagonists. The two best predicted compounds were synthesized and evaluated for AngII-AT1 receptor antagonism. Three different alignment tools for comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) were used. The best 3D QSAR models were obtained using the rigid body (Distill) alignment method. CoMFA and CoMSIA models were found to be statistically significant with leave-one-out correlation coefficients (q(2)) of 0.630 and 0.623, respectively, cross-validated coefficients (r(2)cv) of 0.651 and 0.630, respectively, and conventional coefficients of determination (r(2)) of 0.848 and 0.843, respectively. 3D QSAR models were validated using a test set of 24 compounds, giving satisfactory predicted results (r(2)pred) of 0.727 and 0.689 for the CoMFA and CoMSIA models, respectively. We have identified some key features in substituted benzimidazole derivatives, such as lipophilicity and H-bonding at the 2- and 5-positions of the benzimidazole nucleus, respectively, for AT1 receptor antagonistic activity. We designed 20 novel substituted benzimidazole derivatives and predicted their activity. In silico ADMET properties were also predicted for these designed molecules. Finally, the compounds with best predicted activity were synthesized and evaluated for in vitro angiotensin II-AT1 receptor antagonism.

Chemical and isotopic equilibrium between CO 2 and CH 4 in fumarolic gas discharges: Generation of CH 4 in arc magmatic-hydrothermal systems

NASA Astrophysics Data System (ADS)

Fiebig, Jens; Chiodini, Giovanni; Caliro, Stefano; Rizzo, Andrea; Spangenberg, Jorge; Hunziker, Johannes C.

2004-05-01

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH 4) within two subduction-related magmatic-hydrothermal environments. Apparent temperatures derived from carbon isotope partitioning between CH 4 and CO 2 of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H 2O-H 2-CO 2-CO-CH 4 geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH 4, CO 2 and H 2O implying that carbon isotope partitioning between CO 2 and CH 4 in both systems is controlled by aquifer temperature. N 2/ 3He and CH 4/ 3He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH 4 may have been primarily generated through the reduction of CO 2 by H 2 in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH 4 and subsequent re-equilibration with co-existing CO 2 cannot be ruled out entirely. CO 2/ 3He ratios and δ 13C CO 2 values imply that the evolved CO 2 either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH 4 during thermometamorphism.

Gas adsorption properties of highly porous metal-organic frameworks containing functionalized naphthalene dicarboxylate linkers.

PubMed

Sim, Jaeung; Yim, Haneul; Ko, Nakeun; Choi, Sang Beom; Oh, Youjin; Park, Hye Jeong; Park, SangYoun; Kim, Jaheon

2014-12-28

Three functionalized metal-organic frameworks (MOFs), MOF-205-NH2, MOF-205-NO2, and MOF-205-OBn, formulated as Zn4O(BTB)4/3(L), where BTB is benzene-1,3,5-tribenzoate and L is 1-aminonaphthalene-3,7-dicarboxylate (NDC-NH2), 1-nitronaphthalene-3,7-dicarboxylate (NDC-NO2) or 1,5-dibenzyloxy-2,6-naphthalenedicarboxylate (NDC-(OBn)2), were synthesized and their gas (H2, CO2, or CH4) adsorption properties were compared to those of the un-functionalized, parent MOF-205. Ordered structural models for MOF-205 and its derivatives were built based on the crystal structures and were subsequently used for predicting porosity properties. Although the Brunauer-Emmett-Teller (BET) surface areas of the three MOF-205 derivatives were reduced (MOF-205, 4460; MOF-205-NH2, 4330; MOF-205-NO2, 3980; MOF-205-OBn, 3470 m(2) g(-1)), all three derivatives were shown to have enhanced H2 adsorption capacities at 77 K and CO2 uptakes at 253, 273, and 298 K respectively at 1 bar in comparison with MOF-205. The results indicate the following trend in H2 adsorption: MOF-205 < MOF-205-NO2 < MOF-205-NH2 < MOF-205-OBn. MOF-205-OBn showed good ideal adsorbed solution theory (IAST) selectivity values of 6.5 for CO2/N2 (15/85 in v/v) and 2.7 for CO2/CH4 (50/50 in v/v) at 298 K. Despite the large reduction (-22%) in the surface area, MOF-205-OBn displayed comparable total volumetric CO2 (at 48 bar) and CH4 (at 35 bar) storage capacities with those of MOF-205 at 298 K: MOF-205-OBn, 305 (CO2) and 112 (CH4) cm(3) cm(-3), and for MOF-205, 307 (CO2) and 120 (CH4) cm(3) cm(-3), respectively.

Estimates of CO2 traffic emissions from mobile concentration measurements

NASA Astrophysics Data System (ADS)

Maness, H. L.; Thurlow, M. E.; McDonald, B. C.; Harley, R. A.

2015-03-01

We present data from a new mobile system intended to aid in the design of upcoming urban CO2-monitoring networks. Our collected data include GPS probe data, video-derived traffic density, and accurate CO2 concentration measurements. The method described here is economical, scalable, and self-contained, allowing for potential future deployment in locations without existing traffic infrastructure or vehicle fleet information. Using a test data set collected on California Highway 24 over a 2 week period, we observe that on-road CO2 concentrations are elevated by a factor of 2 in congestion compared to free-flow conditions. This result is found to be consistent with a model including vehicle-induced turbulence and standard engine physics. In contrast to surface concentrations, surface emissions are found to be relatively insensitive to congestion. We next use our model for CO2 concentration together with our data to independently derive vehicle emission rate parameters. Parameters scaling the leading four emission rate terms are found to be within 25% of those expected for a typical passenger car fleet, enabling us to derive instantaneous emission rates directly from our data that compare generally favorably to predictive models presented in the literature. The present results highlight the importance of high spatial and temporal resolution traffic data for interpreting on- and near-road concentration measurements. Future work will focus on transport and the integration of mobile platforms into existing stationary network designs.

Future reef decalcification under a business-as-usual CO2 emission scenario

PubMed Central

Dove, Sophie G.; Kline, David I.; Pantos, Olga; Angly, Florent E.; Tyson, Gene W.; Hoegh-Guldberg, Ove

2013-01-01

Increasing atmospheric partial pressure of CO2 (pCO2) is a major threat to coral reefs, but some argue that the threat is mitigated by factors such as the variability in the response of coral calcification to acidification, differences in bleaching susceptibility, and the potential for rapid adaptation to anthropogenic warming. However the evidence for these mitigating factors tends to involve experimental studies on corals, as opposed to coral reefs, and rarely includes the influence of multiple variables (e.g., temperature and acidification) within regimes that include diurnal and seasonal variability. Here, we demonstrate that the inclusion of all these factors results in the decalcification of patch-reefs under business-as-usual scenarios and reduced, although positive, calcification under reduced-emission scenarios. Primary productivity was found to remain constant across all scenarios, despite significant bleaching and coral mortality under both future scenarios. Daylight calcification decreased and nocturnal decalcification increased sharply from the preindustrial and control conditions to the future scenarios of low (reduced emissions) and high (business-as-usual) increases in pCO2. These changes coincided with deeply negative carbonate budgets, a shift toward smaller carbonate sediments, and an increase in the abundance of sediment microbes under the business-as-usual emission scenario. Experimental coral reefs demonstrated highest net calcification rates and lowest rates of coral mortality under preindustrial conditions, suggesting that reef processes may not have been able to keep pace with the relatively minor environmental changes that have occurred during the last century. Taken together, our results have serious implications for the future of coral reefs under business-as-usual environmental changes projected for the coming decades and century. PMID:24003127

Future reef decalcification under a business-as-usual CO2 emission scenario.

PubMed

Dove, Sophie G; Kline, David I; Pantos, Olga; Angly, Florent E; Tyson, Gene W; Hoegh-Guldberg, Ove

2013-09-17

Increasing atmospheric partial pressure of CO2 (pCO2) is a major threat to coral reefs, but some argue that the threat is mitigated by factors such as the variability in the response of coral calcification to acidification, differences in bleaching susceptibility, and the potential for rapid adaptation to anthropogenic warming. However the evidence for these mitigating factors tends to involve experimental studies on corals, as opposed to coral reefs, and rarely includes the influence of multiple variables (e.g., temperature and acidification) within regimes that include diurnal and seasonal variability. Here, we demonstrate that the inclusion of all these factors results in the decalcification of patch-reefs under business-as-usual scenarios and reduced, although positive, calcification under reduced-emission scenarios. Primary productivity was found to remain constant across all scenarios, despite significant bleaching and coral mortality under both future scenarios. Daylight calcification decreased and nocturnal decalcification increased sharply from the preindustrial and control conditions to the future scenarios of low (reduced emissions) and high (business-as-usual) increases in pCO2. These changes coincided with deeply negative carbonate budgets, a shift toward smaller carbonate sediments, and an increase in the abundance of sediment microbes under the business-as-usual emission scenario. Experimental coral reefs demonstrated highest net calcification rates and lowest rates of coral mortality under preindustrial conditions, suggesting that reef processes may not have been able to keep pace with the relatively minor environmental changes that have occurred during the last century. Taken together, our results have serious implications for the future of coral reefs under business-as-usual environmental changes projected for the coming decades and century.

Extraction of Mg(OH)2 from Mg silicate minerals with NaOH assisted with H2O: implications for CO2 capture from exhaust flue gas.

PubMed

Madeddu, Silvia; Priestnall, Michael; Godoy, Erik; Kumar, R Vasant; Raymahasay, Sugat; Evans, Michael; Wang, Ruofan; Manenye, Seabelo; Kinoshita, Hajime

2015-01-01

The utilisation of Mg(OH)2 to capture exhaust CO2 has been hindered by the limited availability of brucite, the Mg(OH)2 mineral in natural deposits. Our previous study demonstrated that Mg(OH)2 can be obtained from dunite, an ultramafic rock composed of Mg silicate minerals, in highly concentrated NaOH aqueous systems. However, the large quantity of NaOH consumed was considered an obstacle for the implementation of the technology. In the present study, Mg(OH)2 was extracted from dunite reacted in solid systems with NaOH assisted with H2O. The consumption of NaOH was reduced by 97% with respect to the NaOH aqueous systems, maintaining a comparable yield of Mg(OH)2 extraction, i.e. 64.8-66%. The capture of CO2 from a CO2-N2 gas mixture was tested at ambient conditions using a Mg(OH)2 aqueous slurry. Mg(OH)2 almost fully dissolved and reacted with dissolved CO2 by forming Mg(HCO3)2 which remained in equilibrium storing the CO2 in the aqueous solution. The CO2 balance of the process was assessed from the emissions derived from the power consumption for NaOH production and Mg(OH)2 extraction together with the CO2 captured by Mg(OH)2 derived from dunite. The process resulted as carbon neutral when dunite is reacted at 250 °C for durations of 1 and 3 hours and CO2 is captured as Mg(HCO3)2.

Emissions of mercury in Southern Africa derived from long-term observations at Cape Point, South Africa

NASA Astrophysics Data System (ADS)

Brunke, E.-G.; Ebinghaus, R.; Kock, H. H.; Labuschagne, C.; Slemr, F.

2012-05-01

Mercury emissions in South Africa have so far been estimated only by a bottom-up approach from activities and emission factors for different processes. In this paper we derive GEM/CO (GEM being gaseous elemental mercury, Hg0), GEM/CO2, GEM/CH4, CO/CO2, CH4/CO2, and CH4/CO emission ratios from plumes observed during long-term monitoring of these species at Cape Point between March 2007 and December 2009. The average observed GEM/CO, GEM/CO2, GEM/CH4, CO/CO2, CH4/CO2, and CH4/CO emission ratios were 2.40 ± 2.65 pg m-3 ppb-1 (n = 47), 62.7 ± 80.2 pg m-3 ppb-1 (n = 44), 3.61 ± 4.66 pg m-3 ppb-1 (n = 46), 35.6 ± 25.4 ppb ppm-1 (n = 52), 20.2 ± 15.5 ppb ppm-1 (n=48), and 0.876 ± 1.106 ppb ppm-1 (n=42), respectively. The observed CO/CO2, CH4/CO2, and CH4/CO emission ratios agree within the combined uncertainties of the observations and emissions with the ratios calculated from EDGAR (version 4.2) CO2, CO, and CH4 inventories for South Africa and Southern Africa (South Africa, Lesotho, Swaziland, Namibia, Botswana, Zimbabwe, and Mozambique) in 2007 and 2008 (inventories for 2009 are not available yet). Total elemental mercury emission of 13.1, 15.2, and 16.1 t Hg yr-1 are estimated independently using the GEM/CO, GEM/CO2, and GEM/CH4 emission ratios and the annual mean CO, CO2, and CH4 emissions, respectively, of South Africa in 2007 and 2008. The average of these independent estimates of 14.8 ± 1.5 t GEM yr-1 is much less than the total emission of 257 t Hg yr-1 from older inventories. Considering that emission of GEM represents only 50-78% of all mercury emissions, our estimates come close to the total mercury emission estimates ranging between 40-50 t Hg yr-1 from more recent inventories.

Effects of biodiesel made from swine and chicken fat residues on carbon monoxide, carbon dioxide, and nitrogen oxide emissions.

PubMed

Feddern, Vivian; Cunha Junior, Anildo; De Prá, Marina C; Busi da Silva, Marcio L; Nicoloso, Rodrigo da S; Higarashi, Martha M; Coldebella, Arlei; de Abreu, Paulo G

2017-07-01

The effects of two alternative sources of animal fat-derived biodiesel feedstock on CO 2 , CO, NO x tailpipe emissions as well as fuel consumption were investigated. Biodiesel blends were produced from chicken and swine fat waste (FW-1) or floating fat (FW-2) collected from slaughterhouse wastewater treatment processes. Tests were conducted in an unmodified stationary diesel engine operating under idling conditions in attempt to simulate slow traffic in urban areas. Significant reductions in CO (up to 47% for B100; FW-2) and NO x (up to 20% for B5; FW-2 or B100; FW-1) were attained when using biodiesel fuels at the expense of 5% increase in fuel consumption. Principal component analysis (PCA) was performed to elucidate possible associations among gas (CO 2 , CO, and NO x ) emissions, cetane number and iodine index with different sources of feedstock typically employed in the biodiesel industry. NO x , cetane number and iodine index were inversely proportional to CO 2 and biodiesel concentration. High NO x emissions were reported from high iodine index biodiesel derived especially from forestry, fishery and some agriculture feedstocks, while the biodiesel derived from animal sources consistently presented lower iodine index mitigating NO x emissions. The obtained results point out the applicability of biodiesel fuels derived from fat-rich residues originated from animal production on mitigation of greenhouse gas emissions. The information may encourage practitioners from biodiesel industry whilst contributing towards development of sustainable animal production. Emissions from motor vehicles can contribute considerably to the levels of greenhouse gases in the atmosphere. The use of biodiesel to replace or augment diesel can not only decrease our dependency on fossil fuels but also help decrease air pollution. Thus, different sources of feedstocks are constantly being explored for affordable biodiesel production. However, the amount of carbon monoxide (CO), carbon dioxide (CO 2 ), and/or nitrogen oxide (NO x ) emissions can vary largely depending on type of feedstock used to produce biodiesel. In this work, the authors demonstrated animal fat feasibility in replacing petrodiesel with less impact regarding greenhouse gas emissions than other sources.

Sulfur-selective desulfurization of dibenzothiophene and diesel oil by newly isolated Rhodococcus sp. strains.

PubMed

Castorena, Gladys; Suárez, Claudia; Valdez, Idania; Amador, Guadalupe; Fernández, Luis; Le Borgne, Sylvie

2002-09-24

New desulfurizing bacteria able to convert dibenzothiophene into 2-hydroxybiphenyl and sulfate were isolated from contaminated soils collected in Mexican refineries. Random amplified polymorphic DNA analysis showed they were different from previously reported Rhodococcus erythropolis desulfurizing strains. According to 16S rRNA gene sequencing and fatty acid analyses, these new isolates belonged to the genus Rhodococcus. These strains could desulfurize 4,6-dimethyldibenzothiophene which is one of the most difficult dibenzothiophene derivatives to remove by hydrodesulfurization. A deeply hydrodesulfurized diesel oil containing significant amounts of 4,6-dimethyldibenzothiophene was treated with Rhodococcus sp. IMP-S02 cells. Up to 60% of the total sulfur was removed and all the 4,6-dimethyldibenzothiophene disappeared as a result of this treatment.

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

Lu, D.Y.; Hughes, R.W.; Anthony, E.J.

Sintering during calcination/carbonation may introduce substantial economic penalties for a CO{sub 2} looping cycle using limestone/dolomite-derived sorbents. Cyclic carbonation and calcination reactions were investigated for CO{sub 2} capture under fluidized bed combustion (FBC) conditions. The cyclic carbonation characteristics of CaCO{sub 3}-derived sorbents were compared at various calcination temperatures (700-925{sup o} C) and different gas stream compositions: pure -2 and a realistic calciner environment where high concentrations of CO{sub 2}>80-90% are expected. The conditions during carbonation were 700 {sup o}C and 15% CO{sub 2} in N{sub 2} and 0.18% or 0.50% SO{sub 2} in selected tests. Up to 20 calcination/carbonation cyclesmore » were conducted using a thermogravimetric analyzer (TGA) apparatus. Three Canadian limestones were tested: Kelly Rock, Havelock, and Cadomin, using a prescreened particle size range of 400-650 {mu} m. Calcined Kelly Rock and Cadomin samples were hydrated by steam and examined. Sorbent reactivity was reduced whenever SO{sub 2} was introduced to either the calcining or carbonation streams. The multicyclic capture capacity of CaO for CO{sub 2} was substantially reduced at high concentrations of CO{sub 2} during the sorbent regeneration process and carbonation conversion of the Kelly Rock sample obtained after 20 cycles was only 10.5%. Hydrated sorbents performed better for CO{sub 2} capture but showed deterioration following calcination in high CO{sub 2} gas streams indicating that high CO{sub 2} and SO{sub 2} levels in the gas stream lead to lower CaO conversion because of enhanced sintering and irreversible formation of CaSO{sub 4}.« less

Chemical and isotopic characteristics of geothermal fluids from Sulphur Springs, Saint Lucia

NASA Astrophysics Data System (ADS)

Joseph, Erouscilla P.; Fournier, Nicolas; Lindsay, Jan M.; Robertson, Richard; Beckles, Denise M.

2013-03-01

Sulphur Springs is a vigorous, geothermal field associated with the active Soufrière Volcanic Centre in southern Saint Lucia, Lesser Antilles island arc. The 'Sulphur Springs Park' is an important tourist attraction (touted as the 'world's only drive-through volcano') with some of the hot pools being developed into recreational pools. Some 200,000 people visit the park each year. Since 2001, the hydrothermal fluids of Sulphur Springs have been sampled as part of an integrated volcanic monitoring programme for the island. Gas and water samples were analysed to characterise the geochemistry of the hydrothermal system, and to assess the equilibrium state and subsurface temperatures of the reservoir. This has also enabled us, for the first time, to establish baseline data for future geochemical monitoring. The gases are of typical arc-type composition, with N2 excess and low He and Ar content. The dry gas composition is dominated by CO2 (ranging from 601-993 mmol/mol), with deeper magmatic sourced H2S-rich vapour undergoing boiling and redox changes in the geothermal reservoir to emerge with a hydrothermal signature in the fumarolic gases. Fluid contributions from magmatic degassing are also evident, mainly from the moderate to high contents of HCl and deeply-sourced H2S gas, respectively. Sulphur Springs hydrothermal waters have acid-sulphate type compositions (SO4 = 78-4008 mg/L; pH = 3-7), and are of primarily meteoric origin which have been affected by evaporation processes based on the enrichment in both δ18O and δD (δ18O = - 1 to 15‰ and δD = - 9 to 14‰ respectively) in relation to the global meteoric water line (GMWL). These waters are steam-heated water typically formed by absorption of H2S-rich gases in the near surface oxygenated groundwaters. Reservoir temperatures calculated from the evaluation of gas equilibria in the CO2-CH4-H2 system reveal higher temperatures (190 to 300 °C) than those derived from quartz geothermometry (95 to 169 °C), which appeared to be affected by dilution with meteoric waters. Generally, no significant variations in fluid geochemistry of the hydrothermal system were observed between 2001 and 2006, and we propose that there were no changes in the state of volcanic activity during this period.

A role for intracellular zinc in glioma alteration of neuronal chloride equilibrium

PubMed Central

Di Angelantonio, S; Murana, E; Cocco, S; Scala, F; Bertollini, C; Molinari, M G; Lauro, C; Bregestovski, P; Limatola, C; Ragozzino, D

2014-01-01

Glioma patients commonly suffer from epileptic seizures. However, the mechanisms of glioma-associated epilepsy are far to be completely understood. Using glioma-neurons co-cultures, we found that tumor cells are able to deeply influence neuronal chloride homeostasis, by depolarizing the reversal potential of γ-aminobutyric acid (GABA)-evoked currents (EGABA). EGABA depolarizing shift is due to zinc-dependent reduction of neuronal KCC2 activity and requires glutamate release from glioma cells. Consistently, intracellular zinc loading rapidly depolarizes EGABA in mouse hippocampal neurons, through the Src/Trk pathway and this effect is promptly reverted upon zinc chelation. This study provides a possible molecular mechanism linking glioma invasion to excitation/inhibition imbalance and epileptic seizures, through the zinc–mediated disruption of neuronal chloride homeostasis. PMID:25356870

The Search for Carbonates on Mars

NASA Technical Reports Server (NTRS)

Farmer, Jack D.; DesMarais, David J.; Morrison, David (Technical Monitor)

1994-01-01

Liquid water is presently unstable at the Martian surface, where the mean atmospheric pressure is 6 mbar (due to CO2) and the winter diurnal temperature ranges from 150 K at the pole to 220 K at the equator. Liquid water is widely regarded as a basic requirement for living systems, suggesting that life as we know it is not possible in present surface environments on Mars. However, life may survive within "oases" where liquid water is present. Potential oases on Mars include subsurface hydrothermal systems or deeply buried aquifers where chemoautolithotrophic microorganisms may exist. Potential metabolic strategies for primary production in such environments on Mars (and for the microbial mediation of geologic processes!) encompass the full range presently known for subsurface environments on the Earth (e.g. sulphate reduction, methanogenesis, acetogenesis, etc).

Synthesis of Tc-99m labeled 1,2,3-triazole-4-yl c-met binding peptide as a potential c-met receptor kinase positive tumor imaging agent.

PubMed

Kim, Eun-Mi; Joung, Min-Hee; Lee, Chang-Moon; Jeong, Hwan-Jeong; Lim, Seok Tae; Sohn, Myung-Hee; Kim, Dong Wook

2010-07-15

The mesenchymal-epithelial transition factor (c-Met), which is related to tumor cell growth, angiogenesis and metastases, is known to be overexpressed in several tumor types. In this study, we synthesized technetium-99m labeled 1,2,3-triazole-4-yl c-Met binding peptide (cMBP) derivatives, prepared by solid phase peptide synthesis and the 'click-to-chelate' protocol for the introduction of tricarbonyl technetium-99m, as a potential c-Met receptor kinase positive tumor imaging agent, and evaluated their in vitro c-Met binding affinity, cellular uptake, and stability. The (99m)Tc labeled cMBP derivatives ([(99m)Tc(CO)(3)]12, [(99m)Tc(CO)(3)]13, and [(99m)Tc(CO)(3)]14) were prepared in 85-90% radiochemical yields. The cold surrogate cMBP derivatives, [Re(CO)(3)]12, [Re(CO)(3)]13, and [Re(CO)(3)]14, were shown to have high binding affinities (0.13 microM, 0.06 microM, and 0.16 microM, respectively) to a purified cMet/Fc chimeric recombinant protein. In addition, the in vitro cellular uptake and inhibition studies demonstrated the high specific binding of these (99m)Tc labeled cMBP derivatives ([(99m)Tc(CO)(3)]12-14) to c-Met receptor positive U87MG cells. 2010 Elsevier Ltd. All rights reserved.

Distinct Anaerobic Bacterial Consumers of Cellobiose-Derived Carbon in Boreal Fens with Different CO2/CH4 Production Ratios

PubMed Central

Eiler, Alexander; Biasi, Christina; Tuittila, Eeva-Stiina; Yrjälä, Kim; Fritze, Hannu

2016-01-01

ABSTRACT Northern peatlands in general have high methane (CH4) emissions, but individual peatlands show considerable variation as CH4 sources. Particularly in nutrient-poor peatlands, CH4 production can be low and exceeded by carbon dioxide (CO2) production from unresolved anaerobic processes. To clarify the role anaerobic bacterial degraders play in this variation, we compared consumers of cellobiose-derived carbon in two fens differing in nutrient status and the ratio of CO2 to CH4 produced. After [13C]cellobiose amendment, the mesotrophic fen produced equal amounts of CH4 and CO2. The oligotrophic fen had lower CH4 production but produced 3 to 59 times more CO2 than CH4. RNA stable-isotope probing revealed that in the mesotrophic fen with higher CH4 production, cellobiose-derived carbon was mainly assimilated by various recognized fermenters of Firmicutes and by Proteobacteria. The oligotrophic peat with excess CO2 production revealed a wider variety of cellobiose-C consumers, including Firmicutes and Proteobacteria, but also more unconventional degraders, such as Telmatobacter-related Acidobacteria and subphylum 3 of Verrucomicrobia. Prominent and potentially fermentative Planctomycetes and Chloroflexi did not appear to process cellobiose-C. Our results show that anaerobic degradation resulting in different levels of CH4 production can involve distinct sets of bacterial degraders. By distinguishing cellobiose degraders from the total community, this study contributes to defining anaerobic bacteria that process cellulose-derived carbon in peat. Several of the identified degraders, particularly fermenters and potential Fe(III) or humic substance reducers in the oligotrophic peat, represent promising candidates for resolving the origin of excess CO2 production in peatlands. IMPORTANCE Peatlands are major sources of the greenhouse gas methane (CH4), yet in many peatlands, CO2 production from unresolved anaerobic processes exceeds CH4 production. Anaerobic degradation produces the precursors of CH4 production but also represents competing processes. We show that anaerobic degradation leading to high or low CH4 production involved distinct sets of bacteria. Well-known fermenters dominated in a peatland with high CH4 production, while novel and unconventional degraders could be identified in a site where CO2 production greatly exceeds CH4 production. Our results help identify and assign functions to uncharacterized bacteria that promote or inhibit CH4 production and reveal bacteria potentially producing the excess CO2 in acidic peat. This study contributes to understanding the microbiological basis for different levels of CH4 emission from peatlands. PMID:27913414

Distinct Anaerobic Bacterial Consumers of Cellobiose-Derived Carbon in Boreal Fens with Different CO2/CH4 Production Ratios.

PubMed

Juottonen, Heli; Eiler, Alexander; Biasi, Christina; Tuittila, Eeva-Stiina; Yrjälä, Kim; Fritze, Hannu

2017-02-15

Northern peatlands in general have high methane (CH 4 ) emissions, but individual peatlands show considerable variation as CH 4 sources. Particularly in nutrient-poor peatlands, CH 4 production can be low and exceeded by carbon dioxide (CO 2 ) production from unresolved anaerobic processes. To clarify the role anaerobic bacterial degraders play in this variation, we compared consumers of cellobiose-derived carbon in two fens differing in nutrient status and the ratio of CO 2 to CH 4 produced. After [ 13 C]cellobiose amendment, the mesotrophic fen produced equal amounts of CH 4 and CO 2 The oligotrophic fen had lower CH 4 production but produced 3 to 59 times more CO 2 than CH 4 RNA stable-isotope probing revealed that in the mesotrophic fen with higher CH 4 production, cellobiose-derived carbon was mainly assimilated by various recognized fermenters of Firmicutes and by Proteobacteria The oligotrophic peat with excess CO 2 production revealed a wider variety of cellobiose-C consumers, including Firmicutes and Proteobacteria, but also more unconventional degraders, such as Telmatobacter-related Acidobacteria and subphylum 3 of Verrucomicrobia Prominent and potentially fermentative Planctomycetes and Chloroflexi did not appear to process cellobiose-C. Our results show that anaerobic degradation resulting in different levels of CH 4 production can involve distinct sets of bacterial degraders. By distinguishing cellobiose degraders from the total community, this study contributes to defining anaerobic bacteria that process cellulose-derived carbon in peat. Several of the identified degraders, particularly fermenters and potential Fe(III) or humic substance reducers in the oligotrophic peat, represent promising candidates for resolving the origin of excess CO 2 production in peatlands. Peatlands are major sources of the greenhouse gas methane (CH 4 ), yet in many peatlands, CO 2 production from unresolved anaerobic processes exceeds CH 4 production. Anaerobic degradation produces the precursors of CH 4 production but also represents competing processes. We show that anaerobic degradation leading to high or low CH 4 production involved distinct sets of bacteria. Well-known fermenters dominated in a peatland with high CH 4 production, while novel and unconventional degraders could be identified in a site where CO 2 production greatly exceeds CH 4 production. Our results help identify and assign functions to uncharacterized bacteria that promote or inhibit CH 4 production and reveal bacteria potentially producing the excess CO 2 in acidic peat. This study contributes to understanding the microbiological basis for different levels of CH 4 emission from peatlands. Copyright © 2017 American Society for Microbiology.

Hydraulic properties of groundwater systems in the saprolite and sediments of the wheatbelt, Western Australia

NASA Astrophysics Data System (ADS)

George, Richard J.

1992-01-01

Hydraulic properties of deeply weathered basement rocks and variably weathered sedimentary materials were measured by pumping and slug-test methods. Results from over 200 bores in 13 catchments, and eight pumping-test sites across the eastern and central wheatbelt of Western Australia were analysed. Measurements were made in each of the major lithological units, and emphasis placed on a ubiquitous basal saprolite aquifer. Comparisons were made between alternative drilling and analytical procedures to determine the most appropriate methods of investigation. Aquifers with an average hydraulic conductivity of 0.55 m day -1 occur in variably weathered Cainozoic sediments and poorly weathered saprolite grits (0.57 m day -1). These aquifers are separated by an aquitard (0.065 m day -1) comprising the mottled and pallid zones of the deeply weathered profile. Locally higher values of hydraulic conductivity occur in the saprolite aquifer, although after prolonged periods of pumping the values decrease until they are similar to those obtained from the slug-test methods. Hydraulic conductivities measured in bores drilled with rotary auger rigs were approximately an order of magnitude lower than those measured in the same material with bores drilled by the rotary air-blast method. Wheatbelt aquifers range from predominantly unconfined (Cainozoic sediments), to confined (saprolite grit aquifer). The poorly weathered saprolite grit aquifer has moderate to high transmissivities (4-50 m 2 day -1) and is capable of producing from less than 5 to over 230 kl day -1 of ground water, which is often of a quality suitable for livestock. Yields are influenced by the variability in the permeability of isovolumetrically weathered materials from which the aquifer is derived. The overlying aquitard has a low transmissivity (< 1 m 2 day -1), especially when deeply weathered, indurated and silicified. The transmissivity of the variably weathered sedimentary materials ranges from less than 0.5 m 2 day -1 to over 10 m 2 day -1, depending on the texture of the materials and their position within the landscape. Higher transmissivity zones may occur as discrete layers of coarser textured materials. The salinity of the saprolite and sedimentary aquifers ranges from less than 2000 mgl -1 to greater than 250000 mgl -1 (total dissolved solids; TDS), depending on position within the landscape. Secondary soil salinization develops when groundwater discharge occurs from either saprolite or sedimentary aquifers.

Synthesis of highly efficient CaO-based, self-stabilizing CO2 sorbents via structure-reforming of steel slag.

PubMed

Tian, Sicong; Jiang, Jianguo; Yan, Feng; Li, Kaimin; Chen, Xuejing

2015-06-16

Capturing anthropogenic CO2 in a cost-effective and highly efficient manner is one of the most challenging issues faced by scientists today. Herein, we report a novel structure-reforming approach to convert steel slag, a cheap, abundant, and nontoxic calcium-rich industrial waste, as the only feedstock into superior CaO-based, self-stabilizing CO2 sorbents. The CO2 capture capacity of all the steel slag-derived sorbents was improved more than 10-fold compared to the raw slag, with the maximum uptake of CO2 achieving at 0.50 gCO2 gsorbent(-1). Additionally, the initial steel slag-derived sorbent could retain 0.25 gCO2 gsorbent(-1), that is, a decay rate of only 12% over 30 carbonation-calcination cycles, the excellent self-stabilizing property allowed it to significantly outperform conventional CaO, and match with most of the existing synthetic CaO-based sorbents. A synergistic effect that facilitated CO2 capture by CaO-based sorbents was clearly recognized when Mg and Al, the most common elements in steel slag, coexisted with CaO in the forms of MgO and Al2O3, respectively. During the calcium looping process, MgO served as a well spacer to increase the porosity of sorbents together with Al2O3 serving as a durable stabilizer to coresist the sintering of CaCO3 grains at high temperatures.

2,4,6-Trinitrotoluene Reduction by Carbon Monoxide Dehydrogenase from Clostridium thermoaceticum

PubMed Central

Huang, Shouqin; Lindahl, Paul A.; Wang, Chuanyue; Bennett, George N.; Rudolph, Frederick B.; Hughes, Joseph B.

2000-01-01

Purified CO dehydrogenase (CODH) from Clostridium thermoaceticum catalyzed the transformation of 2,4,6-trinitrotoluene (TNT). The intermediates and reduced products of TNT transformation were separated and appear to be identical to the compounds formed by C. acetobutylicum, namely, 2-hydroxylamino-4,6-dinitrotoluene (2HA46DNT), 4-hydroxylamino-2,6-dinitrotoluene (4HA26DNT), 2,4-dihydroxylamino-6-nitrotoluene (24DHANT), and the Bamberger rearrangement product of 2,4-dihydroxylamino-6-nitrotoluene. In the presence of saturating CO, CODH catalyzed the conversion of TNT to two monohydroxylamino derivatives (2HA46DNT and 4HA26DNT), with 4HA26DNT as the dominant isomer. These derivatives were then converted to 24DHANT, which slowly converted to the Bamberger rearrangement product. Apparent Km and kcat values of TNT reduction were 165 ± 43 μM for TNT and 400 ± 94 s−1, respectively. Cyanide, an inhibitor for the CO/CO2 oxidation/reduction activity of CODH, inhibited the TNT degradation activity of CODH. PMID:10742229

Low-energy vibrations of the group 10 metal monocarbonyl MCO (M = Ni, Pd, and Pt): rotational spectroscopy and force field analysis.

PubMed

Okabayashi, Toshiaki; Yamamoto, Takuya; Okabayashi, Emi Y; Tanimoto, Mitsutoshi

2011-03-17

The rotational spectra of NiCO and PdCO in the ground and ν(2) excited vibrational states were observed by employing a source-modulated microwave spectrometer. The NiCO and PdCO molecules were generated in a free space cell by the sputtering reaction of nickel and palladium sheets, respectively, lining the inner surface of a stainless steel cathode with a dc glow plasma of CO and Ar. The molecular constants of NiCO and PdCO were determined by least-squares analysis. By force field analysis for the molecular constants of not only NiCO and PdCO but also of PtCO as previously reported, the harmonic force constants were determined for these three group 10 metal monocarbonyls. The vibrational wavenumbers derived for the lower M-C stretching vibrations were in good agreement with those obtained from the IR spectra in noble gas matrices and those predicted by several quantum chemical calculations published in the past. The bending vibrational wavenumbers derived by the force field analysis were also consistent with most quantum chemical calculations previously reported, but showed systematic discrepancies from the matrix IR values by about 40 cm(-1), even after reassignment (ν(2) band → 2ν(2) band) of the matrix IR spectra of PdCO and PtCO.

Effect of Temperature on the Kinetics of Sorption of Co2+ and Ni2+ Ions by a Sorbent Based on an Inositol Hexaphosphoric Acid Derivative

NASA Astrophysics Data System (ADS)

Yarusova, S. B.; Makarenko, N. V.; Gordienko, P. S.; Karpenko, M. A.; Novikova, E. S.

2018-03-01

Data on the effect temperature has on the kinetics of the removal of Co2+ and Ni2+ ions under static conditions by a sorbent based on a derivative of phytic acid fabricated from rice production waste are presented. It is shown that when the temperature is raised from 20 to 60°C, the sorption capacity of the sorbent based on phytic acid increases over the period of sorption and within 180 min reaches values of 1.4 mmol g-1 for Co2+ ions and 1.3 mmol g-1 for Ni2+ ions. It is established that for the investigated range of temperatures, order n of the sorption of Co2+ and Ni2+ ions is <1, which characterizes the reactions accompanied by diffusion processes. It is found that the process of removal of Co2+ and Ni2+ ions is characterized with low activation energy (20.74 kJ mol-1 for Co2+ ions and 14.2 kJ mol-1 for Ni2+ ions). It is also demonstrated that the sorption process in the considered time frame is best described by a kinetic model of a pseudo-second order, as is indicated by respective correlation coefficients.

CoFe2O4 derived-from bi-metal organic frameworks wrapped with graphene nanosheets as advanced anode for high-performance lithium ion batteries

NASA Astrophysics Data System (ADS)

Yang, Hongxun; Zhang, Kaixuan; Wang, Yang; Yan, Chao; Lin, Shengling

2018-04-01

CoFe2O4/graphene nanosheets (GNS) nanocomposites derived from bi-metal organic frameworks and graphene oxides were firstly synthesized via a facile one-pot chemical precipitation with subsequent thermal decomposition method. The as-prepared CoFe2O4/GNS were characterized by XRD, Raman, SEM, TEM and BET adsorption-desorption. As an anode for lithium ion batteries, the CoFe2O4/GNS nanocomposites exhibited an obvious enhancement electrochemical property in terms of a higher discharge capacity of 1061.7 mAh g-1 after 100 cycles at 100 mA g-1 with 75.1% capacity retention and the excellent reversible capacity of 956.2 mAh g-1 when the charge-discharge rate returned from 2 A g-1 to 0.1 A g-1 after 60 cycles. This enhancement could be attributed to the synergistic effects between Co and Fe oxides, and the graphene nanosheets which could not only accommodate the volume variations of CoFe2O4 nanoparticles during cycling, but also improve the contact area between electrolyte and electrodes.

Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction Investigated with 18 O Labeling.

PubMed

Lum, Yanwei; Ager, Joel W

2018-01-08

Oxide-derived (OD) Cu catalysts have high selectivity towards the formation of multi-carbon products (C 2 /C 3 ) for aqueous electrochemical CO 2 reduction (CO 2 R). It has been proposed that a large fraction of the initial oxide can be surprisingly resistant to reduction, and these residual oxides play a crucial catalytic role. The stability of residual oxides was investigated by synthesizing 18 O-enriched OD Cu catalysts and testing them for CO 2 R. These catalysts maintain a high selectivity towards C 2 /C 3 products (ca. 60 %) for up to 5 h in 0.1 m KHCO 3 at -1.0 V vs. RHE. However, secondary-ion mass spectrometry measurements show that only a small fraction (<1 %) of the original 18 O content remains, showing that residual oxides are not present in significant amounts during CO 2 R. Furthermore, we show that OD Cu can reoxidize rapidly, which could compromise the accuracy of ex situ methods for determining the true oxygen content. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phenotypic and Functional Changes in Blood Monocytes Following Adherence to Endothelium

PubMed Central

Tso, Colin; Rye, Kerry-Anne; Barter, Philip

2012-01-01

Objective Blood monocytes are known to express endothelial-like genes during co-culture with endothelium. In this study, the time-dependent change in the phenotype pattern of primary blood monocytes after adhering to endothelium is reported using a novel HLA-A2 mistyped co-culture model. Methods and Results Freshly isolated human PBMCs were co-cultured with human umbilical vein endothelial cells or human coronary arterial endothelial cells of converse human leukocyte antigen A2 (HLA-A2) status. This allows the tracking of the PBMC-derived cells by HLA-A2 expression and assessment of their phenotype pattern over time. PBMCs that adhered to the endothelium at the start of the co-culture were predominantly CD11b+ blood monocytes. After 24 to 72 hours in co-culture, the endothelium-adherent monocytes acquired endothelial-like properties including the expression of endothelial nitric oxide synthase, CD105, CD144 and vascular endothelial growth factor receptor 2. The expression of monocyte/macrophage lineage antigens CD14, CD11b and CD36 were down regulated concomitantly. The adherent monocytes did not express CD115 after 1 day of co-culture. By day 6, the monocyte-derived cells expressed vascular cell adhesion molecule 1 in response to tumour necrosis factor alpha. Up to 10% of the PBMCs adhered to the endothelium. These monocyte-derived cells contributed up to 30% of the co-cultured cell layer and this was dose-dependent on the PBMC seeding density. Conclusions Human blood monocytes undergo rapid phenotype change to resemble endothelial cells after adhering to endothelium. PMID:22615904

Sediment-water gas exchange in two Swedish lakes measured by Eddy Correlation

NASA Astrophysics Data System (ADS)

Kokic, J.; Sahlee, E.; Brand, A.; Sobek, S.

2014-12-01

Lake sediments are hotspots for carbon (C) cycling, acting both as sinks and sources through C burial and production of carbon dioxide (CO2) and methane. The fate of this CO2 in the water column is controlled by bottom water turbulence, a factor not accounted for in current estimates of sediment CO2 fluxes. This study is aimed to quantify the turbulent CO2 flux across the sediment-water interface (SWI) by measuring the oxygen (O2) flux with the non-invasive Eddy Correlation (EC) method that combines measurements of 3D velocity (ADV) and O2 fluctuations with a microsensor. Using the metabolic relation (respiratory quotient, RQ) of O2 and CO2 derived from a sediment incubation experiment we present the first estimates of turbulent lake sediment CO2 flux from two boreal lakes in Sweden (Erssjön and Erken, 0.07 km2 and 23.7 km2 respectively). Only ~10 % of the total dataset was extracted for flux calculations due to poor signal-to-noise ratio in the velocity and O2 signals. The sediment in Lake Erssjön was both consuming and producing O2, related to bacterial respiration and photosynthesis. Mean O2 flux was -0.19 and 0.17 μmol O2 m-2 sec-1, comparing to 0.04 μmol O2 m-2 sec-1 derived from the sediment incubation experiment. Fluxes for Lake Erken are still to be determined. Experimentally derived RQ of the both lake sediments were close to unity implying that in-situ CO2 fluxes are of similar magnitude as O2 fluxes, varying between -0.15 and 0.18 μmol C m-2 sec-1. The first measurement of turbulent sediment O2 flux and estimate of turbulent CO2 flux from a small boreal lake show higher and more variable fluxes than previously found in experimental studies. The low amount of data extracted for flux calculations (~10%) point towards the difficulties in EC measurement in low-turbulence environments. On-going work focuses on the turbulence structure in lakes and its influence on the gas fluxes at the SWI.

Genotype influences sulfur metabolism in broccoli (Brassica oleracea L.) under elevated CO2 and NaCl stress.

PubMed

Rodríguez-Hernández, María del Carmen; Moreno, Diego A; Carvajal, Micaela; Martínez-Ballesta, María del Carmen

2014-12-01

Climatic change predicts elevated salinity in soils as well as increased carbon dioxide dioxide [CO2] in the atmosphere. The present study aims to determine the effect of combined salinity and elevated [CO2] on sulfur (S) metabolism and S-derived phytochemicals in green and purple broccoli (cv. Naxos and cv. Viola, respectively). Elevated [CO2] involved the amelioration of salt stress, especially in cv. Viola, where a lower biomass reduction by salinity was accompanied by higher sodium (Na(+)) and chloride (Cl(-)) compartmentation in the vacuole. Moreover, salinity and elevated [CO2] affected the mineral and glucosinolate contents and the activity of biosynthetic enzymes of S-derived compounds and the degradative enzyme of glucosinolate metabolism, myrosinase, as well as the related amino acids and the antioxidant glutathione (GSH). In cv. Naxos, elevated [CO2] may trigger the antioxidant response to saline stress by means of increased GSH concentration. Also, in cv. Naxos, indolic glucosinolates were more influenced by the NaCl×CO2 interaction whereas in cv. Viola the aliphatic glucosinolates were significantly increased by these conditions. Salinity and elevated [CO2] enhanced the S cellular partitioning and metabolism affecting the myrosinase-glucosinolate system. © The Author 2014. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Structure and composition of Fe-OM co-precipitates that form in soil-derived solutions

NASA Astrophysics Data System (ADS)

Fritzsche, Andreas; Schröder, Christian; Wieczorek, Arkadiusz K.; Händel, Matthias; Ritschel, Thomas; Totsche, Kai U.

2015-11-01

Iron oxides represent a substantial fraction of secondary minerals and particularly affect the reactive properties of natural systems in which they formed, e.g. in soils and sediments. Yet, it is still obscure how transient conditions in the solution will affect the properties of in situ precipitated Fe oxides. Transient compositions, i.e. compositions that change with time, arise due to predominant non-equilibrium states in natural systems, e.g. between liquid and solid phases in soils. In this study, we characterize Fe-OM co-precipitates that formed in pH-neutral exfiltrates from anoxic topsoils under transient conditions. We applied soil column outflow experiments, in which Fe2+ was discharged with the effluent from anoxic soil and subsequently oxidized in the effluent due to contact with air. Our study features three novel aspects being unconsidered so far: (i) the transient composition of soil-derived solutions, (ii) that pedogenic Fe oxides instead of Fe salts serve as major source for Fe2+ in soil solution and (iii) the presence of exclusively soil-derived organic and inorganic compounds during precipitation. The experiments were carried out with two topsoil materials that differed in composition, texture and land use. Derived from Mössbauer spectroscopy, broad distributions in quadrupole splittings (0-2 mm s-1) and magnetic hyperfine fields (35-53 T) indicated the presence of low-crystalline ferrihydrite and even lower crystalline Fe phases in all Fe-OM co-precipitates. There was no unequivocal evidence for other Fe oxides, i.e. lepidocrocite and (nano)goethite. The Fe-OM co-precipitates contained inorganic (P, sulfate, silicate, Al, As) and organic compounds (proteins, polysaccharides), which were concurrently discharged from the soils. Their content in the Fe-OM co-precipitates was controlled by their respective concentration in the soil-derived solution. On a molar basis, OC and Fe were the main components in the Fe-OM co-precipitates (OC/Fe ratio = 0.5-2). The elemental composition of the Fe-OM co-precipitates was in accordance with the sequential precipitation of Fe(III)phosphates/arsenates prior to the formation of ferrihydrite. This explains decreasing Si contents in the Fe-OM co-precipitates with increasing availability of P. With respect to constant mean quadrupole splittings and slightly decreasing mean magnetic hyperfine fields, increasing contents of OC, P and Al in the Fe-OM co-precipitates did not further increase the structural disorder of the Fe polyhedra, while the crystallite interactions slightly decreased. Scanning electron microscopy and dynamic light scattering revealed the coincidental presence of variably sized aggregates and a considerable amount of Fe-OM co-precipitates, which remained dispersed in solution for months. Thus, variably composed Fe-OM co-precipitates with highly diverse aggregate sizes and comparably constant poor crystallinity can be expected after the oxidation of Fe2+ in transient, soil-derived solutions.

Growth suppression of colorectal cancer by plant-derived multiple mAb CO17-1A × BR55 via inhibition of ERK1/2 phosphorylation.

PubMed

Kwak, Dong Hoon; Moussavou, Ghislain; Lee, Ju Hyoung; Heo, Sung Youn; Ko, Kisung; Hwang, Kyung-A; Jekal, Seung-Joo; Choo, Young-Kug

2014-11-14

We have generated the transgenic Tabaco plants expressing multiple monoclonal antibody (mAb) CO7-1A × BR55 by cross-pollinating with mAb CO17-1A and mAb BR55. We have demonstrated the anti-cancer effect of plant-derived multiple mAb CO17-1A × BR55. We find that co-treatment of colorectal mAbs (anti-epithelial cellular adhesion molecule (EpCAM), plant-derived monoclonal antibody (mAb(P)) CO17-1A and mAb(P) CO17-1A × BR55) with RAW264.7 cells significantly inhibited the cell growth in SW620 cancer cells. In particular, multi mAb(P) CO17-1A × BR55 significantly and efficiently suppressed the growth of SW620 cancer cells compared to another mAbs. Apoptotic death-positive cells were significantly increased in the mAb(P) CO17-1A × BR55-treated. The mAb(P) CO17-1A × BR55 treatment significantly decreased the expression of B-Cell lymphoma-2 (BCl-2), but the expression of Bcl-2-associated X protein (Bax), and cleaved caspase-3 were markedly increased. In vivo, the mAb(P) CO17-1A × BR55 significantly and efficiently inhibited the growth of colon tumors compared to another mAbs. The apoptotic cell death and inhibition of pro-apoptotic proteins expression were highest by treatment with mAb(P) CO17-1A × BR55. In addition, the mAb(P) CO17-1A × BR55 significantly inhibited the extracellular signal-regulated kinase 1 and 2 (ERK1/2) phosphorylation in cancer cells and tumors. Therefore, this study results suggest that multiple mAb(P) CO17-1A × BR55 has a significant effect on apoptosis-mediated anticancer by suppression of ERK1/2 phosphorylation in colon cancer compared to another mAbs. In light of these results, further clinical investigation should be conducted on mAb(P) CO17-1A × BR55 to determine its possible chemopreventive and/or therapeutic efficacy against human colon cancer.

Three years of semicontinuous greenhouse gas measurements at the Puy de Dôme station (central France)

NASA Astrophysics Data System (ADS)

Lopez, M.; Schmidt, M.; Ramonet, M.; Bonne, J.-L.; Colomb, A.; Kazan, V.; Laj, P.; Pichon, J.-M.

2015-09-01

Three years of greenhouse gas measurements, obtained using a gas chromatograph (GC) system located at the Puy de Dôme station at 1465 m a.s.l. in central France, are presented. The GC system was installed in 2010 at Puy de Dôme and was designed for automatic and accurate semicontinuous measurements of atmospheric carbon dioxide, methane, nitrous oxide and sulfur hexafluoride mole fractions. We present in detail the instrumental setup and the calibration strategy, which together allow the GC to reach repeatabilities of 0.1 μmol mol-1, 1.2 nmol mol-1, 0.3 nmol mol-1 and 0.06 pmol mol-1 for CO2, CH4, N2O and SF6, respectively. The analysis of the 3-year atmospheric time series revealed how the planetary boundary layer height drives the mole fractions observed at a mountain site such as Puy de Dôme where air masses alternate between the planetary boundary layer and the free troposphere. Accurate long-lived greenhouse gas measurements collocated with 222Rn measurements as an atmospheric tracer allowed us to determine the CO2, CH4 and N2O emissions in the catchment area of the station. The derived CO2 surface flux revealed a clear seasonal cycle, with net uptake by plant assimilation in the spring and net emission caused by the biosphere and burning of fossil fuel during the remainder of the year. We calculated a mean annual CO2 flux of 1310 ± 680 t CO2 km-2. The derived CH4 and N2O emissions in the station catchment area were 7.0 ± 4.0 t CH4 km-2 yr-1 and 1.8 ± 1.0 t N2O km-2 yr-1, respectively. Our derived annual CH4 flux is in agreement with the national French inventory, whereas our derived N2O flux is 5 times larger than the same inventory.

PdCo nanoparticles supported on carbon fibers derived from cotton: Maximum utilization of Pd atoms for efficient reduction of nitroarenes.

PubMed

Yang, Jin; Wang, Wei David; Dong, Zhengping

2018-08-15

In the present work, a facile and environment-friendly route is illustrated for the efficient fabrication of highly dispersed PdCo nanoparticles (NPs) by modified cotton-derived carbon fibers (PdCo/CCF). Firstly, commercial cotton was impregnated with CoCl 2 , followed by pyrolysis under high calcination temperature to obtain the Co NPs modified CCF sample (Co/CCF). Secondly, Co/CCF was treated with Pd(AcO) 2 aqueous solution, wherein, through a spontaneous replacement reaction process, Pd 2+ is reduced to metallic Pd and mostly covered on the surface of the Co NPs. Thus, the PdCo/CCF catalyst was obtained avoiding the use of toxic reductants like NaBH 4 , NH 2 NH 2 and HCHO. The PdCo/CCF catalyst exhibits excellent catalytic activity and recyclability for the reduction of 4-nitrophenol and other nitroarenes compared with Pd/CCF, PdCo NPs and many other noble metals based catalysts. The reasons could be attributed to the uniformly dispersed and accessible PdCo NPs on the surface of the CCF, and the Pd atoms deposited on the Co NPs surface that makes the Pd active sites available for optimum use. The PdCo/CCF catalyst also exhibits potential application for catalytic reduction of nitroarenes in a fixed bed reactor under mild reaction conditions. Furthermore, the PdCo/CCF catalyst can be magnetically recycled and reused for at least ten cycles without either losing catalytic activity or leaching of Pd active sites, thereby confirming its superior stability. Copyright © 2018 Elsevier Inc. All rights reserved.

Kinetic temperature of massive star-forming molecular clumps measured with formaldehyde. III. The Orion molecular cloud 1

NASA Astrophysics Data System (ADS)

Tang, X. D.; Henkel, C.; Menten, K. M.; Wyrowski, F.; Brinkmann, N.; Zheng, X. W.; Gong, Y.; Lin, Y. X.; Esimbek, J.; Zhou, J. J.; Yuan, Y.; Li, D. L.; He, Y. X.

2018-01-01

We mapped the kinetic temperature structure of the Orion molecular cloud 1 (OMC-1) with para-H2CO (JKaKc = 303-202, 322-221, and 321-220) using the APEX 12 m telescope. This is compared with the temperatures derived from the ratio of the NH3 (2, 2)/(1, 1) inversion lines and the dust emission. Using the RADEX non-LTE model, we derive the gas kinetic temperature modeling the measured averaged line ratios of para-H2CO 322-221/303-202 and 321-220/303-202. The gas kinetic temperatures derived from the para-H2CO line ratios are warm, ranging from 30 to >200 K with an average of 62 ± 2 K at a spatial density of 105 cm-3. These temperatures are higher than those obtained from NH3 (2, 2)/(1, 1) and CH3CCH (6-5) in the OMC-1 region. The gas kinetic temperatures derived from para-H2CO agree with those obtained from warm dust components measured in the mid infrared (MIR), which indicates that the para-H2CO (3-2) ratios trace dense and warm gas. The cold dust components measured in the far infrared (FIR) are consistent with those measured with NH3 (2, 2)/(1, 1) and the CH3CCH (6-5) line series. With dust at MIR wavelengths and para-H2CO (3-2) on one side, and dust at FIR wavelengths, NH3 (2, 2)/(1, 1), and CH3CCH (6-5) on the other, dust and gas temperatures appear to be equivalent in the dense gas (n(H2) ≳ 104 cm-3) of the OMC-1 region, but provide a bimodal distribution, one more directly related to star formation than the other. The non-thermal velocity dispersions of para-H2CO are positively correlated with the gas kinetic temperatures in regions of strong non-thermal motion (Mach number ≳ 2.5) of the OMC-1, implying that the higher temperature traced by para-H2CO is related to turbulence on a 0.06 pc scale. Combining the temperature measurements with para-H2CO and NH3 (2, 2)/(1, 1) line ratios, we find direct evidence for the dense gas along the northern part of the OMC-1 10 km s-1 filament heated by radiation from the central Orion nebula. The reduced datacubes are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/609/A16

Development of design information for molecular-sieve type regenerative CO2-removal systems

NASA Technical Reports Server (NTRS)

Wright, R. M.; Ruder, J. M.; Dunn, V. B.; Hwang, K. C.

1973-01-01

Experimental and analytic studies were conducted with molecular sieve sorbents to provide basic design information, and to develop a system design technique for regenerable CO2-removal systems for manned spacecraft. Single sorbate equilibrium data were obtained over a wide range of conditions for CO2, water, nitrogen, and oxygen on several molecular sieve and silica gel sorbents. The coadsorption of CO2 with water preloads, and with oxygen and nitrogen was experimentally evaluated. Mass-transfer, and some limited heat-transfer performance evaluations were accomplished under representative operating conditions, including the coadsorption of CO2 and water. CO2-removal system performance prediction capability was derived.

Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts.

PubMed

Loewen, Natalia D; Neelakantan, Taruna V; Berben, Louise A

2017-09-19

As a society, we are heavily dependent on nonrenewable petroleum-derived fuels and chemical feedstocks. Rapid depletion of these resources and the increasingly evident negative effects of excess atmospheric CO 2 drive our efforts to discover ways of converting excess CO 2 into energy dense chemical fuels through selective C-H bond formation and using renewable energy sources to supply electrons. In this way, a carbon-neutral fuel economy might be realized. To develop a molecular or heterogeneous catalyst for C-H bond formation with CO 2 requires a fundamental understanding of how to generate metal hydrides that selectively donate H - to CO 2 , rather than recombining with H + to liberate H 2 . Our work with a unique series of water-soluble and -stable, low-valent iron electrocatalysts offers mechanistic and thermochemical insights into formate production from CO 2 . Of particular interest are the nitride- and carbide-containing clusters: [Fe 4 N(CO) 12 ] - and its derivatives and [Fe 4 C(CO) 12 ] 2- . In both aqueous and mixed solvent conditions, [Fe 4 N(CO) 12 ] - forms a reduced hydride intermediate, [H-Fe 4 N(CO) 12 ] - , through stepwise electron and proton transfers. This hydride selectively reacts with CO 2 and generates formate with >95% efficiency. The mechanism for this transformation is supported by crystallographic, cyclic voltammetry, and spectroelectrochemical (SEC) evidence. Furthermore, installation of a proton shuttle onto [Fe 4 N(CO) 12 ] - facilitates proton transfer to the active site, successfully intercepting the hydride intermediate before it reacts with CO 2 ; only H 2 is observed in this case. In contrast, isoelectronic [Fe 4 C(CO) 12 ] 2- features a concerted proton-electron transfer mechanism to form [H-Fe 4 C(CO) 12 ] 2- , which is selective for H 2 production even in the presence of CO 2 , in both aqueous and mixed solvent systems. Higher nuclearity clusters were also studied, and all are proton reduction electrocatalysts, but none promote C-H bond formation. Thermochemical insights into the disparate reactivities of these clusters were achieved through hydricity measurements using SEC. We found that only [H-Fe 4 N(CO) 12 ] - and its derivative [H-Fe 4 N(CO) 11 (PPh 3 )] - have hydricities modest enough to avoid H 2 production but strong enough to make formate. [H-Fe 4 C(CO) 12 ] 2- is a stronger hydride donor, theoretically capable of making formate, but due to an overwhelming thermodynamic driving force and the increased electrostatic attraction between the more negative cluster and H + , only H 2 is observed experimentally. This illustrates the fundamental importance of controlling thermochemistry when designing new catalysts selective for C-H bond formation and establishes a hydricity range of 15.5-24.1 or 44-49 kcal mol -1 where C-H bond formation may be favored in water or MeCN, respectively.

Mass transfers induced by flow of CO2 rich-brine through fractured cement: experiment and modeling

NASA Astrophysics Data System (ADS)

Habdoulghafour, H.; Luquot, L.; Gouze, P.

2011-12-01

Long-term confinement failure is a key issue in the assessment of the confidence levels of CO2 storage. Evaluating the potential for CO2 leakage through wells (casing, cements and interfaces with the cap-rock) is of primary importance for the analysis of latent and short-range risks of confinement failure. Some controversy remains regarding the risk of conventional cements. While some researchers argue that they may fail, EOR oil industry experience suggests the opposite. The issue is non-trivial. Experimental investigations on cement alteration mechanism triggered by CO2-rich brine show that both carbonation and de-carbonation mechanisms may occur and are the dominant mass exchange processes. It is tempting to conclude from the results of batch experiments that cement carbonation tends to decrease porosity and permeability, whereas de-carbonation increases both, but these assumptions must be tested using realistic flow-through experiments. Here we investigated the effect of CO2 rich-brine flowing through fractured portlandite-rich cement plugs. Experiments were carried out under realistic in situ conditions (T=80°C and P=10 MPa). Monitoring the fluid composition at the outlet allows us to measure the rate at which portlandite and CSH are dissolved and Ca-carbonate (calcite) precipitated. The precipitation of carbonate limits the fluid access to the inner part of cement (by diffusion) but, in the condition of forced flow-through CO2-rich brine in the fracture, this carbonate layer is subsequently dissolved as showed by the X-ray micro tomography performed post-mortem. Despite these coupled dissolution-precipitation mechanisms (and the on-going reaction front displacement), the permeability of the fracture remains almost constant during the experiment because the effective aperture controlled by the undissolved fraction of the cement (i.e. silica-rich minerals) is preserved. For the studied conditions, it can be concluded that the flow properties of the fractured cements are conserved, while the chemical and probably the mechanical properties of the cement are deeply modified.

Specific anion effects on copper surface through electrochemical treatment: Enhanced photoelectrochemical CO2 reduction activity of derived nanostructures induced by chaotropic anions

NASA Astrophysics Data System (ADS)

Navaee, Aso; Salimi, Abdollah

2018-05-01

Copper derivatives are the most prominent CO2 reduction electrocatalyst. Herein, the metallic copper has been electrochemically treated with some of common ionic salts such as N3bar, HPO2bar, S2bar, Fbar, Clbar, Brbar and Ibar based on the dissolution of a metallic working electrode in an aqueous solution to derive the surface roughness incorporated with nanostructures. Diverse surface morphology can be obtained when the ionic radii of anions are changed. Surface study reveals various roughness shapes based on the size and polarity of the anions, where the ions with higher ionic radii have higher impact on the Cu surface. In comparison, polyatomic oxyanion such as HPO2bar even with large ionic radii do not have enough strength to create the surface roughness than that of oxygen-free anions with large ionic radii. The photoelectrochemical behavior of the modified surfaces toward CO2 reduction is studied at a wide potential window in bicarbonate aqueous solution. Based on our investigations, treated surfaces by Ibar, Clbar and S2bargive a more surface roughness, while Ibar and N3bar offer higher catalytic activity toward CO2 reduction due to possible complexing ability of these anions with Cu cations, followed by formation of the co-catalyst semiconductor and facilitate electron transfer. This methodology can be applied to investigate the effect of ions on transition metals along with obtaining different surface morphologies tailored to different applications.

CoBr2-TMTU-zinc catalysed-Pauson-Khand reaction.

PubMed

Wang, Yuefan; Xu, Lingmin; Yu, Ruocheng; Chen, Jiahua; Yang, Zhen

2012-08-25

A cobalt-TMTU complex, derived from the in situ reduction of CoBr(2) with Zn in the presence of TMTU, can catalyze Pauson-Khand reaction at a balloon pressure of CO, which enables the synthesis of structurally diverse cyclopentenones. This catalytic system works efficiently for both intermolecular and intramolecular PK reactions.

Progress in interpreting CO2 lidar signatures to obtain cirrus microphysical and optical properties

NASA Technical Reports Server (NTRS)

Eberhard, Wynn L.

1993-01-01

One cloud/radiation issue at FIRE 2 that has been addressed by the CO2 lidar team is the zenith-enhanced backscatter (ZEB) signature from oriented crystals. A second topic is narrow-beam optical depth measurements using CO2 lidar. This paper describes the theoretical models we have developed for these phenomena and the data-processing algorithms derived from them.

Petroleum geology of the mid-Atlantic continental margin, offshore Virginia

USGS Publications Warehouse

Bayer, K.C.; Milici, R.C.

1989-01-01

The Baltimore Canyon Trough, a major sedimentary basin on the Atlantic continental shelf, contains up to 18 km of Mesozoic and Cenozoic strata. The basin has been studied extensively by multichannel common depth point (CDP) seismic reflection profiles and has been tested by drilling for hydrocarbon resources in several places. The Mesozoic and Cenozoic strata contained in the basin were deposited in littoral to bathyal depositional settings and contain immature to marginally mature oil-prone and gas-prone kerogen. The more deeply buried strata of Early Mesozoic age are more likely to be thermally mature than are the younger strata with respect to hydrocarbon generation, but contain terrestrially derived coaly organic matter that would be prone to yield gas, rather than oil. An analysis of available CDP seismic reflection data has indicated that there are several potential hydrocarbon plays in the area offshore of Virginia. These include: (1) Lower Mesozoic synrift basins that appear similar to those exposed in the Appalachian Piedmont, (2) a stratigraphic updip pinchout of strata of Early Mesozoic age in the offshore region near the coast, (3) a deeply buried paleoshelf edge, where seismic reflectors dip sharply seaward; and (4) a Cretaceous/Jurassic shelf edge beneath the present continental rise. Of these, the synrift basins and Cretaceous/Jurassic shelf edge are considered to be the best targets for exploration. ?? 1989.

Interactions of fluid and gas movement and faulting in the Colorado Plateau, southeastern Utah

NASA Astrophysics Data System (ADS)

Shipton, Z. K.; Evans, J. P.; Kirschner, D.; Heath, J.; Williams, A.; Dockrill, B.

2002-12-01

The east-west and west-northwest striking Salt Wash and the Little Grand Wash normal faults in the Colorado Plateau of southeastern Utah emit large amounts of CO2 gas from abandon drill holes, springs and a hydrocarbon seep. The leakage of similar CO2 charged water has also occurred in the past as shown by large localized tufa deposits and horizontal veins along the fault traces. These deposits consist of thick tufa terraces and mound extending up to 50 meters from the fault damage zones. The faults cut a north plunging anticline of siltstones, shales, and sandstones, and the fault rocks are fine-grained with clay-rich gouge. The Little Grand Wash fault displaces these rocks approximately 290 m and the Salt Wash graben offsets rocks approximately 130 m; both faults extend at least to the top of the Pennsylvanian Paradox Formation, which contains thick salt horizons 1.5 - 2 km at depth. Well log, geologic surface and geochemical data indicate the CO2 reservoirs and sources have been cut by the faults at depth providing a conduit for the vertical migration of CO2 to the surface, but limited horizontal flow across the fault plane. Three- dimensional flow modals show how the faults damage zones permeability is adjacent to the faults and the leakage though the damage zones is localized near the regional anticlines fold axis. Analysis of the fluids emanating from the faults aims to locate the sources and determine the chemical evolutions of the fluids. δ2H and δ18O isotopic data show that the ground waters are meteoric and have not circulated deeply enough to experience an oxygen-isotope shift. δ13C data and PCO2 values indicate that the gas is external to the ground water systems (i.e., not from soil zone gas or dissolution of carbonate aquifer material alone). 3He/4He ratio 0.30 - 0.31 from springs and geysers indicate that the majority of the gas is crustally derived and contains a minimal component of mantle or magmatic gases. δ13C values of 4 to 5 per mil from the veins indicate the possible carbon sources of dissolution of isotopically heavy marine carbonates or the thermal decarbonization of carbonates. Thus, our conceptual model is that gases from 1.5 km or greater in the basin are migrate upwards along the faults and charge shallower ground water systems, where chemical exchange occurs during discharge at and near surface. The faults have been active since ~42 Ma, corresponding to the rapid uplift of the region. Fault-fluid interactions are likely trigged by salt movement at depth, and also in response to the modern state of stress, in which north-northeast extension of the area is caused by NNE-oriented σ 3, and that the faults may reflect a critcally stressed crust in the region.

Tree-ring 14C links seismic swarm to CO2 spike at Yellowstone, USA

USGS Publications Warehouse

Evans, William C.; Bergfeld, D.; McGeehin, J.P.; King, J.C.; Heasler, H.

2010-01-01

Mechanisms to explain swarms of shallow seismicity and inflation-deflation cycles at Yellowstone caldera (western United States) commonly invoke episodic escape of magma-derived brines or gases from the ductile zone, but no correlative changes in the surface efflux of magmatic constituents have ever been documented. Our analysis of individual growth rings in a tree core from the Mud Volcano thermal area within the caldera links a sharp ~25% drop in 14C to a local seismic swarm in 1978. The implied fivefold increase in CO2 emissions clearly associates swarm seismicity with upflow of magma-derived fluid and shows that pulses of magmatic CO2 can rapidly traverse the 5-kmthick brittle zone, even through Yellowstone's enormous hydrothermal reservoir. The 1978 event predates annual deformation surveys, but recognized connections between subsequent seismic swarms and changes in deformation suggest that CO2 might drive both processes. ?? 2010 Geological Society of America.

Source-constrained retrieval influences the encoding of new information.

PubMed

Danckert, Stacey L; MacLeod, Colin M; Fernandes, Myra A

2011-11-01

Jacoby, Shimizu, Daniels, and Rhodes (Psychonomic Bulletin & Review, 12, 852-857, 2005) showed that new words presented as foils among a list of old words that had been deeply encoded were themselves subsequently better recognized than new words presented as foils among a list of old words that had been shallowly encoded. In Experiment 1, by substituting a deep-versus-shallow imagery manipulation for the levels-of-processing manipulation, we demonstrated that the effect is robust and that it generalizes, also occurring with a different type of encoding. In Experiment 2, we provided more direct evidence for context-related encoding during tests of deeply encoded words, showing enhanced priming for foils presented among deeply encoded targets when participants made the same deep-encoding judgments on those items as had been made on the targets during study. In Experiment 3, we established that the findings from Experiment 2 are restricted to this specific deep judgment task and are not a general consequence of these foils being associated with deeply encoded items. These findings provide support for the source-constrained retrieval hypothesis of Jacoby, Shimizu, Daniels, and Rhodes: New information can be influenced by how surrounding items are encoded and retrieved, as long as the surrounding items recruit a coherent mode of processing.

Root-derived CO2 efflux via xylem stream rivals soil CO2 efflux

Treesearch

Doug P. Aubrey; Robert O. Teskey

2009-01-01

Respiration consumes a large portion of annual gross primary productivity in forest ecosystems and is dominated by belowground metabolism. Here, we present evidence of a previously unaccounted for internal CO2 flux of large magnitude from tree roots through stems. If this pattern is shown to persist over time and in other forests, it suggests...

Kinetic analysis for cyclic CO2 capture using lithium orthosilicate sorbents derived from different silicon precursors.

PubMed

Zhao, Ming; Fan, Hanlu; Yan, Feng; Song, Yinqiang; He, Xu; Memon, Muhammad Zaki; Bhatia, Suresh K; Ji, Guozhao

2018-06-21

A series of Li4SiO4 was synthesized using LiNO3 and six different silicon precursors. The precipitated-silica-derived Li4SiO4 presented the highest CO2 capacity in a 10 h sorption test, and ZSM-5-derived Li4SiO4 demonstrated the most rapid CO2 sorption. The CO2 sorption kinetics predominantly followed the nucleation mode and could be accurately described by the Avrami-Erofeev model. The Avrami-Erofeev model provided an in-depth analysis of correlation between sorption performance and material properties. Both the nucleation speed and nucleation dimensionality affected the overall sorption kinetics. The kinetics and pore-size distribution suggest that the sorption kinetics was dependent on the quantity of ∼4 nm-pores which favors nucleation dimensionality. For the cyclic tests, the precipitated-silica-derived sample presented the poorest performance with the capacity decreasing from 31.33 wt% at the 1st cycle to only 11.52 wt% at the 30th cycle. However, the sample made from fumed silica displayed an opposite trend with the capacity increasing from 19.90 wt% at the 1st cycle to 34.23 wt% at the 30th cycle. The radically distinct behaviour of samples during cycles was on account of the alternation of sorption kinetics. The decrease in ∼4 nm-pores after cycles was responsible for the decrease of nucleation dimensionality for the precipitated-silica-derived sample. The rearrangement during cycles could enrich the pores of ∼4 nm for the fumed silica-derived sample, which improved the nucleation growth, thus enhancing the kinetics with cycles.

Photon-Induced Thermal Desorption of CO from Small Metal-Carbonyl Clusters

NASA Astrophysics Data System (ADS)

Lüttgens, G.; Pontius, N.; Bechthold, P. S.; Neeb, M.; Eberhardt, W.

2002-02-01

Thermal CO desorption from photoexcited free metal-carbonyl clusters has been resolved in real time using two-color pump-probe photoelectron spectroscopy. Sequential energy dissipation steps between the initial photoexcitation and the final desorption event, e.g., electron relaxation and thermalization, have been resolved for Au2(CO)- and Pt2(CO)-5. The desorption rates for the two clusters differ considerably due to the different numbers of vibrational degrees of freedom. The unimolecular CO-desorption thresholds of Au2(CO)- and Pt2(CO)-5 have been approximated by means of a statistical Rice-Ramsperger-Kassel calculation using the experimentally derived desorption rate constants.

Comment on "Defocusing complex short-pulse equation and its multi-dark-soliton solution"

NASA Astrophysics Data System (ADS)

Youssoufa, Saliou; Kuetche, Victor K.; Kofane, Timoleon C.

2017-08-01

In their recent paper, Feng et al. [Phys. Rev. E 93, 052227 (2016), 10.1103/PhysRevE.93.052227] proposed a complex short-pulse equation of both focusing and defocusing types. They studied in detail the defocusing case and derived its multi-dark-soliton solutions. Nonetheless, from a physical viewpoint in order to better and deeply understand their genuine implications, we find it useful to provide a real and proper background for the derivation of the previous evolution system while showing that the expression of the nonlinear electric polarization the above authors used in their scheme is not suitable for getting the defocusing complex short-pulse equation.

Comment on "Defocusing complex short-pulse equation and its multi-dark-soliton solution".

PubMed

Youssoufa, Saliou; Kuetche, Victor K; Kofane, Timoleon C

2017-08-01

In their recent paper, Feng et al. [Phys. Rev. E 93, 052227 (2016)PREHBM2470-004510.1103/PhysRevE.93.052227] proposed a complex short-pulse equation of both focusing and defocusing types. They studied in detail the defocusing case and derived its multi-dark-soliton solutions. Nonetheless, from a physical viewpoint in order to better and deeply understand their genuine implications, we find it useful to provide a real and proper background for the derivation of the previous evolution system while showing that the expression of the nonlinear electric polarization the above authors used in their scheme is not suitable for getting the defocusing complex short-pulse equation.

Rhodium(I)-Catalyzed Ring-Closing Reaction of Allene-Alkene-Alkynes: One-Step Construction of Tricyclo[6.4.0.02,6 ] and Bicyclo[6.3.0] Skeletons from Linear Carbon Chains.

PubMed

Kawaguchi, Yasuaki; Nagata, Asami; Kurokawa, Kei; Yokosawa, Haruna; Mukai, Chisato

2018-05-02

Treatment of dodecatrienyne derivatives with [RhCl(CO) 2 ] 2 in refluxing toluene effected the cycloisomerization to produce tricyclo[6.4.0.0 2,6 ]dodecadienes. The one-carbon shortened undecatrienyne derivatives, however, afforded bicyclo[6.3.0]undecatriene derivatives instead of tricyclic compounds, the latter of which are well known as a basic skeleton of naturally occurring octanoids. On the basis of two experiments with deuterated substrates, a plausible reaction mechanism for the construction of these products was proposed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Human endothelial progenitor cells-derived exosomes accelerate cutaneous wound healing in diabetic rats by promoting endothelial function.

PubMed

Li, Xiaocong; Jiang, Chunyu; Zhao, Jungong

2016-08-01

Wound healing is deeply dependent on neovascularization to restore blood flow. The neovascularization of endothelial progenitor cells (EPCs) through paracrine secretion has been reported in various tissue repair models. Exosomes, key components of cell paracrine mechanism, have been rarely reported in wound healing. Exosomes were isolated from the media of EPCs obtained from human umbilical cord blood. Diabetic rats wound model was established and treated with exosomes. The in vitro effects of exosomes on the proliferation, migration and angiogenic tubule formation of endothelial cells were investigated. We revealed that human umbilical cord blood EPCs derived exosomes transplantation could accelerate cutaneous wound healing in diabetic rats. We also showed that exosomes enhanced the proliferation, migration and tube formation of vascular endothelial cells in vitro. Furthermore, we found that endothelial cells stimulated with these exosomes would increase expression of angiogenesis-related molecules, including FGF-1, VEGFA, VEGFR-2, ANG-1, E-selectin, CXCL-16, eNOS and IL-8. Taken together, our findings indicated that EPCs-derived exosomes facilitate wound healing by positively modulating vascular endothelial cells function. Copyright © 2016 Elsevier Inc. All rights reserved.

Which plant trait explains the variations in relative growth rate and its response to elevated carbon dioxide concentration among Arabidopsis thaliana ecotypes derived from a variety of habitats?

PubMed

Oguchi, Riichi; Ozaki, Hiroshi; Hanada, Kousuke; Hikosaka, Kouki

2016-03-01

Elevated atmospheric carbon dioxide (CO2) concentration ([CO2]) enhances plant growth, but this enhancement varies considerably. It is still uncertain which plant traits are quantitatively related to the variation in plant growth. To identify the traits responsible, we developed a growth analysis model that included primary parameters associated with morphology, nitrogen (N) use, and leaf and root activities. We analysed the vegetative growth of 44 ecotypes of Arabidopsis thaliana L. grown at ambient and elevated [CO2] (800 μmol mol(-1)). The 44 ecotypes were selected such that they were derived from various altitudes and latitudes. Relative growth rate (RGR; growth rate per unit plant mass) and its response to [CO2] varied by 1.5- and 1.7-fold among ecotypes, respectively. The variation in RGR at both [CO2]s was mainly explained by the variation in leaf N productivity (LNP; growth rate per leaf N),which was strongly related to photosynthetic N use efficiency (PNUE). The variation in the response of RGR to [CO2] was also explained by the variation in the response of LNP to [CO2]. Genomic analyses indicated that there was no phylogenetic constraint on inter-ecotype variation in the CO2 response of RGR or LNP. We conclude that the significant variation in plant growth and its response to [CO2] among ecotypes reflects the variation in N use for photosynthesis among ecotypes, and that the response of PNUE to CO2 is an important target for predicting and/or breeding plants that have high growth rates at elevated [CO2].

Hierarchical Co-based Porous Layered Double Hydroxide Arrays Derived via Alkali Etching for High-performance Supercapacitors

NASA Astrophysics Data System (ADS)

Abushrenta, Nasser; Wu, Xiaochao; Wang, Junnan; Liu, Junfeng; Sun, Xiaoming

2015-08-01

Hierarchical nanoarchitecture and porous structure can both provide advantages for improving the electrochemical performance in energy storage electrodes. Here we report a novel strategy to synthesize new electrode materials, hierarchical Co-based porous layered double hydroxide (PLDH) arrays derived via alkali etching from Co(OH)2@CoAl LDH nanoarrays. This structure not only has the benefits of hierarchical nanoarrays including short ion diffusion path and good charge transport, but also possesses a large contact surface area owing to its porous structure which lead to a high specific capacitance (23.75 F cm-2 or 1734 F g-1 at 5 mA cm-2) and excellent cycling performance (over 85% after 5000 cycles). The enhanced electrode material is a promising candidate for supercapacitors in future application.

Hierarchical Co-based Porous Layered Double Hydroxide Arrays Derived via Alkali Etching for High-performance Supercapacitors

PubMed Central

Abushrenta, Nasser; Wu, Xiaochao; Wang, Junnan; Liu, Junfeng; Sun, Xiaoming

2015-01-01

Hierarchical nanoarchitecture and porous structure can both provide advantages for improving the electrochemical performance in energy storage electrodes. Here we report a novel strategy to synthesize new electrode materials, hierarchical Co-based porous layered double hydroxide (PLDH) arrays derived via alkali etching from Co(OH)2@CoAl LDH nanoarrays. This structure not only has the benefits of hierarchical nanoarrays including short ion diffusion path and good charge transport, but also possesses a large contact surface area owing to its porous structure which lead to a high specific capacitance (23.75 F cm−2 or 1734 F g−1 at 5 mA cm−2) and excellent cycling performance (over 85% after 5000 cycles). The enhanced electrode material is a promising candidate for supercapacitors in future application. PMID:26278334

Asymmetric supercapacitors utilizing highly porous metal-organic framework derived Co3O4 nanosheets grown on Ni foam and polyaniline hydrogel derived N-doped nanocarbon electrode materials

NASA Astrophysics Data System (ADS)

Fan, Xin; Chen, Weiliang; Pang, Shuhua; Lu, Wei; Zhao, Yu; Liu, Zheng; Fang, Dong

2017-12-01

In the present work, asymmetric supercapacitors (ASCs) are assembled using a highly conductive N-doped nanocarbon (NDC) material derived from a polyaniline hydrogel as a cathode, and Ni foam covered with flower-like Co3O4 nanosheets (Co3O4-Ni) prepared from a zeolitic imidazolate metal-organic framework as a single precursor serves as a high gravimetric capacitance anode. At a current of 0.2 A g-1, the Co3O4-Ni electrode provides a gravimetric capacitance of 637.7 F g-1, and the NDC electrode provides a gravimetric capacitance of 359.6 F g-1. The ASC assembled with an optimal active material loading operates within a wide potential window of 0-1.1 V, and provides a high areal capacitance of 25.7 mF cm-2. The proposed ASC represents a promising strategy for designing high-performance supercapacitors.

Synthesis, spectral, and structural studies of porphyrins having sterically hindered [η(5)-CpCo(η(4)-C4Ph4)] cobalt sandwich units at the meso positions.

PubMed

Keshav, Karunesh; Kumar, Dheeraj; Elias, Anil J

2013-11-04

Synthesis, spectral, and structural studies of the first examples of porphyrins substituted at the meso positions with sterically hindered η(5)-CpCo(η(4)-C4Ph4) cobalt sandwich units are described. The novel dipyrromethane derived cobalt sandwich compound {η(5)-[(C4H4N)2CH]C5H4}Co(η(4)-C4Ph4) 1, as well as its parent aldehyde, η(5)-[C5H4(CHO)]Co(η(4)-C4Ph4), were used in the synthesis of porphyrins having one or two η(5)-CpCo(η(4)-C4Ph4) groups at their meso positions. 1,9-Diformyldipyrromethane derived η(5)-CpCo(η(4)-C4Ph4) 2 was synthesized using dipyrromethane 1 under Vilsmeier conditions. A reaction of 2 with unsubstituted dipyrromethane under basic conditions in the presence of Pd(C6H5CN)2Cl2 yielded an A-type palladium coordinated porphyrin 3 [where A = η(5)-CpCo(η(4)-C4Ph4)]. A similar reaction of 2 with meso aryl and ferrocenyl-substituted dipyrromethanes yielded trans-AB type palladium coordinated porphyrins 4-6 [where A = η(5)-CpCo(η(4)-C4Ph4) and B = 4-tert-butylphenyl 4, ferrocenyl 5, and pentafluorophenyl 6]. Reactions of 2 with 5-ferrocenyl dipyrromethane under the same reaction conditions in the presence of Ni(acac)2 and Zn(OAc)2 gave the trimetallic nickel(II) and zinc(II) complexed trans-AB type porphyrins 7 and 8 having both cobalt and iron sandwich units at the meso positions. Crystal structure of the Pd(II) porphyrin 5 and nickel(II) porphyrin 7 showed nonplanar structures having distinct ruffle type distortion of the porphyrin ring. Demetalation of the zinc(II) trans-AB type porphyrin 8 in the presence of trifluoroacetic acid gave the metal free base porphyrin 9. Reactions of the cobalt sandwich aldehyde [(η(5)-C5H4(CHO)]Co(η(4)-C4Ph4) with sterically hindered dipyrromethane derivatives under acid-catalyzed condensation reactions gave trans-A2B2 type porphyrins [where A = η(5)-CpCo(η(4)-C4Ph4) and B = pentafluorophenyl, 10 mesityl 11]. In contrast, reactions of [η(5)-C5H4(CHO)]Co(η(4)-C4Ph4) with sterically unhindered meso-4-tert-butylphenyl dipyrromethane resulted in both AB3 12 and cis-A2B2 13 type porphyrins [where A = η(5)-CpCo(η(4)-C4Ph4) and B = (4-tert-butylphenyl] as a result of scrambling. The new porphyrin derivatives have been structurally characterized, and their spectral and electrochemical features were determined.

Atmospheric Airborne Pressure Measurements Using the Oxygen A Band for the ASCENDS Mission

NASA Technical Reports Server (NTRS)

Riris, Haris; Rodriguez, Mike; Stephen, Mark; Hasselbrack, William; Allan, Graham; Mao, Jianping; Kawa, Stephen R.; Weaver, Clark J.

2010-01-01

We report on airborne atmospheric pressure measurements using new fiber-based laser technology and the oxygen A-band at 765 nm. Remote measurements of atmospheric temperature and pressure are required for a number of NASA Earth science missions and specifically for the Active Sensing of CO2 Emissions Over Nights, Days, and Seasons (ASCENDS) mission. Accurate measurements of tropospheric CO2 on a global scale are very important in order to better understand its sources and sinks and to improve predictions on any future climate change. The ultimate goal of a CO2 remote sensing mission, such as ASCENDS, is to derive the CO2 concentration in the atmosphere in terms of mole fraction in unit of parts-per-million (ppmv) with regard to dry air. Therefore, both CO2 and the dry air number of molecules in the atmosphere are needed in deriving this quantity. O2 is a stable molecule and uniformly mixed in the atmosphere. Measuring the O2 absorption in the atmosphere can thus be used to infer the dry air number of molecules and then used to calculate CO2 concentration. With the knowledge of atmospheric water vapor, we can then estimate the total surface pressure needed for CO2 retrievals. Our work, funded by the ESTO IIP program, uses fiber optic technology and non-linear optics to generate 765 nm laser radiation coincident with the Oxygen A-band. Our pulsed, time gated technique uses several on- and off-line wavelengths tuned to the O2 absorption line. The choice of wavelengths allows us to measure the pressure by using two adjacent O2 absorptions in the Oxygen A-band. Our retrieval algorithm fits the O2 lineshapes and derives the pressure. Our measurements compare favorably with a local weather monitor mounted outside our laboratory and a local weather station.

Atmospheric Airborne Pressure Measurements Using the Oxygen A Band for the ASCENDS Mission

NASA Technical Reports Server (NTRS)

Riris, Haris; Rodriguez, Mike; Stephen, Mark; Hasselbrack, William; Allan, Graham; Mao, Jiamping,; Kawa, Stephan R.; Weaver, Clark J.

2011-01-01

We report on airborne atmospheric pressure measurements using new fiber-based laser technology and the oxygen A-band at 765 nm. Remote measurements of atmospheric temperature and pressure are required for a number of NASA Earth science missions and specifically for the Active Sensing of CO2 Emissions Over Nights, Days, and Seasons (ASCENDS) mission. Accurate measurements of tropospheric CO2 on a global scale are very important in order to better understand its sources and sinks and to improve predictions on any future climate change. The ultimate goal of a CO2 remote sensing mission, such as ASCENDS, is to derive the CO2 concentration in the atmosphere in terms of mole fraction in unit of parts-per-million (ppmv) with regard to dry air. Therefore, both CO2 and the dry air number of molecules in the atmosphere are needed in deriving this quantity. O2 is a stable molecule and uniformly mixed in the atmosphere. Measuring the O2 absorption in the atmosphere can thus be used to infer the dry air number of molecules and then used to calculate CO2 concentration. With the knowledge of atmospheric water vapor, we can then estimate the total surface pressure needed for CO2 retrievals. Our work, funded by the ESTO IIP program, uses fiber optic technology and non-linear optics to generate 765 nm laser radiation coincident with the Oxygen A-band. Our pulsed, time gated technique uses several on- and off-line wavelengths tuned to the O2 absorption line. The choice of wavelengths allows us to measure the pressure by using two adjacent O2 absorptions in the Oxygen A-band. Our retrieval algorithm fits the O2 lineshapes and derives the pressure. Our measurements compare favorably with a local weather monitor mounted outside our laboratory and a local weather station.

Two isomorphous Co(ii) coordination polymers based on new α,α-disubstituted derivatives of zoledronic acid: synthesis, structures and properties.

PubMed

Rojek, Tomasz; Goldeman, Waldemar; Slepokura, Katarzyna; Duczmal, Marek; Wojciechowska, Agnieszka; Matczak-Jon, Ewa

2017-05-30

Two novel α,α-disubstituted derivatives of zoledronic acid, namely 1-hydroxy-2-(1H-imidazol-1-yl)-2-methylpropylidene-1,1-diphosphonic acid (H 4 L1) and 1-hydroxy-2-[1-(1H-imidazol-1-yl)cyclopropyl]ethylidene-1,1-diphosphonic acid (H 4 L2) were synthesized and structurally characterized by single-crystal X-ray diffraction. The reaction of cobalt acetate with H 4 L1 and H 4 L2 carried out under hydrothermal conditions afforded two isomorphous Co 3 (HL1) 2 (H 2 O) 6 ·6H 2 O (1a) and Co 3 (HL2) 2 (H 2 O) 6 ·6H 2 O (2a) complexes. Both compounds are characterized by means of X-ray crystallography, IR and NIR-Vis-UV spectroscopic methods. Furthermore, their magnetic properties and thermal stabilities are reported. The crystals of 1a and 2a feature infinite 1D polymeric chains built from alternately arranged dinuclear [Co2(HL1/HL2)(H 2 O) 2 ] 2 units and {Co1O 6 } octahedra running along the [1[combining macron]10] crystallographic direction. In both compounds, crystallographically distinct Co1 and Co2 atoms are six-coordinated. As is reflected in T values (T - index of tetragonality), the coordination environment of Co1 generates a slightly elongated octahedron (T = 0.94), whereas a slightly compressed octahedron (T = 1.06 for 1a and 1.05 for 2a) is formed around Co2. An assumption that the d-d type absorption is mainly attributed to the inversion related Co2 centers, whose population is two times higher than that of Co1, afforded a good correlation between calculated transition energies and experimental NIR-Vis-UV spectra. The magnetic susceptibility measurements analyzed in terms of a spin-3/2 Heisenberg trimer chain revealed that Co1Co2 interactions within the trimer are antiferromagnetic whereas Co2Co2 intertrimer interactions are ferromagnetic.

Can Nocturnal Cold Air Drainage be Used to Monitor Ecosystem Function?

NASA Astrophysics Data System (ADS)

Pypker, T. G.; Unsworth, M. H.; Sulzman, E. W.; Lamb, B.; Allwine, G.; Mix, A. C.; Bond, B. J.

2005-12-01

Ecosystem carbon dynamics in flat, uniform terrain are commonly studied using standard micrometeorological techniques such as eddy covariance or gradient methods. But many of the world's ecosystems are in complex topography that is inappropriate for these methods. Nocturnal cold air drainage commonly occurs in mountainous terrain. This drainage provides an opportunity to monitor ecosystem carbon dynamics because as air flows downhill through a watershed, it collects respired CO2 from the soil and vegetation. If the nocturnal drainage can be treated as a river of air flowing down a valley, sampling this air from a tower at the base of a watershed could provide an estimate of ecosystem respiration and the 12C/13C ratio. To interpret the measured CO2 and the 12C/13C ratio, the characteristics of the drainage and the footprint (source area) of air passing the tower must be understood. To explore the potential of using nocturnal cold air drainage we built a 37 m tower at the base of a deeply incised watershed of ~40 y-old Douglas-fir in the Oregon Cascades. At various heights on the tower we monitored air temperature, wind speed/direction, and the CO2 concentration and 12C/13C isotopic ratio with a combination of thermistors, sonic anemometers (2-D and 3-D) and a CO2 profile system. The temperature gradient along the axis of the watershed was monitored by 30 temperature sensors from the base to the top of the watershed. The maximum drainage windspeeds on the tower occurred near sunset and, unlike past reports of cold air drainage, this drainage was very deep (> 37 m). The drainage became well mixed when the vertical profile of potential temperature became isothermal. It remained well mixed through the night into the early morning. The drainage occurred on most summer nights and typically provided a range of CO2 (> 60 ppm) sufficient for "Keeling plot" analysis. In September 2005, we released a tracer in the watershed (SF6) to determine the varying footprint size of the tower. The footprint size and windspeed varied throughout the night, resulting in a change in the CO2 concentration at the tower. Further analysis will determine how the CO2 passing the tower is altered by entrainment of the air overlying the drainage and the change in the source area of the drainage.

First images of a possible CO(+)-tail of comet P/Schwassmann-Wachmann 1 observed against the dust coma background

NASA Technical Reports Server (NTRS)

Jockers, Klaus; Bonev, T.; Ivanova, Violeta; Rauer, H.

1992-01-01

Comet P/Schwassmann-Wachmann 1 was observed with the 2m-Ritchey-Cretien Telescope of the Bulgarian National Observatory, Rozhen, Bulgaria, using the CCD-camera and focal reducer of the Max-Planck-Institute for Aeronomy. Images were taken in a red continuum window and in the 2-0 A(exp 2)Pi - X(exp 2)Sigma(+) band of CO(+) located in the blue part of the spectrum. The red images reveal an extended dust coma. From a comparison of the red and blue images a dust reddening of 13.2 percent per 1000 A is derived. At 642 nm the magnitude of the comet with a square diaphragm of 4.5 arcsec is 16.6. The blue images, taken in the CO(+) band, show a significantly different brightness distribution which is interpreted as presence of a CO(+) coma and tail superimposed on the continuum. A column density of several 10(exp 10) CO(+) molecules cm(exp -2) is derived. The tail thickness of 10(exp 5) km is unexpectedly small. We estimate the CO(+) production rate to about 6 x 10(exp 26) CO(+) particles s(exp -1). This value does not support the idea that the outbursts of this comet are caused by crystallization of amorphous water ice.

Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free, zinc(II), copper(II) and cobalt(II) phthalocyanines

NASA Astrophysics Data System (ADS)

Demirbaş, Ümit; Akçay, Hakkı Türker; Koca, Atıf; Kantekin, Halit

2017-08-01

In this study novel peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free phthalocyanine (4) and its zinc(II) (5), copper(II) (6) and cobalt(II) (7) derivatives were synthesized and characterized by a combination of various spectroscopic techniques such as FT-IR, 1H-NMR, UV-vis and MALDI-TOF mass. Electrochemical characterizations of metallo-phthalocyanine complexes were conducted by voltammetric and in situ spectroelectrochemical measurements. CoIIPc went [CoIIPc-2]/[CoIPc-2]1-, [CoIPc-2]1-/[CoIPc-3]2-, [CoIPc-3]2-/[CoIPc-4]3- and [CoIIPc-2]/[CoIIPc-2]1+ reduction and oxidation processes respectively. Differently ZnIIPc only showed four ligand-based reductions and two ligand based oxidation processes.

A survey of the cold molecular gas in gravitationally lensed star-forming galaxies at z > 2

NASA Astrophysics Data System (ADS)

Aravena, M.; Spilker, J. S.; Bethermin, M.; Bothwell, M.; Chapman, S. C.; de Breuck, C.; Furstenau, R. M.; Gónzalez-López, J.; Greve, T. R.; Litke, K.; Ma, J.; Malkan, M.; Marrone, D. P.; Murphy, E. J.; Stark, A.; Strandet, M.; Vieira, J. D.; Weiss, A.; Welikala, N.; Wong, G. F.; Collier, J. D.

2016-04-01

Using the Australia Telescope Compact Array, we conducted a survey of CO J = 1 - 0 and J = 2 - 1 line emission towards strongly lensed high-redshift dusty star-forming galaxies (DSFGs) previously discovered with the South Pole Telescope (SPT). Our sample comprises 17 sources that had CO-based spectroscopic redshifts obtained with the Atacama Large Millimeter/submillimeter Array and the Atacama Pathfinder Experiment. We detect all sources with known redshifts in either CO J = 1 - 0 or J = 2 - 1. 12 sources are detected in the 7-mm continuum. The derived CO luminosities imply gas masses in the range (0.5-11) × 1010 M⊙ and gas depletion time-scales tdep < 200 Myr, using a CO to gas mass conversion factor αCO = 0.8 M⊙ (K km s-1 pc2)-1. Combining the CO luminosities and dust masses, along with a fixed gas-to-dust ratio, we derive αCO factors in the range 0.4-1.8 M⊙ (K km s-1 pc2)-1, similar to what is found in other starbursting systems. We find small scatter in αCO values within the sample, even though inherent variations in the spatial distribution of dust and gas in individual cases could bias the dust-based αCO estimates. We find that lensing magnification factors based on the CO linewidth to luminosity relation (μCO) are highly unreliable, but particularly when μ < 5. Finally, comparison of the gas and dynamical masses suggest that the average molecular gas fraction stays relatively constant at z = 2-5 in the SPT DSFG sample.

Modelling urban δ13C variations in the Greater Toronto Area

NASA Astrophysics Data System (ADS)

Pugliese, S.; Vogel, F. R.; Murphy, J. G.; Worthy, D. E. J.; Zhang, J.; Zheng, Q.; Moran, M. D.

2015-12-01

Even in urbanized regions, carbon dioxide (CO2) emissions are derived from a variety of biogenic and anthropogenic sources and are influenced by atmospheric transport across borders. As policies are introduced to reduce the emission of CO2, there is a need for independent verification of emissions reporting. In this work, we aim to use carbon isotope (13CO2 and 12CO2) simulations in combination with atmospheric measurements to distinguish between CO2 sources in the Greater Toronto Area (GTA), Canada. This is being done by developing an urban δ13C framework based on existing CO2 emission data and forward modelling using a chemistry transport model, CHIMERE. The framework is designed to use region specific δ13C signatures of the dominant CO2 sources together with a CO2 inventory at a fine spatial and temporal resolution; the product is compared against highly accurate 13CO2 and 12CO2 ambient data. The strength of this framework is its potential to estimate both locally produced and regionally transported CO­2. Locally, anthropogenic CO­2 in urban areas is often derived from natural gas combustion (for heating) and gasoline/diesel combustion (for transportation); the isotopic signatures of these processes are significantly different (approximately d13CVPDB = -40 ‰ and -26 ‰ respectively) and can be used to infer their relative contributions. Furthermore, the contribution of transported CO2 can also be estimated as nearby regions often rely on other sources of heating (e.g. coal combustion), which has a very different signature (approximately d13CVPDB = -23 ‰). We present an analysis of the GTA in contrast to Paris, France where atmospheric observations are also available and 13CO2 has been studied. Utilizing our δ13C framework and differences in sectoral isotopic signatures, we quantify the relative contribution of CO2 sources on the overall measured concentration and assess the ability of this framework as a tool for tracing the evolution of sector-specific emissions.

Reproducibility of the exponential rise technique of CO(2) rebreathing for measuring P(v)CO(2) and C(v)CO(2 )to non-invasively estimate cardiac output during incremental, maximal treadmill exercise.

PubMed

Cade, W Todd; Nabar, Sharmila R; Keyser, Randall E

2004-05-01

The purpose of this study was to determine the reproducibility of the indirect Fick method for the measurement of mixed venous carbon dioxide partial pressure (P(v)CO(2)) and venous carbon dioxide content (C(v)CO(2)) for estimation of cardiac output (Q(c)), using the exponential rise method of carbon dioxide rebreathing, during non-steady-state treadmill exercise. Ten healthy participants (eight female and two male) performed three incremental, maximal exercise treadmill tests to exhaustion within 1 week. Non-invasive Q(c) measurements were evaluated at rest, during each 3-min stage, and at peak exercise, across three identical treadmill tests, using the exponential rise technique for measuring mixed venous PCO(2) and CCO(2) and estimating venous-arterio carbon dioxide content difference (C(v-a)CO(2)). Measurements were divided into measured or estimated variables [heart rate (HR), oxygen consumption (VO(2)), volume of expired carbon dioxide (VCO(2)), end-tidal carbon dioxide (P(ET)CO(2)), arterial carbon dioxide partial pressure (P(a)CO(2)), venous carbon dioxide partial pressure ( P(v)CO(2)), and C(v-a)CO(2)] and cardiorespiratory variables derived from the measured variables [Q(c), stroke volume (V(s)), and arteriovenous oxygen difference ( C(a-v)O(2))]. In general, the derived cardiorespiratory variables demonstrated acceptable (R=0.61) to high (R>0.80) reproducibility, especially at higher intensities and peak exercise. Measured variables, excluding P(a)CO(2) and C(v-a)CO(2), also demonstrated acceptable (R=0.6 to 0.79) to high reliability. The current study demonstrated acceptable to high reproducibility of the exponential rise indirect Fick method in measurement of mixed venous PCO(2) and CCO(2) for estimation of Q(c) during incremental treadmill exercise testing, especially at high-intensity and peak exercise.

Decellularized heart ECM hydrogel using supercritical carbon dioxide for improved angiogenesis.

PubMed

Seo, Yoojin; Jung, Youngmee; Kim, Soo Hyun

2018-02-01

Initial angiogenesis within the first 3 days is critical for healing ischemic diseases such as myocardial infarction. Recently, decellularized extracellular matrix (dECM) has been reported to provide tissue-derived ECM components and can be used as a scaffold for cell delivery for angiogenesis in tissue engineering. Decellularization by various detergents such as sodium dodecyl sulfate (SDS) and triton X-100 can remove the cell nuclei in tissue organs. However, this leads to ECM structure denaturation, decreased presence of various ECM proteins and cytokines, and loss of mechanical properties. To overcome these limitations, in this study, we developed a supercritical carbon dioxide and ethanol co-solvent (scCO 2 -EtOH) decellularization method, which is a detergent-free system that prevents ECM structure disruption and retains various angiogenic proteins in the heart dECM, and tested on rat heart tissues. The heart tissue was placed into the scCO 2 reactor and decellularized at 37 °C and 350 bar. After scCO 2 -EtOH treatment, the effects were evaluated by DNA, collagen, and glycosaminoglycan (GAG) quantification and hematoxylin and eosin and immunofluorescence staining to determine the absence of nucleic acids and preservation of heart ECM components. Similar to the native group, the scCO 2 -EtOH group contained more ECM components such as collagen, GAGs, collagen I, laminin, and fibronectin and angiogenic factors including vascular endothelial growth factor, fibroblast growth factor, and platelet-derived growth factor and others in comparison to the detergent group. In addition, to estimate angiogenesis of the dECM hydrogels, the neutralized dECM solution was injected in a rat subcutaneous layer (n = 6 in each group: collagen, scCO 2 -EOH, and detergent group), after which the solution naturally formed gelation in the subcutaneous layer. After 3 days, the gels were harvested and estimated by immunofluorescence staining and the ImageJ program for angiogenesis analysis. Consequently, blood vessel formation and density of vWF and α-SMA in the scCO 2 -EtOH group were significantly greater than that in the collagen group. Here we suggest that heart-derived decellularized extracellular matrix (dECM) with scCO 2 -EtOH treatment is a highly promising angiogenic material for healing in ischemic disease. Supercritical carbon dioxide (scCO 2 ) in a supercritical phase has low viscosity and high diffusivity between gas and liquid properties and is known to be affordable, non-toxic, and eco-friendly. Therefore, scCO 2 extraction technology has been extensively used in commercial and industrial fields. Recently, decellularized extracellular matrix (dECM) was applied to tissue engineering and regenerative medicine as a scaffold, therapeutic material, and bio-ink for 3D printing. Moreover, the general decellularization method using detergents has limitations including eliminating tissue-derived ECM components and disrupting their structures after decellularization. To overcome these limitations, heart tissues were treated with scCO 2 -EtOH for decellularization, resulting in preserving of tissue due to the various ECM and angiogenic factors derived. In addition, initiation of angiogenesis was highly induced even after 3 days of injection. Copyright © 2017. Published by Elsevier Ltd.

Study of the natural occurrence of T-2 and HT-2 toxins and their glucosyl derivatives from field barley to malt by high-resolution Orbitrap mass spectrometry

USDA-ARS?s Scientific Manuscript database

This paper reports a new method for the determination of T-2 and HT-2 toxins and their glucosylated derivatives in cereals, and some survey data aimed at obtaining more comprehensive information on the co-occurrence of T-2 and HT-2 toxins and their glucosylated derivatives in naturally contaminated ...

Rhenium(I)-based Double-heterostranded Helicates.

PubMed

Saxena, Priya; Shankar, Bhaskaran; Sathyanarayana, Arruri; Prabusankar, Ganesan; Sathiyendiran, Malaichamy

2015-01-01

Rhenium(I)-based supramolecular coordination complexes were obtained using Re2(CO)10, (2-hydroxyphenyl)benzimidazole-derived bis-chelating N∩O donors and a benzimidazolyl-derived ditopic monodentate N-donor possessing Troger's base spacer in a one-pot approach.

Atmospheric effects on the mapping of Martian thermal inertia and thermally derived albedo

NASA Technical Reports Server (NTRS)

Hayashi, Joan N.; Jakosky, Bruce M.; Haberle, Robert M.

1995-01-01

We examine the effects of a dusty CO2 atmosphere on the thermal inertia and thermally derived albedo of Mars and we present a new map of thermal inertias. This new map was produced using a coupled surface atmosphere (CSA) model, dust opacities from Viking infrared thermal mapper (IRTM) data, and CO2 columns based on topography. The CSA model thermal inertias are smaller than the 2% model thermal inertias, with the difference largest at large thermal inertia. Although the difference between the thermal inertias obtained with the two models is moderate for much of the region studied, it is largest in regions of either high dust opacity or of topographic lows, including the Viking Lander 1 site and some geologically interesting regions. The CSA model thermally derived albedos do not acurately predict the IRTM measured albedos and are very similar to the thermally derived albedos obtained with models making the 2% assumption.

Synergistic effects in ambiphilic phosphino-borane catalysts for the hydroboration of CO2.

PubMed

Tlili, Anis; Voituriez, Arnaud; Marinetti, Angela; Thuéry, Pierre; Cantat, Thibault

2016-06-18

The benefit of combining both a Lewis acid and a Lewis base in a catalytic system has been established for the hydroboration of CO2, using ferrocene-based phosphine, borane and phosphino-borane derivatives.

Controls of streamwater dissolved inorganic carbon dynamics in a forested watershed

USGS Publications Warehouse

Finlay, J.C.

2003-01-01

I investigated controls of stream dissolved inorganic carbon (DIC) sources and cycling along a stream size and productivity gradient in a temperate forested watershed in northern California. Dissolved CO2 (CO2 (aq)) dynamics in heavily shaded streams contrasted strongly with those of larger, open canopied sites. In streams with canopy cover > 97%, CO2 (aq) was highest during baseflow periods (up to 540 ??M) and was negatively related to discharge. Effects of algal photosynthesis on CO2 (aq) were minimal and stream CO2 (aq) was primarily controlled by groundwater CO2 (aq) inputs and degassing losses to the atmosphere. In contrast to the small streams. CO2 (aq) in larger, open-canopied streams was often below atmospheric levels at midday during baseflow and was positively related to discharge. Here, stream CO2 (aq) was strongly influenced by the balance between autotrophic and heterotrophic processes. Dynamics of HCO3- were less complex. HCO3- and Ca2+ were positively correlated, negatively related to discharge, and showed no pattern with stream size. Stable carbon isotope ratios of DIC (i.e. ??13C DIC) increased with stream size and discharge, indicating contrasting sources of DIC to streams and rivers. During summer baseflows, ??13C DIC were 13C-depleted in the smallest streams (minimum of -17.7???) due to the influence of CO2 (aq) derived from microbial respiration and HCO3- derived from carbonate weathering. ??13C DIC were higher (up to -6.6???) in the larger streams and rivers due to invasion of atmospheric CO2 enhanced by algal CO2 (aq) uptake. While small streams were influenced by groundwater inputs, patterns in CO2 (aq) and evidence from stable isotopes demonstrate the strong influence of stream metabolism and CO2 exchange with the atmosphere on stream and river carbon cycles.

Structural Basis for Substrate Fatty Acyl Chain Specificity

PubMed Central

McAndrew, Ryan P.; Wang, Yudong; Mohsen, Al-Walid; He, Miao; Vockley, Jerry; Kim, Jung-Ja P.

2008-01-01

Very-long-chain acyl-CoA dehydrogenase (VLCAD) is a member of the family of acyl-CoA dehydrogenases (ACADs). Unlike the other ACADs, which are soluble homotetramers, VLCAD is a homodimer associated with the mitochondrial membrane. VLCAD also possesses an additional 180 residues in the C terminus that are not present in the other ACADs. We have determined the crystal structure of VLCAD complexed with myristoyl-CoA, obtained by co-crystallization, to 1.91-Å resolution. The overall fold of the N-terminal ∼400 residues of VLCAD is similar to that of the soluble ACADs including medium-chain acyl-CoA dehydrogenase (MCAD). The novel C-terminal domain forms an α-helical bundle that is positioned perpendicular to the two N-terminal helical domains. The fatty acyl moiety of the bound substrate/product is deeply imbedded inside the protein; however, the adenosine pyrophosphate portion of the C14-CoA ligand is disordered because of partial hydrolysis of the thioester bond and high mobility of the CoA moiety. The location of Glu-422 with respect to the C2-C3 of the bound ligand and FAD confirms Glu-422 to be the catalytic base. In MCAD, Gln-95 and Glu-99 form the base of the substrate binding cavity. In VLCAD, these residues are glycines (Gly-175 and Gly-178), allowing the binding channel to extend for an additional 12Å and permitting substrate acyl chain lengths as long as 24 carbons to bind. VLCAD deficiency is among the more common defects of mitochondrial β-oxidation and, if left undiagnosed, can be fatal. This structure allows us to gain insight into how a variant VLCAD genotype results in a clinical phenotype. PMID:18227065

The Derivation Of A CO2 Fugacity Climatology From SOCAT's Global In SITU Data

NASA Astrophysics Data System (ADS)

Goddijn-Murphy, L. M.; Woolf, D. K.; Land, P. E.; Shutler, J. D.

2013-12-01

The Surface Ocean CO2 Atlas (SOCAT) has made millions of global underway sea surface measurements of CO2 publicly available, all in a uniform format and presented as fugacity, fCO2. However, these fCO2 values are valid strictly only for the instantaneous temperature at measurement and are not ideal for climatology. We recomputed these fCO2 values for the measurement month to be applicable to climatological sea surface temperatures, extrapolated to reference year 2010. The data were then spatially interpolated on a 1°×1° grid of the global oceans to produce 12 monthly fCO2 distributions. Our climatology data will be shared with the science community.

Use of wastewater treatment plant biogas for the operation of Solid Oxide Fuel Cells (SOFCs).

PubMed

Lackey, Jillian; Champagne, Pascale; Peppley, Brant

2017-12-01

Solid Oxide Fuel Cells (SOFCs) perform well on light hydrocarbon fuels, and the use of biogas derived from the anaerobic digestion (AD) of municipal wastewater sludges could provide an opportunity for the CH 4 produced to be used as a renewable fuel. Greenhouse gas (GHG), NO x , SO x , and hydrocarbon pollutant emissions would also be reduced. In this study, SOFCs were operated on AD derived biogas. Initially, different H 2 dilutions were tested (N 2 , Ar, CO 2 ) to examine the performance of tubular SOFCs. With inert gases as diluents, a decrease in cell performance was observed, however, the use of CO 2 led to a higher decrease in performance as it promoted the reverse water-gas shift (WGS) reaction, reducing the H 2 partial pressure in the gas mixture. A model was developed to predict system efficiency and GHG emissions. A higher electrical system efficiency was noted for a steam:carbon ratio of 2 compared to 1 due to the increased H 2 partial pressure in the reformate resulting from higher H 2 O concentration. Reductions in GHG emissions were estimated at 2400 tonnes CO 2 , 60 kg CH 4 and 18 kg N 2 O. SOFCs were also tested using a simulated biogas reformate mixture (66.7% H 2 , 16.1% CO, 16.5% CO 2 , 0.7% N 2 , humidified to 2.3 or 20 mol% H 2 O). Higher humidification yielded better performance as the WGS reaction produced more H 2 with additional H 2 O. It was concluded that AD-derived biogas, when cleaned to remove H 2 S, Si compounds, halides and other contaminants, could be reformed to provide a clean, renewable fuel for SOFCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

A contribution to the rational design of Ru(CO)3Cl2L complexes for in vivo delivery of CO.

PubMed

Seixas, João D; Santos, Marino F A; Mukhopadhyay, Abhik; Coelho, Ana C; Reis, Patrícia M; Veiros, Luís F; Marques, Ana R; Penacho, Nuno; Gonçalves, Ana M L; Romão, Maria J; Bernardes, Gonçalo J L; Santos-Silva, Teresa; Romão, Carlos C

2015-03-21

A few ruthenium based metal carbonyl complexes, e.g. CORM-2 and CORM-3, have therapeutic activity attributed to their ability to deliver CO to biological targets. In this work, a series of related complexes with the formula [Ru(CO)3Cl2L] (L = DMSO (3), L-H3CSO(CH2)2CH(NH2)CO2H) (6a); D,L-H3CSO(CH2)2CH(NH2)CO2H (6b); 3-NC5H4(CH2)2SO3Na (7); 4-NC5H4(CH2)2SO3Na (8); PTA (9); DAPTA (10); H3CS(CH2)2CH(OH)CO2H (11); CNCMe2CO2Me (12); CNCMeEtCO2Me (13); CN(c-C3H4)CO2Et) (14)) were designed, synthesized and studied. The effects of L on their stability, CO release profile, cytotoxicity and anti-inflammatory properties are described. The stability in aqueous solution depends on the nature of L as shown using HPLC and LC-MS studies. The isocyanide derivatives are the least stable complexes, and the S-bound methionine oxide derivative is the more stable one. The complexes do not release CO gas to the headspace, but release CO2 instead. X-ray diffraction of crystals of the model protein Hen Egg White Lysozyme soaked with 6b (4UWN) and 8 (4UWN) shows the addition of Ru(II)(CO)(H2O)4 at the His15 binding site. Soakings with 7(4UWN) produced the metallacarboxylate [Ru(COOH)(CO)(H2O)3](+) bound to the His15 site. The aqueous chemistry of these complexes is governed by the water-gas shift reaction initiated with the nucleophilic attack of HO(-) on coordinated CO. DFT calculations show this addition to be essentially barrierless. The complexes have low cytotoxicity and low hemolytic indices. Following i.v. administration of CORM-3, the in vivo bio-distribution of CO differs from that obtained with CO inhalation or with heme oxygenase stimulation. A mechanism for CO transport and delivery from these complexes is proposed.

Design of novel quinazolinone derivatives as inhibitors for 5HT7 receptor.

PubMed

Chitta, Aparna; Jatavath, Mohan Babu; Fatima, Sabiha; Manga, Vijjulatha

2012-02-01

To study the pharmacophore properties of quinazolinone derivatives as 5HT(7) inhibitors, 3D QSAR methodologies, namely Comparative Molecular Field Analysis (CoMFA) and Comparative Molecular Similarity Indices Analysis (CoMSIA) were applied, partial least square (PLS) analysis was performed and QSAR models were generated. The derived model showed good statistical reliability in terms of predicting the 5HT(7) inhibitory activity of the quinazolione derivative, based on molecular property fields like steric, electrostatic, hydrophobic, hydrogen bond donor and hydrogen bond acceptor fields. This is evident from statistical parameters like q(2) (cross validated correlation coefficient) of 0.642, 0.602 and r(2) (conventional correlation coefficient) of 0.937, 0.908 for CoMFA and CoMSIA respectively. The predictive ability of the models to determine 5HT(7) antagonistic activity is validated using a test set of 26 molecules that were not included in the training set and the predictive r(2) obtained for the test set was 0.512 & 0.541. Further, the results of the derived model are illustrated by means of contour maps, which give an insight into the interaction of the drug with the receptor. The molecular fields so obtained served as the basis for the design of twenty new ligands. In addition, ADME (Adsorption, Distribution, Metabolism and Elimination) have been calculated in order to predict the relevant pharmaceutical properties, and the results are in conformity with required drug like properties.

Proton-coupled electron-transfer reduction of dioxygen catalyzed by a saddle-distorted cobalt phthalocyanine.

PubMed

Honda, Tatsuhiko; Kojima, Takahiko; Fukuzumi, Shunichi

2012-03-07

Proton-coupled electron-transfer reduction of dioxygen (O(2)) to afford hydrogen peroxide (H(2)O(2)) was investigated by using ferrocene derivatives as reductants and saddle-distorted (α-octaphenylphthalocyaninato)cobalt(II) (Co(II)(Ph(8)Pc)) as a catalyst under acidic conditions. The selective two-electron reduction of O(2) by dimethylferrocene (Me(2)Fc) and decamethylferrocene (Me(10)Fc) occurs to yield H(2)O(2) and the corresponding ferrocenium ions (Me(2)Fc(+) and Me(10)Fc(+), respectively). Mechanisms of the catalytic reduction of O(2) are discussed on the basis of detailed kinetics studies on the overall catalytic reactions as well as on each redox reaction in the catalytic cycle. The active species to react with O(2) in the catalytic reaction is switched from Co(II)(Ph(8)Pc) to protonated Co(I)(Ph(8)PcH), depending on the reducing ability of ferrocene derivatives employed. The protonation of Co(II)(Ph(8)Pc) inhibits the direct reduction of O(2); however, the proton-coupled electron transfer from Me(10)Fc to Co(II)(Ph(8)Pc) and the protonated [Co(II)(Ph(8)PcH)](+) occurs to produce Co(I)(Ph(8)PcH) and [Co(I)(Ph(8)PcH(2))](+), respectively, which react immediately with O(2). The rate-determining step is a proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) in the Co(II)(Ph(8)Pc)-catalyzed cycle with Me(2)Fc, whereas it is changed to the electron-transfer reduction of [Co(II)(Ph(8)PcH)](+) by Me(10)Fc in the Co(I)(Ph(8)PcH)-catalyzed cycle with Me(10)Fc. A single crystal of monoprotonated [Co(III)(Ph(8)Pc)](+), [Co(III)Cl(2)(Ph(8)PcH)], produced by the proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) with HCl, was obtained, and the crystal structure was determined in comparison with that of Co(II)(Ph(8)Pc). © 2012 American Chemical Society

3D QSAR based design of novel oxindole derivative as 5HT7 inhibitors.

PubMed

Chitta, Aparna; Sivan, Sree Kanth; Manga, Vijjulatha

2014-06-01

To understand the structural requirements of 5-hydroxytryptamine (5HT7) receptor inhibitors and to design new ligands against 5HT7 receptor with enhanced inhibitory potency, a three-dimensional quantitative structure-activity relationship study with comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) for a data set of 56 molecules consisting of oxindole, tetrahydronaphthalene, aryl ketone substituted arylpiperazinealkylamide derivatives was performed. Derived model showed good statistical reliability in terms of predicting 5HT7 inhibitory activity of the molecules, based on molecular property fields like steric, electrostatic, hydrophobic, hydrogen bond donor and hydrogen bond acceptor fields. This is evident from statistical parameters like conventional r2 and a cross validated (q2) values of 0.985, 0.743 for CoMFA and 0.970, 0.608 for CoMSIA, respectively. Predictive ability of the models to determine 5HT7 antagonistic activity is validated using a test set of 16 molecules that were not included in the training set. Predictive r2 obtained for the test set was 0.560 and 0.619 for CoMFA and CoMSIA, respectively. Steric, electrostatic fields majorly contributed toward activity which forms the basis for design of new molecules. Absorption, distribution, metabolism and elimination (ADME) calculation using QikProp 2.5 (Schrodinger 2010, Portland, OR) reveals that the molecules confer to Lipinski's rule of five in majority of the cases.

Synthesis and Structure of an Extended Cluster Lead(II) Carboxylate, [Pb{(CO)(9)Co(3)(&mgr;(3)-CCO(2))}(2)](n)(). Role of Core Metals in Cluster-Derived Hydrogenation Catalysts.

PubMed

Lei, Xinjian; Shang, Maoyu; Patil, Atul; Wolf, Eduardo E.; Fehlner, Thomas P.

1996-05-22

The reaction of lead acetate with (CO)(9)Co(3)(&mgr;(3)-CCOOH) leads to the formation of [Pb{(CO)(9)Co(3)(&mgr;(3)-CCO(2))}(2)](n)(), I, in high yield. The structure of I exhibits unusual six-coordinate Pb(II) centers with two asymmetrical chelating cluster carboxylates (C(22)Co(6)PbO(22); triclinic P&onemacr;; a = 8.119(1), b = 14.346(2), c = 14.660(2) Å; alpha = 102.18(1), beta = 99.01(1), gamma = 97.30(1) degrees; Z = 2). One oxygen of each cluster carboxylate ligand bridges between adjacent lead atoms such that a chainlike extended structure is found in the solid state without the presence of solvent or water. I is converted stepwise on pyrolysis into two metastable forms of solid materials (designated LT and HT), each of which has been characterized spectroscopically. The hydrogenation of 2-butenal as a test reaction shows that the LT catalyst exhibits selectivities similar to previous LT materials derived from other cobalt cluster metal carboxylates and that the HT material is totally inactive. The observed release of the lead core metal under HT activation conditions totally inactivates the catalyst and demonstrates exposure of the core metal in the HT form of these novel catalysts.

Practical synthesis of phthalimides and benzamides by a multicomponent reaction involving arynes, isocyanides, and CO2/H2O.

PubMed

Kaicharla, Trinadh; Thangaraj, Manikandan; Biju, Akkattu T

2014-03-21

Transition-metal-free multicomponent reactions involving arynes and isocyanides with either CO2 or H2O have been reported. With CO2 as the third component, the reactions resulted in the formation of N-substituted phthalimides. The utility of water as the third component furnished benzamide derivatives in moderate to good yields. These reactions took place under mild conditions with broad scope.

Rhodium-catalyzed tandem Pauson-Khand type reactions of 1,4-enynes tethered by a cyclopropyl group.

PubMed

Chen, Gen-Qiang; Shi, Min

2013-01-25

The tandem Pauson-Khand type reactions of 1,4-enynes tethered by a cyclopropyl group with two molecules of CO proceed smoothly in the presence of [Rh(CO)(2)Cl](2) under a CO atmosphere to give the corresponding 6-hydroxy-2,3-dihydro-1H-inden-1-one derivatives in moderate yields under mild conditions.

Organismal, genetic, and transcriptional variation in the deeply sequenced gut microbiomes of identical twins

PubMed Central

Turnbaugh, Peter J.; Quince, Christopher; Faith, Jeremiah J.; McHardy, Alice C.; Yatsunenko, Tanya; Niazi, Faheem; Affourtit, Jason; Egholm, Michael; Henrissat, Bernard; Knight, Rob; Gordon, Jeffrey I.

2010-01-01

We deeply sampled the organismal, genetic, and transcriptional diversity in fecal samples collected from a monozygotic (MZ) twin pair and compared the results to 1,095 communities from the gut and other body habitats of related and unrelated individuals. Using a new scheme for noise reduction in pyrosequencing data, we estimated the total diversity of species-level bacterial phylotypes in the 1.2-1.5 million bacterial 16S rRNA reads obtained from each deeply sampled cotwin to be ~800 (35.9%, 49.1% detected in both). A combined 1.1 million read 16S rRNA dataset representing 281 shallowly sequenced fecal samples from 54 twin pairs and their mothers contained an estimated 4,018 species-level phylotypes, with each sample having a unique species assemblage (53.4 ± 0.6% and 50.3 ± 0.5% overlap with the deeply sampled cotwins). Of the 134 phylotypes with a relative abundance of >0.1% in the combined dataset, only 37 appeared in >50% of the samples, with one phylotype in the Lachnospiraceae family present in 99%. Nongut communities had significantly reduced overlap with the deeply sequenced twins’ fecal microbiota (18.3 ± 0.3%, 15.3 ± 0.3%). The MZ cotwins’ fecal DNA was deeply sequenced (3.8-6.3 Gbp/sample) and assembled reads were assigned to 25 genus-level phylogenetic bins. Only 17% of the genes in these bins were shared between the cotwins. Bins exhibited differences in their degree of sequence variation, gene content including the repertoire of carbohydrate active enzymes present within and between twins (e.g., predicted cellulases, dockerins), and transcriptional activities. These results provide an expanded perspective about features that make each of us unique life forms and directions for future characterization of our gut ecosystems. PMID:20363958

PREDICTION OF FORBIDDEN ULTRAVIOLET AND VISIBLE EMISSIONS IN COMET 67P/CHURYUMOV–GERASIMENKO

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

Raghuram, Susarla; Galand, Marina; Bhardwaj, Anil, E-mail: raghuramsusarla@gmail.com

Remote observation of spectroscopic emissions is a potential tool for the identification and quantification of various species in comets. The CO Cameron band (to trace CO{sub 2}) and atomic oxygen emissions (to trace H{sub 2}O and/or CO{sub 2}, CO) have been used to probe neutral composition in the cometary coma. Using a coupled-chemistry-emission model, various excitation processes controlling the CO Cameron band and different atomic oxygen and atomic carbon emissions have been modeled in comet 67P/Churyumov–Gerasimenko at 1.29 AU (perihelion) and at 3 AU heliocentric distances, which is being explored by ESA's Rosetta mission. The intensities of the CO Cameronmore » band, atomic oxygen, and atomic carbon emission lines as a function of projected distance are calculated for different CO and CO{sub 2} volume mixing ratios relative to water. Contributions of different excitation processes controlling these emissions are quantified. We assess how CO{sub 2} and/or CO volume mixing ratios with respect to H{sub 2}O can be derived based on the observed intensities of the CO Cameron band, atomic oxygen, and atomic carbon emission lines. The results presented in this work serve as baseline calculations to understand the behavior of low out-gassing cometary coma and compare them with the higher gas production rate cases (e.g., comet Halley). Quantitative analysis of different excitation processes governing the spectroscopic emissions is essential to study the chemistry of inner coma and to derive neutral gas composition.« less

Sorption of CO 2 in a hydrogen-bonded diamondoid network of sulfonylcalix[4]arene

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

Sinnwell, Michael A.; Atwood, Jerry L.; Thallapally, Praveen K.

An organic material, p-tert-butyltetrasulfonylcalix[4]arene, self-assembles via hydrogen bonding to form a diamondoid supramolecular network. Possessing discrete, zero-dimensional (0D) microcavities, the thiacalixarene derivative adsorbs CO2 at high pressures

Immobilization of pectinase from Leucoagaricus gongylophorus on magnetic particles.

PubMed

Adalberto, Paulo Roberto; José dos Santos, Francisco; Golfeto, Camilla Calemi; Costa Iemma, Mônica Rosas; Ferreira de Souza, Dulce Helena; Cass, Quezia Bezerra

2012-10-21

Polygalacturonases (EC 3.2.1.15) hydrolyze the α-1,4-glycosidic linkages in polygalacturonic acid chains. The interest on specific inhibitors of pectinase and the versatility of magnetic support for enzyme immobilization endorsed the preparation of an immobilized enzyme reactor (IMER). This work presents the synthesis of CoFe(2)O(4) amino-derivatives, which was employed as the support for the immobilization of pectinases from Leucoagaricus gongylophorus. Amino-functionalized CoFe(2)O(4) was obtained from glyceryl-derivatized CoFe(2)O(4) and was characterized by infrared spectroscopy and electronic microscopy. The immobilized enzyme maintained the same thermal, chemical and kinetic behaviour of the free enzyme (T(opt) 60 °C; pH(opt) 5.0; K(app)(M) = 0.5 mg min(-1); V(app)(M) ≈ 5.0 μmol min(-1) mL(-1)). The straightforward synthesis of CoFe(2)O(4) derivatives and the efficiency of immobilization offer wide perspectives for the use of the developed new IMER.

CO2 Biofixation by the Cyanobacterium Spirulina sp. LEB 18 and the Green Alga Chlorella fusca LEB 111 Grown Using Gas Effluents and Solid Residues of Thermoelectric Origin.

PubMed

da Silva Vaz, Bruna; Costa, Jorge Alberto Vieira; de Morais, Michele Greque

2016-01-01

The concentration of carbon dioxide (CO2) in the atmosphere has increased from 280 to 400 ppm in the last 10 years, and the coal-fired power plants are responsible for approximately 22 % of these emissions. The burning of fossil fuel also produces a great amount of solid waste that causes serious industrial and environmental problems. The biological processes become interesting alternative in combating pollution and developing new products. The objective of this study was to evaluate the CO2 biofixation potential of microalgae that were grown using gaseous effluents and solid residues of thermoelectric origin. The microalgae Chlorella fusca LEB 111 presented higher rate of CO2 biofixation (42.8 %) (p < 0.01) than did Spirulina sp. LEB 18. The values for the CO2 biofixation rates and the kinetic parameters of Spirulina and Chlorella cells grown using combustion gas did not differ significantly from those of cells grown using CO2 and a carbon source in the culture media. These microalgae could be grown using ash derived from coal combustion, using the minerals present in this residue as the source of the essential metals required for their growth and the CO2 derived from the combustion gas as their carbon source.

Two Bacterial Diterpene Synthases from Allokutzneria albata for Bonnadiene and for Phomopsene and Allokutznerene.

PubMed

Lauterbach, Lukas; Rinkel, Jan; Dickschat, Jeroen Sidney

2018-05-14

Two diterpene synthases from Allokutzneria albata were studied for their products, resulting in the identification of the new compound bonnadiene from the first enzyme. Although phylogenetically unrelated to fungal phomopsene synthase, the second enzyme produced a mixture of phomopsene and a biosynthetically linked new compound, allokutznerene, besides spiroviolene. Both enzymes were deeply studied for their mechanisms by isotopic labelling experiments, metal cofactor variation and site-directed mutagenesis. Oxidation products of phomopsene and allokutznerene are also discussed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A global view of the extratropical tropopause transition layer from Atmospheric Chemistry Experiment Fourier Transform Spectrometer O3, H2O, and CO

NASA Astrophysics Data System (ADS)

Hegglin, M. I.; Boone, C. D.; Manney, G. L.; Walker, K. A.

2009-04-01

The global behavior of the extratropical tropopause transition layer (ExTL) is investigated using O3, H2O, and CO measurements from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on Canada's SCISAT-1 satellite obtained between February 2004 and May 2007. The ExTL depth is derived using H2O-O3 and CO-O3 correlations. The ExTL top derived from H2O-O3 shows an increase from roughly 1-1.5 km above the thermal tropopause in the subtropics to 3-4 km (2.5-3.5 km) in the north (south) polar region, implying somewhat weaker troposphere-stratosphere-transport in the Southern Hemisphere. The ExTL bottom extends ˜1 km below the thermal tropopause, indicating a persistent stratospheric influence on the troposphere at all latitudes. The ExTL top derived from the CO-O3 correlation is lower, at 2 km or ˜345 K (1.5 km or ˜335 K) in the Northern (Southern) Hemisphere. Its annual mean coincides with the relative temperature maximum just above the thermal tropopause. The vertical CO gradient maximizes at the thermal tropopause, indicating a local minimum in mixing within the tropopause region. The seasonal changes in and the scales of the vertical H2O gradients show a similar pattern as the static stability structure of the tropopause inversion layer (TIL), which provides observational support for the hypothesis that H2O plays a radiative role in forcing and maintaining the structure of the TIL.

Electron-spectroscopy studies of clean thorium and uranium surfaces. Chemisorption and initial stages of reaction with O2, CO, and CO2

NASA Astrophysics Data System (ADS)

McLean, W.; Colmenares, C. A.; Smith, R. L.; Somorjai, G. A.

1982-01-01

The adsorption of O2, CO, and CO2 on the thorium (111) crystal face and on polycrystalline α-uranium has been investigated by x-ray photoelectron spectroscopy, Auger electron spectroscopy (AES), and secondary-ion mass spectroscopy (SIMS) at 300 K. Oxygen adsorption on both metals resulted in the formation of the metal dioxide. CO and CO2 adsorption on Th(111) produced species derived from atomic carbon and oxygen; the presence of molecular CO was also detected. Only atomic carbon and oxygen were observed on uranium. Elemental depth profiles by AES and SIMS indicated that the carbon produced by the dissociation of CO or CO2 diffused into the bulk of the metals to form a carbide, while the oxygen remained on their surfaces as an oxide.

ZIF-67-derived hollow nanocages with layered double oxides shell as high-Efficiency catalysts for CO oxidation

NASA Astrophysics Data System (ADS)

Kong, Wenpeng; Li, Jing; Chen, Yao; Ren, Yuqing; Guo, Yonghua; Niu, Shengli; Yang, Yanzhao

2018-04-01

Constructing non-precious hybrid metal oxides with specific morphology as cost-effective and highly efficient catalysts is a promising way for the automotive exhaust purification. In this work, we report a facile strategy for the fabrication of a unique hollow Co-Ni layered double oxides (HLDO) nanocages by using zeolitic imidazole frameworks (ZIFs) as template. The synthesis of intermediate core-shell and hollow Co-Ni layered double hydroxides (HLDH) nanoflakes as well as the corresponding Co-Ni oxides products were successfully controlled, and the formation process was also explained. Among ZIF-67-derived oxides, HLDO exhibits excellent catalytic activities (complete conversion of CO into CO2 at 118 °C) and long-term stability for CO oxidation. The remarkable catalytic activities of HLDO can be attributed to high surface area (258 m2 g-1) inherited from the HLDH, which could provide more active sites for CO oxidation. In addition, active oxygen species indicated by the O 1 s XPS spectrum and improved synergistic effect between NiO and Co3O4 reflected by H2-TPR, further explain the enhanced performance of the HLDO catalysts. The presented strategy for controlled design and synthesis of hollow multicomponent metal oxides will provide prospects in developing highly effective catalysts.

A comparison of cellulosic fuel yields and separated soil-surface CO2 fluxes in maize and prairie biofuel cropping systems

NASA Astrophysics Data System (ADS)

Nichols, Virginia A.

It has been suggested that strategic incorporation of perennial vegetation into agricultural landscapes could provide ecosystem services while maintaining agricultural productivity. To evaluate potential use of prairie as a Midwestern cellulosic feedstock, we investigated theoretical cellulosic fuel yields, as well as soil-surface carbon dioxide emissions of prairie-based biofuel systems as compared to maize-based systems on fertile soils in Boone County, IA, USA. Investigated systems were: a maize-soybean rotation grown for grain only, continuous maize grown for grain and stover both with and without a winter rye cover crop, and a 31-species reconstructed prairie grown with and without spring nitrogen fertilization for fall-harvested biomass. From 2009-2013, the highest producing system was N-fertilized prairie, averaging 10.4 Mg ha -1 yr-1 above-ground biomass with average harvest removals of 7.8 Mg ha-1 yr-1. The unfertilized prairie produced 7.4 Mg ha-1 yr-1, averaging harvests of 5.3 Mg ha-1 yr-1. Lowest cellulosic biomass harvests were realized from continuous maize systems, averaging 3.5 Mg ha -1 yr-1 when grown with, and 3.7 Mg ha-1 yr-1 when grown without a winter rye cover crop, respectively. Un-fertilized prairie biomass and maize stover had equivalent dietary conversion ratios at 330 g ethanol kg-1 dry biomass, but N-fertilized prairie was lower at 315. Over four years prairie systems averaged 1287 L cellulosic ethanol ha-1 yr-1 more than maize systems, with fertilization increasing prairie ethanol production by 865 L ha-1 yr-1. Harvested biomass accounted for >90% of ethanol yield variation. A major hurdle in carbon cycling studies is the separation of the soil-surface CO2 flux into its respective components. From 2012-2013 we used a shading method to separate soil-surface CO2 resulting from oxidation of soil organic matter and CO2 derived from live-root activity in three systems: unfertilized prairie, N-fertilized prairie, and continuous maize. Contrary to our hypothesis, total growing-season root CO2 flux was not proportional to end-of-season root biomass of cropping systems; unfertilized prairie contained nearly twice the root biomass of N-fertilized prairie, but the two systems' total root CO2 fluxes were not significantly different in either year. We found that the total growing-season flux of both root- and organic matter-derived CO 2 was higher in the prairie systems compared to the maize system. However, on a percentage basis, the prairies' soil-surface CO2 flux from May-September averaged 29% root-derived while from mid-June through September the maize averaged 22% root-derived. The percentage of the total CO2 flux that was root-derived in a given system varied from year to year, indicating there is no set relationship for a given cropping system.

Phosphatidylinositol 3-kinase coordinately activates the MEK/ERK and AKT/NFkappaB pathways to maintain osteoclast survival.

PubMed

Gingery, Anne; Bradley, Elizabeth; Shaw, Aubie; Oursler, Merry Jo

2003-05-01

We have examined highly purified osteoclasts that were generated in vitro from murine co-culture of marrow precursors with stromal support cells and have found evidence of activation of the MEK/ERK and AKT/NFkappaB survival pathways. Many mature marrow-derived osteoclasts survived for at least 48 h in culture whether or not they are maintained with stromal cells. Moreover, supplementing purified osteoclasts with RANKL and/or M-CSF had no impact on their survival pattern. In addition, spleen-derived osteoclasts generated with RANKL and M-CSF treatment exhibited a similar survival pattern. Blocking MEK, AKT, or NFkappaB activity resulted in apoptosis of many, but not all, of the osteoclasts in purified marrow-derived osteoclasts, marrow-derived osteoclasts co-cultured with stromal cells, and spleen-derived osteoclasts maintained with RANKL and M-CSF. These data support that both the MEK/ERK and AKT/NFkappaB pathways contribute to osteoclast survival. Since PI3K has been shown to activate either of these pathways, we have examined its role in osteoclast survival. PI3K inhibition caused apoptosis of nearly all osteoclasts in purified and co-cultured marrow-derived osteoclasts and spleen-derived osteoclasts maintained with RANKL and M-CSF. Interestingly, in marrow-derived co-cultures, the apoptotic response was restricted to osteoclasts as there was no evidence of stromal support cell apoptosis. PI3K inhibition also blocked MEK1/2, ERK1/2, and AKT phosphorylation and NFkappaB activation in purified osteoclasts. Simultaneous blockage of both AKT and MEK1/2 caused rapid apoptosis of nearly all osteoclasts, mimicking the response to PI3K inhibition. These data reveal that PI3K coordinately activates two distinct survival pathways that are both important in osteoclast survival. Copyright 2003 Wiley-Liss, Inc.

Effect of structural promoters on Fe-based Fischer-Tropsch synthesis of biomass derived syngas

Treesearch

Pratibha Sharma; Thomas Elder; Leslie H. Groom; James J. Spivey

2014-01-01

Biomass gasification and subsequent conversion of this syngas to liquid hydrocarbons using Fischer–Tropsch (F–T) synthesis is a promising source of hydrocarbon fuels. However, biomass-derived syngas is different from syngas obtained from other sources such as steam reforming of methane. Specifically the H2/CO ratio is less than 1/1 and the CO

Drivers of pCO2 dynamics in two contrasting coral reef lagoons: The influence of submarine groundwater discharge (Invited)

NASA Astrophysics Data System (ADS)

Cyronak, T.; Santos, I. R.; Erler, D.; Maher, D. T.; Eyre, B.

2013-12-01

The carbon chemistry of coral reef lagoons can be highly variable over short time scales. While much of the diel variability in seawater carbon chemistry is explained by biological processes, external sources such as river and groundwater seepage may deliver large amounts of organic and inorganic carbon to coral reefs and represent a poorly understood feedback to ocean acidification. Here, we assess the impact of submarine groundwater discharge (SGD) on pCO2 variability in two coral reef lagoons with distinct SGD driving mechanisms. Diel variability of pCO2 in the two ecosystems was explained by a combination of biological drivers and SGD inputs. In Rarotonga, a South Pacific volcanic island, SGD was driven primarily by a steep terrestrial hydraulic gradient, and the lagoon was influenced by the high pCO2 (5,501 μatm) of the fresh groundwater. In Heron Island, a Great Barrier Reef coral cay, SGD was dominated by seawater recirculation through sediments (i.e. tidal pumping) and pCO2 was mainly impacted through the stimulation of biological processes. The Rarotonga water column had a relatively higher average pCO2 (549 μatm) than Heron Island (471 μatm). However, pCO2 exhibited a greater diel range in Heron Island (778 μatm) than in Rarotonga (507 μatm). The Rarotonga lagoon received 31.2 mmol CO2 m-2 d-1 from SGD, while the Heron Island lagoon received 12.3 mmol CO2 m-2 d-1. Over the course of this study both systems were sources of CO2 to the atmosphere (3.00 to 9.67 mmol CO2 m-2 d-1), with SGD-derived CO2 contributing a large portion to the air-sea CO2 flux. The relationship between both water column pH and aragonite saturation state (ΩAr) and radon (222Rn) concentrations indicate that SGD may enhance the local acidification of some coral reef lagoons. Studies measuring the carbon chemistry of coral reefs (e.g. community metabolism, calcification rates) may need to consider SGD-derived CO2.

Formation of bimetallic metal-organic framework nanosheets and their derived porous nickel-cobalt sulfides for supercapacitors.

PubMed

Chen, Chen; Wu, Meng-Ke; Tao, Kai; Zhou, Jiao-Jiao; Li, Yan-Li; Han, Xue; Han, Lei

2018-04-24

Metal-organic frameworks (MOFs) show great advantages as new kinds of active materials for energy storage. In this study, bimetallic metal-organic frameworks (Ni/Co-MOFs) with nanosheet-assembled flower-like structures were synthesized by etching Ni-MOF microspheres in a cobalt nitrate solution. It can be clearly observed that the amount of Co(NO3)2 and etching time play crucial roles in the formation of Ni/Co-MOF nanosheets. The Ni/Co-MOFs were used as electrode materials for supercapacitors and the optimized Ni/Co-MOF-5 exhibited the highest capacitances of 1220.2 F g-1 and 986.7 F g-1 at current densities of 1 A g-1 and 10 A g-1, respectively. Ni/Co-MOF-5 was further sulfurized, and the derived Ni-Co-S electrode showed a higher specific capacitance of 1377.5 F g-1 at a current density of 1 A g-1 and a retention of 89.4% when the current density was increased to 10 A g-1, indicating superior rate capability. Furthermore, Ni/Co-MOF-5 and Ni-Co-S showed excellent cycling stability, i.e. about 87.8% and 93.7% of initial capacitance can be still maintained after 3000 cycles of charge-discharge. More interestingly, the Ni/Co-MOF-5//AC ASC shows an energy density of 30.9 W h kg-1 at a power density of 1132.8 W kg-1, and the Ni-Co-S//AC ASC displays a high energy density of 36.9 W h kg-1 at a power density of 1066.42 W kg-1. These results demonstrate that the as-synthesized bimetallic Ni/Co-MOF nanosheets and their derived nickel-cobalt sulfides have promising applications in electrochemical supercapacitors.

Carbon and oxygen isotopic composition of coal and carbon dioxide derived from laboratory coal combustion: A preliminary study

USGS Publications Warehouse

Warwick, Peter D.; Ruppert, Leslie F.

2016-01-01

The concentration of carbon dioxide (CO2) in the atmosphere has dramatically increased from the start of the industrial revolution in the mid-1700s to present levels exceeding 400 ppm. Carbon dioxide derived from fossil fuel combustion is a greenhouse gas and a major contributor to on-going climate change. Carbon and oxygen stable isotope geochemistry is a useful tool to help model and predict the contributions of anthropogenic sources of CO2 in the global carbon cycle. Surprisingly few studies have addressed the carbon and oxygen isotopic composition of CO2 derived from coal combustion. The goal of this study is to document the relationships between the carbon and oxygen isotope signatures of coal and signatures of the CO2 produced from laboratory coal combustion in atmospheric conditions.Six coal samples were selected that represent various geologic ages (Carboniferous to Tertiary) and coal ranks (lignite to bituminous). Duplicate splits of the six coal samples were ignited and partially combusted in the laboratory at atmospheric conditions. The resulting coal-combustion gases were collected and the molecular composition of the collected gases and isotopic analyses of δ13C of CO2, δ13C of CH4, and δ18O of CO2 were analysed by a commercial laboratory. Splits (~ 1 g) of the un-combusted dried ground coal samples were analyzed for δ13C and δ18O by the U.S. Geological Survey Reston Stable Isotope Laboratory.The major findings of this preliminary work indicate that the isotopic signatures of δ13C (relative to the Vienna Pee Dee Belemnite scale, VPDB) of CO2 resulting from coal combustion are similar to the δ13CVPDB signature of the bulk coal (− 28.46 to − 23.86 ‰) and are not similar to atmospheric δ13CVPDB of CO2 (~ − 8 ‰, see http://www.esrl.noaa.gov/gmd/outreach/isotopes/c13tellsus.html). The δ18O values of bulk coal are strongly correlated to the coal dry ash yields and appear to have little or no influence on the δ18O values of CO2 resulting from coal combustion in open atmospheric conditions. There is a wide range of δ13C values of coal reported in the literature and the δ13C values from this study generally follow reported ranges for higher plants over geologic time. The values of δ18O (relative to Vienna Standard Mean Ocean Water) of CO2 derived from atmospheric combustion of coal and other high-carbon fuels (peat and coal) range from + 19.03 to + 27.03‰ and are similar to atmospheric oxygen δ18OVSMOW values which average + 23.8‰. Further work is needed on a broader set of samples to better define the relationships between coal composition and combustion-derived gases.

CO2 Conversion into Esters by Fluoride-Mediated Carboxylation of Organosilanes and Halide Derivatives.

PubMed

Frogneux, Xavier; von Wolff, Niklas; Thuéry, Pierre; Lefèvre, Guillaume; Cantat, Thibault

2016-02-24

A one-step conversion of CO2 into heteroaromatic esters is presented under metal-free conditions. Using fluoride anions as promoters for the C-Si bond activation, pyridyl, furanyl, and thienyl organosilanes are successfully carboxylated with CO2 in the presence of an electrophile. The mechanism of this unprecedented reaction has been elucidated based on experimental and computational results, which show a unique catalytic influence of CO2 in the C-Si bond activation of pyridylsilanes. The methodology is applied to 18 different esters, and it has enabled the incorporation of CO2 into a polyester material for the first time. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mean Ages of Stratospheric Air Derived From in Situ Observations of CO2, CH4, and N2O

NASA Technical Reports Server (NTRS)

Andrews, A. E.; Boering, K. A.; Daube, B. C.; Wofsy, S. C.; Loewenstein, M.; Jost, H.; Podolske, J. R.; Webster, C. R.; Herman, R. L.; Scott, D. C.;

Apportionment of carbon dioxide over central Europe: insights from combined measurements of atmospheric CO2 mixing ratios and carbon isotope composition

NASA Astrophysics Data System (ADS)

Zimnoch, M.; Jelen, D.; Galkowski, M.; Kuc, T.; Necki, J.; Chmura, L.; Gorczyca, Z.; Jasek, A.; Rozanski, K.

2012-04-01

The European continent, due to high population density and numerous sources of anthropogenic CO2 emissions, plays an important role in the global carbon budget. Nowadays, precise measurements of CO2 mixing ratios performed by both global and regional monitoring networks, combined with appropriate models of carbon cycle, allow quantification of the European input to the global atmospheric CO2 load. However, measurements of CO2 mixing ratios alone cannot provide the information necessary for the apportionment of fossil-fuel related and biogenic contributions to the total CO2 burden of the regional atmosphere. Additional information is required, for instance obtained through measurements of radiocarbon content in atmospheric carbon dioxide. Radiocarbon is a particularly useful tracer for detecting fossil carbon in the atmosphere on different spatial and temporal scales. Regular observations of atmospheric CO2mixing ratios and their isotope compositions have been performed during the period of 2005-2009 at two sites located in central Europe (southern Poland). The sites, only ca. 100 km apart, represent two extreme environments with respect to the extent of anthropogenic pressure: (i) the city of Krakow, representing typical urban environment with numerous sources of anthropogenic CO2, and (ii) remote mountain site Kasprowy Wierch, relatively free of local influences. Regular, quasi-continuous measurements of CO2 mixing ratios have been performed at both sites. In addition, cumulative samples of atmospheric CO2 have been collected (weekly sampling regime for Krakow and monthly for Kasprowy Wierch) to obtain mean carbon isotope signature (14C/12C and 13C/12C ratios) of atmospheric CO2 at both sampling locations. Partitioning of the local atmospheric CO2 load at both locations has been performed using isotope- and mass balance approach. In Krakow, the average fossil-fuel related contribution to the local atmospheric CO2 load was equal to approximately 3.4%. The biogenic component turned out to be of the same magnitude. Both components revealed a distinct seasonality, with the fossil-fuel related component reaching maximum values during winter months and the biogenic component shifted in phase by ca. 6 months. Seasonality of fossil-fuel related CO2 load in the local atmosphere is linked with seasonality of local CO2sources, mostly burning of fossil fuels for heating purposes. Positive values of biogenic component indicate prevalence of the local respiration and biomass burning processes over local photosynthesis. Summer maxima of biogenic CO2 component represent mostly local respiration activity. Direct measurements of soil CO2 fluxes in the Krakow region showed an approximately 10-fold increase of those fluxes during the summer months. Partitioning of the local CO2 budget for Kasprowy Wierch site revealed large differences in the derived components when compared to urban atmosphere of Krakow: the fossil-fuel related component was ca. 5 times lower whereas the biogenic component was negative in summer, pointing to the importance of photosynthetic sink associated with extensive forests in the neighborhood of the station. The isotope- and mass balance approach was also used to derive mean monthly 13C isotope signature of fossil-fuel related CO2 emissions in Krakow. Although the derived δ13CO2 values revealed large variability, they are confined in the range of 13C isotope composition being reported for various sources of CO2 emissions in the city (burning of coal and oil, burning of methane gas, traffic).

3D-QSAR studies on the inhibitory activity of trimethoprim analogues against Escherichia coli dihydrofolate reductase.

PubMed

Vijayaraj, Ramadoss; Devi, Mekapothula Lakshmi Vasavi; Subramanian, Venkatesan; Chattaraj, Pratim Kumar

2012-06-01

Three-dimensional quantitative structure activity relationship (3D-QSAR) study has been carried out on the Escherichia coli DHFR inhibitors 2,4-diamino-5-(substituted-benzyl)pyrimidine derivatives to understand the structural features responsible for the improved potency. To construct highly predictive 3D-QSAR models, comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) methods were used. The predicted models show statistically significant cross-validated and non-cross-validated correlation coefficient of r2 CV and r2 nCV, respectively. The final 3D-QSAR models were validated using structurally diverse test set compounds. Analysis of the contour maps generated from CoMFA and CoMSIA methods reveals that the substitution of electronegative groups at the first and second position along with electropositive group at the third position of R2 substitution significantly increases the potency of the derivatives. The results obtained from the CoMFA and CoMSIA study delineate the substituents on the trimethoprim analogues responsible for the enhanced potency and also provide valuable directions for the design of new trimethoprim analogues with improved affinity. © 2012 John Wiley & Sons A/S.

Abundant carbon in the mantle beneath Hawai`i

NASA Astrophysics Data System (ADS)

Anderson, Kyle R.; Poland, Michael P.

2017-09-01

Estimates of carbon concentrations in Earth’s mantle vary over more than an order of magnitude, hindering our ability to understand mantle structure and mineralogy, partial melting, and the carbon cycle. CO2 concentrations in mantle-derived magmas supplying hotspot ocean island volcanoes yield our most direct constraints on mantle carbon, but are extensively modified by degassing during ascent. Here we show that undegassed magmatic and mantle carbon concentrations may be estimated in a Bayesian framework using diverse geologic information at an ocean island volcano. Our CO2 concentration estimates do not rely upon complex degassing models, geochemical tracer elements, assumed magma supply rates, or rare undegassed rock samples. Rather, we couple volcanic CO2 emission rates with probabilistic magma supply rates, which are obtained indirectly from magma storage and eruption rates. We estimate that the CO2 content of mantle-derived magma supplying Hawai`i’s active volcanoes is 0.97-0.19+0.25 wt%--roughly 40% higher than previously believed--and is supplied from a mantle source region with a carbon concentration of 263-62+81 ppm. Our results suggest that mantle plumes and ocean island basalts are carbon-rich. Our data also shed light on helium isotope abundances, CO2/Nb ratios, and may imply higher CO2 emission rates from ocean island volcanoes.

Analytical Investigation of the Decrease in the Size of the Habitable Zone Due to a Limited CO2 Outgassing Rate

NASA Astrophysics Data System (ADS)

Abbot, Dorian S.

2016-08-01

The habitable zone concept is important because it focuses the scientific search for extraterrestrial life and aids the planning of future telescopes. Recent work has shown that planets near the outer edge of the habitable zone might not actually be able to stay warm and habitable if CO2 outgassing rates are not large enough to maintain high CO2 partial pressures against removal by silicate weathering. In this paper, I use simple equations for the climate and CO2 budget of a planet in the habitable zone that can capture the qualitative behavior of the system. With these equations I derive an analytical formula for an effective outer edge of the habitable zone, including limitations imposed by the CO2 outgassing rate. I then show that climate cycles between a snowball state and a warm climate are only possible beyond this limit if the weathering rate in the snowball climate is smaller than the CO2 outgassing rate (otherwise stable snowball states result). I derive an analytical solution for the climate cycles including a formula for their period in this limit. This work allows us to explore the qualitative effects of weathering processes on the effective outer edge of the habitable zone, which is important because weathering parameterizations are uncertain.

Analytical Investigation of the Decrease in the Size of the Habitable Zone due to Limited CO2 Outgassing Rate

NASA Astrophysics Data System (ADS)

Abbot, D. S.

2016-12-01

The habitable zone concept is important because it focuses the scientific search for extraterrestrial life and aids the planning of future telescopes. Recent work has shown that planets near the outer edge of the habitable zone might not actually be able to stay warm and habitable if CO2 outgassing rates are not large enough to maintain high CO2 partial pressures against removal by silicate weathering. I use simple equations for the climate and CO2 budget of a planet in the habitable zone that can capture the qualitative behavior of the system. With these equations I derive an analytical formula for an effective outer edge of the habitable zone, including limitations imposed by the CO2 outgassing rate. I then show that climate cycles between a Snowball state and a warm climate are only possible beyond this limit if the weathering rate in the Snowball climate is smaller than the CO2 outgassing rate (otherwise stable Snowball states result). I derive an analytical solution for the climate cycles including a formula for their period in this limit. This work allows us to explore the qualitative effects of weathering processes on the effective outer edge of the habitable zone, which is important because weathering parameterizations are uncertain.

RNASeq-derived transcriptome comparisons reveal neuromodulatory deficiency in the CO2 insensitive brown Norway rat

PubMed Central

Puissant, Madeleine M; Echert, Ashley E; Yang, Chun; Mouradian, Gary C; Novotny, Tyler; Liu, Pengyuan; Liang, Mingyu; Hodges, Matthew R

2015-01-01

Raphé-derived serotonin (5-HT) and thyrotropin-releasing hormone (TRH) play important roles in fundamental, homeostatic control systems such as breathing and specifically the ventilatory CO2 chemoreflex. Brown Norway (BN) rats exhibit an inherent and severe ventilatory insensitivity to hypercapnia but also exhibit relatively normal ventilation at rest and during other conditions, similar to multiple genetic models of 5-HT system dysfunction in mice. Herein, we tested the hypothesis that the ventilatory insensitivity to hypercapnia in BN rats is due to altered raphé gene expression and the consequent deficiencies in raphé-derived neuromodulators such as TRH. Medullary raphé transcriptome comparisons revealed lower expression of multiple 5-HT neuron-specific genes in BN compared to control Dahl salt-sensitive rats, predictive of reduced central nervous system monoamines by bioinformatics analyses and confirmed by high-performance liquid chromatography measurements. In particular, raphé Trh mRNA and peptide levels were significantly reduced in BN rats, and injections of the stable TRH analogue Taltirelin (TAL) stimulated breathing dose-dependently, with greater effects in BN versus control Sprague–Dawley rats. Importantly, TAL also effectively normalized the ventilatory CO2 chemoreflex in BN rats, but TAL did not affect CO2 sensitivity in control Sprague–Dawley rats. These data establish a molecular basis of the neuromodulatory deficiency in BN rats, and further suggest an important functional role for TRH signalling in the mammalian CO2 chemoreflex. PMID:25630262

Asphalt-derived high surface area activated porous carbons for carbon dioxide capture.

PubMed

Jalilov, Almaz S; Ruan, Gedeng; Hwang, Chih-Chau; Schipper, Desmond E; Tour, Josiah J; Li, Yilun; Fei, Huilong; Samuel, Errol L G; Tour, James M

2015-01-21

Research activity toward the development of new sorbents for carbon dioxide (CO2) capture have been increasing quickly. Despite the variety of existing materials with high surface areas and high CO2 uptake performances, the cost of the materials remains a dominant factor in slowing their industrial applications. Here we report preparation and CO2 uptake performance of microporous carbon materials synthesized from asphalt, a very inexpensive carbon source. Carbonization of asphalt with potassium hydroxide (KOH) at high temperatures (>600 °C) yields porous carbon materials (A-PC) with high surface areas of up to 2780 m(2) g(-1) and high CO2 uptake performance of 21 mmol g(-1) or 93 wt % at 30 bar and 25 °C. Furthermore, nitrogen doping and reduction with hydrogen yields active N-doped materials (A-NPC and A-rNPC) containing up to 9.3% nitrogen, making them nucleophilic porous carbons with further increase in the Brunauer-Emmett-Teller (BET) surface areas up to 2860 m(2) g(-1) for A-NPC and CO2 uptake to 26 mmol g(-1) or 114 wt % at 30 bar and 25 °C for A-rNPC. This is the highest reported CO2 uptake among the family of the activated porous carbonaceous materials. Thus, the porous carbon materials from asphalt have excellent properties for reversibly capturing CO2 at the well-head during the extraction of natural gas, a naturally occurring high pressure source of CO2. Through a pressure swing sorption process, when the asphalt-derived material is returned to 1 bar, the CO2 is released, thereby rendering a reversible capture medium that is highly efficient yet very inexpensive.

Imaging volcanic CO2 and SO2

NASA Astrophysics Data System (ADS)

Gabrieli, A.; Wright, R.; Lucey, P. G.; Porter, J. N.

2017-12-01

Detecting and quantifying volcanic carbon dioxide (CO2) and sulfur dioxide (SO2) emissions is of relevance to volcanologists. Changes in the amount and composition of gases that volcanoes emit are related to subsurface magma movements and the probability of eruptions. Volcanic gases and related acidic aerosols are also an important atmospheric pollution source that create environmental health hazards for people, animals, plants, and infrastructures. For these reasons, it is important to measure emissions from volcanic plumes during both day and night. We present image measurements of the volcanic plume at Kīlauea volcano, HI, and flux derivation, using a newly developed 8-14 um hyperspectral imaging spectrometer, the Thermal Hyperspectral Imager (THI). THI is capable of acquiring images of the scene it views from which spectra can be derived from each pixel. Each spectrum contains 50 wavelength samples between 8 and 14 um where CO2 and SO2 volcanic gases have diagnostic absorption/emission features respectively at 8.6 and 14 um. Plume radiance measurements were carried out both during the day and the night by using both the lava lake in the Halema'uma'u crater as a hot source and the sky as a cold background to detect respectively the spectral signatures of volcanic CO2 and SO2 gases. CO2 and SO2 path-concentrations were then obtained from the spectral radiance measurements using a new Partial Least Squares Regression (PLSR)-based inversion algorithm, which was developed as part of this project. Volcanic emission fluxes were determined by combining the path measurements with wind observations, derived directly from the images. Several hours long time-series of volcanic emission fluxes will be presented and the SO2 conversion rates into aerosols will be discussed. The new imaging and inversion technique, discussed here, are novel allowing for continuous CO2 and SO2 plume mapping during both day and night.

Raman Spectroscopic Measurements of Co2 Dissolved in Seawater for Laser Remote Sensing in Water

NASA Astrophysics Data System (ADS)

Somekawa, Toshihiro; Fujita, Masayuki

2016-06-01

We examined the applicability of Raman lidar technique as a laser remote sensing tool in water. The Raman technique has already been used successfully for measurements of CO2 gas dissolved in water and bubbles. Here, the effect of seawater on CO2 Raman spectra has been evaluated. A frequency doubled Q-switched Nd:YAG laser (532 nm) was irradiated to CO2 gas dissolved in a standard seawater. In seawater, the Raman signals at 984 and 1060-1180 cm-1 from SO42- were detected, which shows no spectral interference caused by Raman signals derived from CO2.

Construction of an in vitro primary lung co-culture platform derived from New Zealand white rabbits

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

Powell, Joshua D.; Hess, Becky M.; Hutchison, Janine R.

2015-05-01

We report the construction of an in vitro three dimensional (3D) co-culture platform consisting of differentiated lung epithelial cells and monocytes from New Zealand white rabbits. Rabbit lung epithelial cells were successfully grown at air-liquid interface, produced mucus, and expressed both sialic acid alpha-2,3 and alpha-2,6. Blood-derived CD14+ monocytes were deposited above the epithelial layer resulting in the differentiation of a subset of monocytes into CD11c+ cells within the co-culture. These proof-of-concept findings provide a convenient means to comparatively study in vitro versus in vivo rabbit lung responses as they relate to inhalation or lung-challenge studies.

Dryland Flood-Irrigation and its Impact on CO2 Production and the Accumulation of Pedogenic Carbonate in West Texas

NASA Astrophysics Data System (ADS)

Ortiz, A. C.; Jin, L.

2016-12-01

Agricultural fields in drylands are intensively irrigated. Indeed, pecan orchards at the El Paso, TX region are flooded with over one meter of water per growing season. The waters are usually oversaturated in calcite (CaCO3) and continuous evapotranspiration drives CaCO3 precipitation, releasing CO2. As such, the loading of CaCO3 through flood irrigation in drylands impacts Ca and C cycles greatly. We characterized soil, soil gas and soil water samples to quantify rates of pedogenic carbonate accumulation and CO2 release, identify the sources of C and Ca in pedogenic carbonates, and investigate kinetic and environmental controls of CaCO3 formation. Simple calculations show that up to 112000kg/km2/yr of Ca is loaded onto the fields by irrigation, evidenced by high water-soluble and acid-leachable Ca in soils, especially in clayey soils. We used 87Sr/86Sr ratios to quantify the relative importance of different Ca end-members including flood irrigation. Data show that water-soluble soil leachates have similar 87Sr/86Sr ratios as irrigation waters at depth, but lighter signatures at surface, probably due dust and fertilizer inputs. We measured daily soil-atmosphere CO2 efflux, δ13CCO2 and concentrations of CO2 gas samples at different soil depths between two irrigation events and at two sites with sandy versus clayey soils. These data help determine if sources of soil CO2 change with depth, irrigation event and if CO2 transport is controlled by texture. Correlations of δ13CCO2 and soil CO2 concentrations indicate mixing of organically respired, atmospheric and CaCO3-derived CO2. We found co-variation of δ13CCO2 and soil CO2 with time, where soil CO2 became heavier in carbon isotopes and more abundant in concentrations, illustrating shifts from soil respired CO2, characterized by lighter C, to increased proportions of CaCO3-derived CO2 with heavier C. Efflux data show peak values as soils dried, indicating supersaturation of soil waters and precipitation of pedogenic calcite. This efflux is also controlled by soil texture, as sandy soils emitted more CO2 than clayey soils, even if fine-textured soils contained more CaCO3. These findings can significantly impact CO2 modeling and can aid in extrapolating to larger scales.

Water level, vegetation composition, and plant productivity explain greenhouse gas fluxes in temperate cutover fens after inundation

NASA Astrophysics Data System (ADS)

Minke, Merten; Augustin, Jürgen; Burlo, Andrei; Yarmashuk, Tatsiana; Chuvashova, Hanna; Thiele, Annett; Freibauer, Annette; Tikhonov, Vitalij; Hoffmann, Mathias

2016-07-01

Peat extraction leaves a land surface with a strong relief of deep cutover areas and higher ridges. Rewetting inundates the deep parts, while less deeply extracted zones remain at or above the water level. In temperate fens the flooded areas are colonized by helophytes such as Eriophorum angustifolium, Carex spp., Typha latifolia or Phragmites australis dependent on water depth. Reeds of Typha and Phragmites are reported as large sources of methane, but data on net CO2 uptake are contradictory for Typha and rare for Phragmites. Here, we analyze the effect of vegetation, water level and nutrient conditions on greenhouse gas (GHG) emissions for representative vegetation types along water level gradients at two rewetted cutover fens (mesotrophic and eutrophic) in Belarus. Greenhouse gas emissions were measured campaign-wise with manual chambers every 2 to 4 weeks for 2 years and interpolated by modelling. All sites had negligible nitrous oxide exchange rates. Most sites were carbon sinks and small GHG sources. Methane emissions generally increased with net ecosystem CO2 uptake. Mesotrophic small sedge reeds with water table around the land surface were small GHG sources in the range of 2.3 to 4.2 t CO2 eq. ha-1 yr-1. Eutrophic tall sedge - Typha latifolia reeds on newly formed floating mats were substantial net GHG emitters in the range of 25.1 to 39.1 t CO2 eq. ha-1 yr. They represent transient vegetation stages. Phragmites reeds ranged between -1.7 to 4.2 t CO2 eq. ha-1 yr-1 with an overall mean GHG emission of 1.3 t CO2 eq. ha-1 yr-1. The annual CO2 balance was best explained by vegetation biomass, which includes the role of vegetation composition and species. Methane emissions were obviously driven by biological activity of vegetation and soil organisms. Shallow flooding of cutover temperate fens is a suitable measure to arrive at low GHG emissions. Phragmites australis establishment should be promoted in deeper flooded areas and will lead to moderate, but variable GHG emissions or even occasional sinks. The risk of large GHG emissions is higher for eutrophic than mesotrophic peatlands. Nevertheless, flooding of eutrophic temperate fens still represents a safe GHG mitigation option because even the hotspot of our study, the floating tall sedge - Typha latifolia reeds, did not exceed the typical range of GHG emissions from drained fen grasslands and the spatially dominant Phragmites australis reed emitted by far less GHG than drained fens.

Partial reactive crystallization of variable CO2-bearing siliceous MORB-eclogite-derived melt in fertile peridotite and genesis of alkalic basalts with signatures of crustal recycling

NASA Astrophysics Data System (ADS)

Mallik, A.; Dasgupta, R.

2013-12-01

The presence of heterogeneity in the form of recycled altered oceanic crust (MORB-eclogite) has been proposed in the source of HIMU ocean island basalts (OIBs) [1]. Partial melts of recycled oceanic crust, however, are siliceous and Mg-poor and thus do not resemble the major element compositions of alkalic OIBs that are silica-poor and Mg-rich. In an upwelling heterogenous mantle, MORB-eclogite undergoes melting deeper than volatile-free peridotite, hence, andesitic partial melt derived from eclogite will react with subsolidus peridotite. We have examined the effect of such a melt-rock reaction under volatile-free conditions at 1375 °C, 3 GPa by varying the melt-rock ratio from 8 to 50 wt.% [2]. We concluded that the reacted melts reproduce certain major element characteristics of oceanic basanites, but not nephelinites. Also, the melt-rock reaction produces olivine and garnet-bearing websteritic residue. Because presence of CO2 has been invoked in the source of many HIMU ocean islands, the effect of CO2 on such a melt-rock reaction needs to be evaluated. Accordingly, we performed reaction experiments on mixtures of 25% and 33% CO2-bearing andesitic partial melt and peridotite at 1375 °C, 3 GPa by varying the dissolved CO2 content of the reacting melts from 1 to 5 wt.% (bulk CO2 from 0.25 to 1.6 wt.%) [3, this study]. Owing to melt-rock reaction, with increasing CO2 in the bulk mixture, (a) modes of olivine and cpx decrease while melt, opx and garnet increase, (b) reacted melts evolve to greater degree of Si-undersaturation (from andesite through basanite to nephelinite), (c) enhanced crystallization of garnet take place with higher CO2 in the melt, reducing alumina content of the reacted melts, and (d) CaO and MgO content of the reacted melts increase, without affecting FeO* and Na2O contents (indicating greater propensity of Ca2+ and Mg2+ over Fe2+ and Na+ to enter silicate melt as carbonate). For a given melt-MgO, the CO2-bearing reacted melts are a better match for alkalic basalts in terms of SiO2, Al2O3, CaO and CaO/Al2O3 than the CO2-free ones [3]. Using the experimental data, we have further developed an empirical model to predict mineral modes in residue and reacted melt compositions for olivine-opx saturated lithologies as a function of melt:rock ratio and bulk CO2 content. For example, in case of 5 wt.% eclogite melt infiltrating in fertile peridotite, with bulk CO2 from 0 to 2 wt.%, the derivative melts show an increase in CaO and MgO from 11 to 16 wt.%, 15 to 24 wt.%, respectively and decrease in SiO2 and Al2O3 from 45 to 39 wt.% and 14 to 5 wt.%, respectively. From this model, we have created a major element composition space of MORB-eclogite-derived reactive melt mass vs. bulk CO2 and we predict that primary HIMU-type magmas require <5 to 10 wt.% of MORB-eclogite melt input and up to 0.8 wt.% bulk CO2 in their source. Our model also allows determining the residual lithology at the source of alkalic basalts, produced owing to eclogite melt-peridotite reaction with or without CO2. [1] Jackson & Dasgupta (2008) EPSL 276, 175-186. [2] Mallik & Dasgupta (2012) EPSL 329-330, 97-108. [3] Mallik & Dasgupta (in press) JPetrol.

3D shape recovery from image focus using gray level co-occurrence matrix

NASA Astrophysics Data System (ADS)

Mahmood, Fahad; Munir, Umair; Mehmood, Fahad; Iqbal, Javaid

2018-04-01

Recovering a precise and accurate 3-D shape of the target object utilizing robust 3-D shape recovery algorithm is an ultimate objective of computer vision community. Focus measure algorithm plays an important role in this architecture which convert the color values of each pixel of the acquired 2-D image dataset into corresponding focus values. After convolving the focus measure filter with the input 2-D image dataset, a 3-D shape recovery approach is applied which will recover the depth map. In this document, we are concerned with proposing Gray Level Co-occurrence Matrix along with its statistical features for computing the focus information of the image dataset. The Gray Level Co-occurrence Matrix quantifies the texture present in the image using statistical features and then applies joint probability distributive function of the gray level pairs of the input image. Finally, we quantify the focus value of the input image using Gaussian Mixture Model. Due to its little computational complexity, sharp focus measure curve, robust to random noise sources and accuracy, it is considered as superior alternative to most of recently proposed 3-D shape recovery approaches. This algorithm is deeply investigated on real image sequences and synthetic image dataset. The efficiency of the proposed scheme is also compared with the state of art 3-D shape recovery approaches. Finally, by means of two global statistical measures, root mean square error and correlation, we claim that this approach -in spite of simplicity generates accurate results.

Two-dimensional nitrides as highly efficient potential candidates for CO2 capture and activation.

PubMed

Morales-Salvador, Raul; Morales-García, Ángel; Viñes, Francesc; Illas, Francesc

2018-06-13

The performance of novel two-dimensional nitrides in carbon capture and storage (CCS) is analyzed for a broad range of pressures and temperatures. Employing an integrated theoretical framework where CO2 adsorption/desorption rates on the M2N (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) surfaces are derived from transition state theory and density functional theory based calculations, the present theoretical simulations consistently predict that, depending on the particular composition, CO2 can be strongly adsorbed and even activated at temperatures above 1000 K. For practical purposes, Ti2N, Zr2N, Hf2N, V2N, Nb2N, and Ta2N are predicted as the best suited materials for CO2 activation. Moreover, the estimated CO2 uptake of 2.32-7.96 mol CO2 kg-1 reinforces the potential of these materials for CO2 abatement.

On the thermal behavior of model Li-Li xCoO 2 systems containing ionic liquids in standard electrolyte solutions

NASA Astrophysics Data System (ADS)

Larush, L.; Borgel, V.; Markevich, E.; Haik, O.; Zinigrad, E.; Aurbach, D.; Semrau, G.; Schmidt, M.

We report herein on the possibility of using ionic liquids (ILs) as additives to conventional electrolyte solutions, based on alkyl carbonates and LiPF 6 for attenuating thermal reactions in Li battery systems. As a model, a Li-Li 0.5CoO 2 system was used. The ionic liquids chosen included cations based on derivatives of pyrrolidinium and imidazolium, and the anions bioxalato borate (C 4O 8B -, BOB), (CH 3SO 2) 2N - (TFSI), and PF 3(C 2S 5) 3 - (FAP). The thermal behavior of solutions alone, solutions with Li metal, Li 0.5CoO 2 and Li metal + Li 0.5CoO 2 was studied. It was found that the presence of 10% of ILs, with derivatives of pyrrolidinium cations and FAP or TFSI anions in standard EC-DMC/LiPF 6 solutions, improves considerably the thermal stability of Li 0.5CoO 2 in electrolyte solutions. The onset temperatures of the thermal reactions of Li 0.5CoO 2 with solution species are higher and their heat evolution is considerably lower, when they contain these ionic liquids as additives. This finding opens the door for further studies and optimization of the use of selected ILs as additives that may improve the safety features of Li-ion batteries.

Carbon recycling by cyanobacteria: improving CO2 fixation through chemical production.

PubMed

Zhang, Angela; Carroll, Austin L; Atsumi, Shota

2017-09-01

Atmospheric CO2 levels have reached an alarming level due to industrialization and the burning of fossil fuels. In order to lower the level of atmospheric carbon, strategies to sequester excess carbon need to be implemented. The CO2-fixing mechanism in photosynthetic organisms enables integration of atmospheric CO2 into biomass. Additionally, through exogenous metabolic pathways in these photosynthetic organisms, fixed CO2 can be routed to produce various commodity chemicals that are currently produced from petroleum. This review will highlight studies and modifications to different components of cyanobacterial CO2-fixing systems, as well as the application of these systems toward CO2-derived chemical production. 2,3-Butanediol is given particular focus as one of the most thoroughly studied systems for conversion of CO2 to a bioproduct. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Melting phase relation of nominally anhydrous, carbonated pelitic-eclogite at 2.5-3.0 GPa and deep cycling of sedimentary carbon

NASA Astrophysics Data System (ADS)

Tsuno, Kyusei; Dasgupta, Rajdeep

2011-05-01

We have experimentally investigated melting phase relation of a nominally anhydrous, carbonated pelitic eclogite (HPLC1) at 2.5 and 3.0 GPa at 900-1,350°C in order to constrain the cycling of sedimentary carbon in subduction zones. The starting composition HPLC1 (with 5 wt% bulk CO2) is a model composition, on a water-free basis, and is aimed to represent a mixture of 10 wt% pelagic carbonate unit and 90 wt% hemipelagic mud unit that enter the Central American trench. Sub-solidus assemblage comprises clinopyroxene + garnet + K-feldspar + quartz/coesite + rutile + calcio-ankerite/ankeritess. Solidus temperature is at 900-950°C at 2.5 GPa and at 900-1,000°C at 3.0 GPa, and the near-solidus melt is K-rich granitic. Crystalline carbonates persist only 50-100°C above the solidus and at temperatures above carbonate breakdown, carbon exists in the form of dissolved CO2 in silica-rich melts and as a vapor phase. The rhyodacitic to dacitic partial melt evolves from a K-rich composition at near-solidus condition to K-poor, and Na- and Ca-rich composition with increasing temperature. The low breakdown temperatures of crystalline carbonate in our study compared to those of recent studies on carbonated basaltic eclogite and peridotite owes to Fe-enrichment of carbonates in pelitic lithologies. However, the conditions of carbonate release in our study still remain higher than the modern depth-temperature trajectories of slab-mantle interface at sub-arc depths, suggesting that the release of sedimentary carbonates is unlikely in modern subduction zones. One possible scenario of carbonate release in modern subduction zones is the detachment and advection of sedimentary piles to hotter mantle wedge and consequent dissolution of carbonate in rhyodacitic partial melt. In the Paleo-NeoProterozoic Earth, on the other hand, the hotter slab-surface temperatures at subduction zones likely caused efficient liberation of carbon from subducting sedimentary carbonates. Deeply subducted carbonated sediments, similar to HPLC1, upon encountering a hotter mantle geotherm in the oceanic province can release carbon-bearing melts with high K2O, K2O/TiO2, and high silica, and can contribute to EM2-type ocean island basalts. Generation of EM2-type mantle end-member may also occur through metasomatism of mantle wedge by carbonated metapelite plume-derived partial melts.

Photocatalyst of Perovskite CaTiO3 Nanopowder Synthesized from CaO derived from Snail Shell in Comparison with The Use of CaO and CaCO3

NASA Astrophysics Data System (ADS)

Fatimah, I.; Rahmadianti, Y.; Pudiasari, R. A.

2018-04-01

Calcium titanate belongs to the important group of compounds with a perovskite structure having high dielectric loss for various applications including photocatalysis mechanism. Refer to the principles of green chemistry, in this work preparation of CaTiO3 was conducted by using CaO derived from snail shell. Aim of this research are to study the physicochemical character of perovskite derived from snail shell and its comparison with CaO and CaCO3 as Ca sources. Material preparation was performed by solid reaction of Ca sources with TiO2 under comparison with CaO and CaCO3 precursors. Mixture of Ca sources with TiO2 in certain proportion were ground and calcined at the temperature of 200 °C for 2 hs. Materials were characterized by using X-ray diffractometer (XRD), Fourier Transform-Infra Red (FTIR) and the photocatalytic activity was tested by using methylene blue photooxidation. Perovskite synthesized using CaO derived from snail shell exhibits the similar XRD pattern with that were prepared by using CaO and CaCO3. From the photooxidation activity test, it is proven that CaTiO3 shows similar photocatalytic activity correspond to that were prepared by CaO and CaCO3. Utilazation of shell as agricultural waste of the synthesis of CaTiO3 perovskite is the novelty of this work. Furthermore, the study on material structure and photoactivity is the main focuses for the application in industry and environment.

Synthetic biology for CO2 fixation.

PubMed

Gong, Fuyu; Cai, Zhen; Li, Yin

2016-11-01

Recycling of carbon dioxide (CO 2 ) into fuels and chemicals is a potential approach to reduce CO 2 emission and fossil-fuel consumption. Autotrophic microbes can utilize energy from light, hydrogen, or sulfur to assimilate atmospheric CO 2 into organic compounds at ambient temperature and pressure. This provides a feasible way for biological production of fuels and chemicals from CO 2 under normal conditions. Recently great progress has been made in this research area, and dozens of CO 2 -derived fuels and chemicals have been reported to be synthesized by autotrophic microbes. This is accompanied by investigations into natural CO 2 -fixation pathways and the rapid development of new technologies in synthetic biology. This review first summarizes the six natural CO 2 -fixation pathways reported to date, followed by an overview of recent progress in the design and engineering of CO 2 -fixation pathways as well as energy supply patterns using the concept and tools of synthetic biology. Finally, we will discuss future prospects in biological fixation of CO 2 .

The role of CO2 variability and exposure time for biological impacts of ocean acidification

NASA Astrophysics Data System (ADS)

Shaw, Emily C.; Munday, Philip L.; McNeil, Ben I.

2013-09-01

impacts of ocean acidification have mostly been studied using future levels of CO2 without consideration of natural variability or how this modulates both duration and magnitude of CO2 exposure. Here we combine results from laboratory studies on coral reef fish with diurnal in situ CO2 data from a shallow coral reef, to demonstrate how natural variability alters exposure times for marine organisms under increasingly high-CO2 conditions. Large in situ CO2 variability already results in exposure of coral reef fish to short-term CO2 levels higher than laboratory-derived critical CO2 levels (~600 µatm). However, we suggest that the in situ exposure time is presently insufficient to induce negative effects observed in laboratory studies. Our results suggest that both exposure time and the magnitude of CO2 levels will be important in determining the response of organisms to future ocean acidification, where both will increase markedly with future increases in CO2.

Introducing and Validating the New Aura CO Product Derived from Joined TES and MLS Measurements

NASA Astrophysics Data System (ADS)

Luo, M.; Schwartz, M. J.; Read, W. G.; Herman, R. L.; Kulawik, S. S.; Worden, J.; Livesey, N. J.; Bowman, K. W.; Sweeney, C.

2014-12-01

The new Aura CO product consists of CO vertical profiles derived from TES and MLS measurements. This product has been released to the public. We describe the algorithms for generating the product and the evaluations of it using in-situ measurements. TES and MLS standalone CO profile retrievals are sensitive respectively to lower-mid troposphere and upper troposphere and above. We pair TES nadir and MLS limb tangent locations within 6-8 min and less than 220 km. The paired radiance measurements of the two instruments per location are optimally combined to retrieve a single CO profile along with other interfering species. This combined CO profile has improved vertical resolution and vertical range over the two standalone products, especially in the upper-troposphere/lower-stratosphere. For example, the degree of freedom for signal (DOFS) between surface and 50hPa for TES alone is < 2, and for the combined CO profiles is 2-4. We will present the comparison results between the Aura CO and AirCore, HIPPO, and MOZAIC observations. The new Aura CO product provides a unique data set to studies on tropospheric transport of air pollutants and troposphere-stratospheric exchange processes.

Carbonate-derived CO 2 purging magma at depth: Influence on the eruptive activity of Somma-Vesuvius, Italy

NASA Astrophysics Data System (ADS)

Dallai, Luigi; Cioni, Raffaello; Boschi, Chiara; D'Oriano, Claudia

2011-10-01

Mafic phenocrysts from selected products of the last 4 ka volcanic activity at Mt. Vesuvius were investigated for their chemical and O-isotope composition, as a proxy for primary magmas feeding the system. 18O/ 16O ratios of studied Mg-rich olivines suggest that near-primary shoshonitic to tephritic melts experienced a flux of sedimentary carbonate-derived CO 2, representing the early process of magma contamination in the roots of the volcanic structure. Bulk carbonate assimilation (physical digestion) mainly occurred in the shallow crust, strongly influencing magma chamber evolution. On a petrological and geochemical basis the effects of bulk sedimentary carbonate digestion on the chemical composition of the near-primary melts are resolved from those of carbonate-released CO 2 fluxed into magma. An important outcome of this process lies in the effect of external CO 2 in changing the overall volatile solubility of the magma, enhancing the ability of Vesuvius mafic magmas to rapidly rise and explosively erupt at the surface.

A gas chromatograph system for semi-continuous greenhouse gas measurements at Puy de Dôme station, Central France

NASA Astrophysics Data System (ADS)

Lopez, M.; Schmidt, M.; Ramonet, M.; Bonne, J.-L.; Colomb, A.; Kazan, V.; Laj, P.; Pichon, J.-M.

2015-03-01

Three years of greenhouse gases measurements, obtained using a gas chromatograph (GC) system located at the Puy de Dôme station at 1465 m a.s.l. in Central France are presented. The GC system was installed in 2010 at Puy de Dôme and was designed for automatic and accurate semi-continuous measurements of atmospheric carbon dioxide, methane, nitrous oxide and sulfur hexafluoride mole fractions. We present in detail the instrumental set up and the calibration strategy, which together allow the GC to reach repeatabilities of 0.1 μmol mol-1, 1.2, 0.3 nmol mol-1 and 0.06 pmol mol-1 for CO2, CH4, N2O and SF6, respectively. Comparisons of the atmospheric time series with those obtained using other instruments shown that the GC system meets the World Meteorological Organization recommendations. The analysis of the three-year atmospheric time series revealed how the planetary boundary layer height drives the mole fractions observed at a mountain site such as Puy de Dôme where air masses alternate between the planetary boundary layer and the free troposphere. Accurate long-lived greenhouse gases measurements collocated with 222Rn measurements as an atmospheric tracer, allowed us to determine the CO2, CH4 and N2O emissions in the catchment area of the station. The derived CO2 surface flux revealed a clear seasonal cycle with net uptake by plant assimilation in the spring and net emission caused by the biosphere and burning of fossil fuel during the remainder of the year. We calculated a mean annual CO2 flux of 1150 t(CO2) km-2. The derived CH4 and N2O emissions in the station catchment area were 5.6 t(CH4) km-2 yr-1 and 1.5 t(N2O) km-2 yr-1, respectively. Our derived annual CH4 flux is in agreement with the national French inventory, whereas our derived N2O flux is five times larger than the same inventory.

Estimation of the geothermal potential of the Caldara di Manziana site in the Mts Sabatini Volcanic District (Central Italy) by integrating geochemical data and 3D-GIS modelling.

NASA Astrophysics Data System (ADS)

Ranaldi, Massimo; Lelli, Matteo; Tarchini, Luca; Carapezza, Maria Luisa; Patera, Antonio

2016-04-01

High-enthalpy geothermal fields of Central Italy are hosted in deeply fractured carbonate reservoirs occurring in thermally anomalous and seismically active zones. However, the Mts. Sabatini volcanic district, located north of Rome, has an interesting deep temperatures (T), but it is characterized by low to very low seismicity and permeability in the reservoir rocks (mostly because of hydrothermal self-sealing processes). Low PCO2 facilitates the complete sealing of the reservoir fractures, preventing hot fluids rising and, determining a low CO2 flux at the surface. Conversely, high CO2 flux generally reflects a high pressure of CO2, suggesting that an active geothermal reservoir is present at depth. In Mts. Sabatini district, the Caldara of Manziana (CM) is the only zone characterized by a very high CO2 flux (188 tons/day) from a surface of 0.15 km2) considering both the diffuse and viscous CO2 emission. This suggests the likely presence of an actively degassing geothermal reservoir at depth. Emitted gas is dominated by CO2 (>97 vol.%). Triangular irregular networks (TINs) have been used to represent the morphology of the bottom of the surficial volcanic deposits, the thickness of the impervious formation and the top of the geothermal reservoir. The TINs, integrated by T-gradient and deep well data, allowed to estimate the depth and the temperature of the top of the geothermal reservoir, respectively to ~-1000 m from the surface and to ~130°C. These estimations are fairly in agreement with those obtained by gas chemistry (818

Longitudinal target-spin asymmetries for deeply virtual compton scattering.

PubMed

Seder, E; Biselli, A; Pisano, S; Niccolai, S; Smith, G D; Joo, K; Adhikari, K; Amaryan, M J; Anderson, M D; Anefalos Pereira, S; Avakian, H; Battaglieri, M; Bedlinskiy, I; Bono, J; Boiarinov, S; Bosted, P; Briscoe, W; Brock, J; Brooks, W K; Bültmann, S; Burkert, V D; Carman, D S; Carlin, C; Celentano, A; Chandavar, S; Charles, G; Colaneri, L; Cole, P L; Contalbrigo, M; Crabb, D; Crede, V; D'Angelo, A; Dashyan, N; De Vita, R; De Sanctis, E; Deur, A; Djalali, C; Doughty, D; Dupre, R; El Fassi, L; Elouadrhiri, L; Eugenio, P; Fedotov, G; Fegan, S; Filippi, A; Fleming, J A; Fradi, A; Garillon, B; Garçon, M; Gevorgyan, N; Ghandilyan, Y; Giovanetti, K L; Girod, F X; Goetz, J T; Gohn, W; Gothe, R W; Griffioen, K A; Guegan, B; Guidal, M; Guo, L; Hafidi, K; Hakobyan, H; Hanretty, C; Harrison, N; Hattawy, M; Hirlinger Saylor, N; Holtrop, M; Hughes, S M; Ilieva, Y; Ireland, D G; Ishkhanov, B S; Isupov, E L; Jo, H S; Joosten, S; Keith, C D; Keller, D; Khachatryan, G; Khandaker, M; Kim, A; Kim, W; Klein, A; Klein, F J; Koirala, S; Kubarovsky, V; Kuhn, S E; Lenisa, P; Livingston, K; Lu, H Y; MacGregor, I J D; Markov, N; Mayer, M; McKinnon, B; Meekins, D G; Mineeva, T; Mirazita, M; Mokeev, V; Montgomery, R; Moody, C I; Moutarde, H; Movsisyan, A; Munoz Camacho, C; Nadel-Turonski, P; Niculescu, I; Osipenko, M; Ostrovidov, A I; Paolone, M; Pappalardo, L L; Park, K; Park, S; Pasyuk, E; Peng, P; Phelps, W; Pogorelko, O; Price, J W; Prok, Y; Protopopescu, D; Puckett, A J R; Ripani, M; Rizzo, A; Rosner, G; Rossi, P; Roy, P; Sabatié, F; Salgado, C; Schott, D; Schumacher, R A; Senderovich, I; Simonyan, A; Skorodumina, I; Sokhan, D; Sparveris, N; Stepanyan, S; Stoler, P; Strakovsky, I I; Strauch, S; Sytnik, V; Taiuti, M; Tang, W; Tian, Y; Ungaro, M; Voskanyan, H; Voutier, E; Walford, N K; Watts, D P; Wei, X; Weinstein, L B; Wood, M H; Zachariou, N; Zana, L; Zhang, J; Zonta, I

2015-01-23

A measurement of the electroproduction of photons off protons in the deeply inelastic regime was performed at Jefferson Lab using a nearly 6 GeV electron beam, a longitudinally polarized proton target, and the CEBAF Large Acceptance Spectrometer. Target-spin asymmetries for ep→e^{'}p^{'}γ events, which arise from the interference of the deeply virtual Compton scattering and the Bethe-Heitler processes, were extracted over the widest kinematics in Q^{2}, x_{B}, t, and ϕ, for 166 four-dimensional bins. In the framework of generalized parton distributions, at leading twist the t dependence of these asymmetries provides insight into the spatial distribution of the axial charge of the proton, which appears to be concentrated in its center. These results also bring important and necessary constraints for the existing parametrizations of chiral-even generalized parton distributions.

Longitudinal Target-Spin Asymmetries for Deeply Virtual Compton Scattering

NASA Astrophysics Data System (ADS)

Seder, E.; Biselli, A.; Pisano, S.; Niccolai, S.; Smith, G. D.; Joo, K.; Adhikari, K.; Amaryan, M. J.; Anderson, M. D.; Anefalos Pereira, S.; Avakian, H.; Battaglieri, M.; Bedlinskiy, I.; Bono, J.; Boiarinov, S.; Bosted, P.; Briscoe, W.; Brock, J.; Brooks, W. K.; Bültmann, S.; Burkert, V. D.; Carman, D. S.; Carlin, C.; Celentano, A.; Chandavar, S.; Charles, G.; Colaneri, L.; Cole, P. L.; Contalbrigo, M.; Crabb, D.; Crede, V.; D'Angelo, A.; Dashyan, N.; De Vita, R.; De Sanctis, E.; Deur, A.; Djalali, C.; Doughty, D.; Dupre, R.; El Fassi, L.; Elouadrhiri, L.; Eugenio, P.; Fedotov, G.; Fegan, S.; Filippi, A.; Fleming, J. A.; Fradi, A.; Garillon, B.; Garçon, M.; Gevorgyan, N.; Ghandilyan, Y.; Giovanetti, K. L.; Girod, F. X.; Goetz, J. T.; Gohn, W.; Gothe, R. W.; Griffioen, K. A.; Guegan, B.; Guidal, M.; Guo, L.; Hafidi, K.; Hakobyan, H.; Hanretty, C.; Harrison, N.; Hattawy, M.; Hirlinger Saylor, N.; Holtrop, M.; Hughes, S. M.; Ilieva, Y.; Ireland, D. G.; Ishkhanov, B. S.; Isupov, E. L.; Jo, H. S.; Joosten, S.; Keith, C. D.; Keller, D.; Khachatryan, G.; Khandaker, M.; Kim, A.; Kim, W.; Klein, A.; Klein, F. J.; Koirala, S.; Kubarovsky, V.; Kuhn, S. E.; Lenisa, P.; Livingston, K.; Lu, H. Y.; MacGregor, I. J. D.; Markov, N.; Mayer, M.; McKinnon, B.; Meekins, D. G.; Mineeva, T.; Mirazita, M.; Mokeev, V.; Montgomery, R.; Moody, C. I.; Moutarde, H.; Movsisyan, A.; Munoz Camacho, C.; Nadel-Turonski, P.; Niculescu, I.; Osipenko, M.; Ostrovidov, A. I.; Paolone, M.; Pappalardo, L. L.; Park, K.; Park, S.; Pasyuk, E.; Peng, P.; Phelps, W.; Pogorelko, O.; Price, J. W.; Prok, Y.; Protopopescu, D.; Puckett, A. J. R.; Ripani, M.; Rizzo, A.; Rosner, G.; Rossi, P.; Roy, P.; Sabatié, F.; Salgado, C.; Schott, D.; Schumacher, R. A.; Senderovich, I.; Simonyan, A.; Skorodumina, I.; Sokhan, D.; Sparveris, N.; Stepanyan, S.; Stoler, P.; Strakovsky, I. I.; Strauch, S.; Sytnik, V.; Taiuti, M.; Tang, W.; Tian, Y.; Ungaro, M.; Voskanyan, H.; Voutier, E.; Walford, N. K.; Watts, D. P.; Wei, X.; Weinstein, L. B.; Wood, M. H.; Zachariou, N.; Zana, L.; Zhang, J.; Zonta, I.; CLAS Collaboration

2015-01-01

A measurement of the electroproduction of photons off protons in the deeply inelastic regime was performed at Jefferson Lab using a nearly 6 GeV electron beam, a longitudinally polarized proton target, and the CEBAF Large Acceptance Spectrometer. Target-spin asymmetries for e p →e'p'γ events, which arise from the interference of the deeply virtual Compton scattering and the Bethe-Heitler processes, were extracted over the widest kinematics in Q2 , xB, t , and ϕ , for 166 four-dimensional bins. In the framework of generalized parton distributions, at leading twist the t dependence of these asymmetries provides insight into the spatial distribution of the axial charge of the proton, which appears to be concentrated in its center. These results also bring important and necessary constraints for the existing parametrizations of chiral-even generalized parton distributions.

Deep permeable fault-controlled helium transport and limited mantle flux in two extensional geothermal systems in the Great Basin, United States

USGS Publications Warehouse

Banerjee, Amlan; Person, Mark; Hofstra, Albert; Sweetkind, Donald S.; Cohen, Denis; Sabin, Andrew; Unruh, Jeff; Zyvoloski, George; Gable, Carl W.; Crossey, Laura; Karlstrom, Karl

2011-01-01

This study assesses the relative importance of deeply circulating meteoric water and direct mantle fluid inputs on near-surface 3He/4He anomalies reported at the Coso and Beowawe geothermal fields of the western United States. The depth of meteoric fluid circulation is a critical factor that controls the temperature, extent of fluid-rock isotope exchange, and mixing with deeply sourced fluids containing mantle volatiles. The influence of mantle fluid flux on the reported helium anomalies appears to be negligible in both systems. This study illustrates the importance of deeply penetrating permeable fault zones (10-12 to 10-15 m2) in focusing groundwater and mantle volatiles with high 3He/4He ratios to shallow crustal levels. These continental geothermal systems are driven by free convection.

The Nature of Deeply Buried Ultraluminous Infrared Galaxies: A Unified Model for Highly Obscured Dusty Galaxy Emission

NASA Astrophysics Data System (ADS)

Marshall, J. A.; Elitzur, M.; Armus, L.; Diaz-Santos, T.; Charmandaris, V.

2018-05-01

We present models of deeply buried ultraluminous infrared galaxy (ULIRG) spectral energy distributions (SEDs) and use them to construct a three-dimensional diagram for diagnosing the nature of observed ULIRGs. Our goal is to construct a suite of SEDs for a very simple model ULIRG structure, and to explore how well this simple model can (by itself) explain the full range of observed ULIRG properties. We use our diagnostic to analyze archival Spitzer Space Telescope Infrared Spectrograph data of ULIRGs and find that: (1) in general, our model does provide a comprehensive explanation of the distribution of mid-IR ULIRG properties; (2) >75% (in some cases 100%) of the bolometric luminosities of the most deeply buried ULIRGs must be powered by a dust-enshrouded active galactic nucleus; (3) an unobscured “keyhole” view through ≲10% of the obscuring medium surrounding a deeply buried ULIRG is sufficient to make it appear nearly unobscured in the mid-IR; (4) the observed absence of deeply buried ULIRGs with large polycyclic aromatic hydrocarbon (PAH) equivalent widths is naturally explained by our models, showing that deep absorption features are “filled-in” by small quantities of foreground unobscured PAH emission (e.g., from the host galaxy disk) at the level of ∼1% the bolometric nuclear luminosity. The modeling and analysis we present will also serve as a powerful tool for interpreting the high angular resolution spectra of high-redshift sources to be obtained with the James Webb Space Telescope.

Active-site models for the nickel-iron hydrogenases: effects of ligands on reactivity and catalytic properties.

PubMed

Carroll, Maria E; Barton, Bryan E; Gray, Danielle L; Mack, Amanda E; Rauchfuss, Thomas B

2011-10-03

Described are new derivatives of the type [HNiFe(SR)(2)(diphosphine)(CO)(3)](+), which feature a Ni(diphosphine) group linked to a Fe(CO)(3) group by two bridging thiolate ligands. Previous work had described [HNiFe(pdt)(dppe)(CO)(3)](+) ([1H](+)) and its activity as a catalyst for the reduction of protons (J. Am. Chem. Soc. 2010, 132, 14877). Work described in this paper focuses on the effects on properties of NiFe model complexes of the diphosphine attached to nickel as well as the dithiolate bridge, 1,3-propanedithiolate (pdt) vs 1,2-ethanedithiolate (edt). A new synthetic route to these Ni-Fe dithiolates is described, involving reaction of Ni(SR)(2)(diphosphine) with FeI(2)(CO)(4) followed by in situ reduction with cobaltocene. Evidence is presented that this route proceeds via a metastable μ-iodo derivative. Attempted isolation of such species led to the crystallization of NiFe(Me(2)pdt)(dppe)I(2), which features tetrahedral Fe(II) and square planar Ni(II) centers (H(2)Me(2)pdt = 2,2-dimethylpropanedithiol). The new tricarbonyls prepared in this work are NiFe(pdt)(dcpe)(CO)(3) (2, dcpe = 1,2-bis(dicyclohexylphosphino)ethane), NiFe(edt)(dppe)(CO)(3) (3), and NiFe(edt)(dcpe)(CO)(3) (4). Attempted preparation of a phenylthiolate-bridged complex via the FeI(2)(CO)(4) + Ni(SPh)(2)(dppe) route gave the tetrametallic species [(CO)(2)Fe(SPh)(2)Ni(CO)](2)(μ-dppe)(2). Crystallographic analysis of the edt-dcpe compund [2H]BF(4) and the edt-dppe compound [3H]BF(4) verified their close resemblance. Each features pseudo-octahedral Fe and square pyramidal Ni centers. Starting from [3H]BF(4) we prepared the PPh(3) derivative [HNiFe(edt)(dppe)(PPh(3))(CO)(2)]BF(4) ([5H]BF(4)), which was obtained as a ∼2:1 mixture of unsymmetrical and symmetrical isomers. Acid-base measurements indicate that changing from Ni(dppe) (dppe = Ph(2)PCH(2)CH(2)PPh(2)) to Ni(dcpe) decreases the acidity of the cationic hydride complexes by 2.5 pK(a)(PhCN) units, from ∼11 to ∼13.5 (previous work showed that substitution at Fe leads to more dramatic effects). The redox potentials are more strongly affected by the change from dppe to dcpe, for example the [2](0/+) couple occurs at E(1/2) = -820 for [2](0/+) vs -574 mV (vs Fc(+/0)) for [1](0/+). Changes in the dithiolate do not affect the acidity or the reduction potentials of the hydrides. The acid-independent rate of reduction of CH(2)ClCO(2)H by [2H](+) is about 50 s(-1) (25 °C), twice that of [1H](+). The edt-dppe complex [2H](+) proved to be the most active catalyst, with an acid-independent rate of 300 s(-1).

Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

NASA Astrophysics Data System (ADS)

Wiegel, Aaron A.; Cole, Amanda S.; Hoag, Katherine J.; Atlas, Elliot L.; Schauffler, Sue M.; Boering, Kristie A.

2013-10-01

We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the 17O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O(1D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of 17O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

CO EMISSION IN OPTICALLY OBSCURED (TYPE-2) QUASARS AT REDSHIFTS z Almost-Equal-To 0.1-0.4

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

Krips, M.; Neri, R.; Cox, P., E-mail: krips@iram.fr, E-mail: neri@iram.fr, E-mail: cox@iram.fr

We present a search for CO emission in a sample of 10 type-2 quasar host galaxies with redshifts of z Almost-Equal-To 0.1-0.4. We detect CO(J = 1-0) line emission with {>=}5{sigma} in the velocity integrated intensity maps of five sources. A sixth source shows a tentative detection at the {approx}4.5{sigma} level of its CO(J = 1-0) line emission. The CO emission of all six sources is spatially coincident with the position at optical, infrared, or radio wavelengths. The spectroscopic redshifts derived from the CO(J = 1-0) line are very close to the photometric ones for all five detections except formore » the tentative detection for which we find a much larger discrepancy. We derive gas masses of {approx}(2-16) Multiplication-Sign 10{sup 9} M{sub Sun} for the CO emission in the six detected sources, while we constrain the gas masses to upper limits of M{sub gas} {<=} 8 Multiplication-Sign 10{sup 9} M{sub Sun} for the four non-detections. These values are of the order or slightly lower than those derived for type-1 quasars. The line profiles of the CO(J = 1-0) emission are rather narrow ({approx}<300 km s{sup -1}) and single peaked, unveiling no typical signatures for current or recent merger activity, and are comparable to that of type-1 quasars. However, at least one of the observed sources shows a tidal-tail-like emission in the optical that is indicative of an ongoing or past merging event. We also address the problem of detecting spurious {approx}5{sigma} emission peaks within the field of view.« less

Emissions of mercury in southern Africa derived from long-term observations at Cape Point, South Africa

NASA Astrophysics Data System (ADS)

Brunke, E.-G.; Ebinghaus, R.; Kock, H. H.; Labuschagne, C.; Slemr, F.

2012-08-01

Mercury emissions in South Africa have so far been estimated only by a bottom-up approach from activities and emission factors for different processes. In this paper we derive GEM/CO (GEM being gaseous elemental mercury, Hg0), GEM/CO2, GEM/CH4, CO/CO2, CH4/CO2, and CH4/CO emission ratios from plumes observed during long-term monitoring of these species at Cape Point between March 2007 and December 2009. The average observed GEM/CO, GEM/CO2, GEM/CH4, CO/CO2, CH4/CO2, and CH4/CO emission ratios were 2.40 ± 2.65 pg m-3 ppb-1 (n = 47), 62.7 ± 80.2 pg m-3 ppm-1 (n = 44), 3.61 ± 4.66 pg m-3 ppb-1 (n = 46), 35.6 ± 25.4 ppb ppm-1 (n = 52), 20.2 ± 15.5 ppb ppm-1 (n = 48), and 0.876 ± 1.106 ppb ppb-1 (n = 42), respectively. The observed CO/CO2, CH4/CO2, and CH4/CO emission ratios agree within the combined uncertainties of the observations and emissions with the ratios calculated from EDGAR (version 4.2) CO2, CO, and CH4 inventories for South Africa and southern Africa (South Africa, Lesotho, Swaziland, Namibia, Botswana, Zimbabwe, and Mozambique) in 2007 and 2008 (inventories for 2009 are not available yet). Total elemental mercury emission of 13.1, 15.2, and 16.1 t Hg yr-1 are estimated independently using the GEM/CO, GEM/CO2, and GEM/CH4 emission ratios and the annual mean CO, CO2, and CH4 emissions, respectively, of South Africa in 2007 and 2008. The average of these independent estimates of 14.8 t GEM yr-1 is much less than the total emission of 257 t Hg yr-1 shown by older inventories which are now considered to be wrong. Considering the uncertainties of our emission estimate, of the emission inventories, and the fact that emission of GEM represents 50-78 % of all mercury emissions, our estimate is comparable to the currently cited GEM emissions in 2004 and somewhat smaller than emissions in 2006. A further increase of mercury emissions due to increasing electricity consumption will lead to a more pronounced difference. A quantitative assessment of the difference and its significance, however, will require emission inventories for the years of observations (2007-2009) as well as better data on the speciation of the total mercury emissions in South Africa.

Spatially-controlled NiCo2O4@MnO2 core–shell nanoarray with hollow NiCo2O4 cores and MnO2 flake shells: an efficient catalyst for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Xue, Hairong; Yu, Hongjie; Li, Yinghao; Deng, Kai; Xu, You; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-07-01

Control of structures and components of the nanoarray catalysts is very important for electrochemical energy conversion. Herein, unique NiCo2O4@MnO2 core–shell nanoarray with hollow NiCo2O4 Cores and MnO2 flake shells is in situ fabricated on carbon textile via a two-step hydrothermal treatment followed by a subsequent annealing. The as-made nanoarray is highly active and durable catalyst for oxygen evolution reaction in alkaline media attribute to the synergetic effect derived from spatially separated nanoarray with favorable NiCo2O4 and MnO2 compositions.

Spatially-controlled NiCo2O4@MnO2 core-shell nanoarray with hollow NiCo2O4 cores and MnO2 flake shells: an efficient catalyst for oxygen evolution reaction.

PubMed

Xue, Hairong; Yu, Hongjie; Li, Yinghao; Deng, Kai; Xu, You; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-07-13

Control of structures and components of the nanoarray catalysts is very important for electrochemical energy conversion. Herein, unique NiCo 2 O 4 @MnO 2 core-shell nanoarray with hollow NiCo 2 O 4 Cores and MnO 2 flake shells is in situ fabricated on carbon textile via a two-step hydrothermal treatment followed by a subsequent annealing. The as-made nanoarray is highly active and durable catalyst for oxygen evolution reaction in alkaline media attribute to the synergetic effect derived from spatially separated nanoarray with favorable NiCo 2 O 4 and MnO 2 compositions.

Solar energy utilization in the direct photocarboxylation of 2,3-dihydrofuran using CO2.

PubMed

Aresta, Michele; Dibenedetto, Angela; Baran, Tomasz; Wojtyła, Szymon; Macyk, Wojciech

2015-01-01

The conversion of CO2 into high energy products (fuels) and the direct carboxylation of C-H bonds require a high energy input. Energy cannot be derived from fossil carbon, in this case. Solar energy can be used instead, with a low environmental impact and good profit. We have studied the use of white light or solar energy in the photoreduction of CO2 and in photocarboxylation reactions, using different semiconductors modified at their surface. Two examples of reduction of CO2 to methanol and CO will be shortly discussed, and two cases of carboxylation of organic substrates. The case of carboxylation of 2,3-dihydrofuran will be discussed in detail.

Optimization of A 2-Micron Laser Frequency Stabilization System for a Double-Pulse CO2 Differential Absorption Lidar

NASA Technical Reports Server (NTRS)

Chen, Songsheng; Yu, Jirong; Bai, Yingsin; Koch, Grady; Petros, Mulugeta; Trieu, Bo; Petzar, Paul; Singh, Upendra N.; Kavaya, Michael J.; Beyon, Jeffrey

2010-01-01

A carbon dioxide (CO2) Differential Absorption Lidar (DIAL) for accurate CO2 concentration measurement requires a frequency locking system to achieve high frequency locking precision and stability. We describe the frequency locking system utilizing Frequency Modulation (FM), Phase Sensitive Detection (PSD), and Proportional Integration Derivative (PID) feedback servo loop, and report the optimization of the sensitivity of the system for the feed back loop based on the characteristics of a variable path-length CO2 gas cell. The CO2 gas cell is characterized with HITRAN database (2004). The method can be applied for any other frequency locking systems referring to gas absorption line.

RE-EXAMINING LARSON'S SCALING RELATIONSHIPS IN GALACTIC MOLECULAR CLOUDS

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

Heyer, Mark; Krawczyk, Coleman; Duval, Julia

The properties of Galactic molecular clouds tabulated by Solomon et al. (SRBY) are re-examined using the Boston University-FCRAO Galactic Ring Survey of {sup 13}CO J = 1-0 emission. These new data provide a lower opacity tracer of molecular clouds and improved angular and spectral resolution compared with previous surveys of molecular line emission along the Galactic Plane. We calculate giant molecular cloud (GMC) masses within the SRBY cloud boundaries assuming local thermodynamic equilibrium (LTE) conditions throughout the cloud and a constant H{sub 2} to {sup 13}CO abundance, while accounting for the variation of the {sup 12}C/{sup 13}C with galactocentric radius.more » The LTE-derived masses are typically five times smaller than the SRBY virial masses. The corresponding median mass surface density of molecular hydrogen for this sample is 42 M{sub sun} pc{sup -2}, which is significantly lower than the value derived by SRBY (median 206 M{sub sun} pc{sup -2}) that has been widely adopted by most models of cloud evolution and star formation. This discrepancy arises from both the extrapolation by SRBY of velocity dispersion, size, and CO luminosity to the 1 K antenna temperature isophote that likely overestimates the GMC masses and our assumption of constant {sup 13}CO abundance over the projected area of each cloud. Owing to the uncertainty of molecular abundances in the envelopes of clouds, the mass surface density of GMCs could be larger than the values derived from our {sup 13}CO measurements. From velocity dispersions derived from the {sup 13}CO data, we find that the coefficient of the cloud structure functions, v{sup 0} = {sigma}{sub v}/R {sup 1/2}, is not constant, as required to satisfy Larson's scaling relationships, but rather systematically varies with the surface density of the cloud as {approx}{sigma}{sup 0.5} as expected for clouds in self-gravitational equilibrium.« less

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

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopymore » at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. Finally, this latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.« less

Extraction of microalgae derived lipids with supercritical carbon dioxide in an industrial relevant pilot plant.

PubMed

Lorenzen, Jan; Igl, Nadine; Tippelt, Marlene; Stege, Andrea; Qoura, Farah; Sohling, Ulrich; Brück, Thomas

2017-06-01

Microalgae are capable of producing up to 70% w/w triglycerides with respect to their dry cell weight. Since microalgae utilize the greenhouse gas CO 2 , they can be cultivated on marginal lands and grow up to ten times faster than terrestrial plants, the generation of algae oils is a promising option for the development of sustainable bioprocesses, that are of interest for the chemical lubricant, cosmetic and food industry. For the first time we have carried out the optimization of supercritical carbon dioxide (SCCO 2 ) mediated lipid extraction from biomass of the microalgae Scenedesmus obliquus and Scenedesmus obtusiusculus under industrrially relevant conditions. All experiments were carried out in an industrial pilot plant setting, according to current ATEX directives, with batch sizes up to 1.3 kg. Different combinations of pressure (7-80 MPa), temperature (20-200 °C) and CO 2 to biomass ratio (20-200) have been tested on the dried biomass. The most efficient conditions were found to be 12 MPa pressure, a temperature of 20 °C and a CO 2 to biomass ratio of 100, resulting in a high extraction efficiency of up to 92%. Since the optimized CO 2 extraction still yields a crude triglyceride product that contains various algae derived contaminants, such as chlorophyll and carotenoids, a very effective and scalable purification procedure, based on cost efficient bentonite based adsorbers, was devised. In addition to the sequential extraction and purification procedure, we present a consolidated online-bleaching procedure for algae derived oils that is realized within the supercritical CO 2 extraction plant.

Atmospheric CO2 Column Measurements with an Airborne Intensity-Modulated Continuous-Wave 1.57-micron Fiber Laser Lidar

NASA Technical Reports Server (NTRS)

Dobler, Jeremy T.; Harrison, F. Wallace; Browell, Edward V.; Lin, Bing; McGregor, Doug; Kooi, Susan; Choi, Yonghoon; Ismail, Syed

2013-01-01

The 2007 National Research Council (NRC) Decadal Survey on Earth Science and Applications from Space recommended Active Sensing of CO2 Emissions over Nights, Days, and Seasons (ASCENDS) as a mid-term, Tier II, NASA space mission. ITT Exelis, formerly ITT Corp., and NASA Langley Research Center have been working together since 2004 to develop and demonstrate a prototype Laser Absorption Spectrometer for making high-precision, column CO2 mixing ratio measurements needed for the ASCENDS mission. This instrument, called the Multifunctional Fiber Laser Lidar (MFLL), operates in an intensity-modulated, continuous-wave mode in the 1.57- micron CO2 absorption band. Flight experiments have been conducted with the MFLL on a Lear-25, UC-12, and DC-8 aircraft over a variety of different surfaces and under a wide range of atmospheric conditions. Very high-precision CO2 column measurements resulting from high signal-to-noise (great than 1300) column optical depth measurements for a 10-s (approximately 1 km) averaging interval have been achieved. In situ measurements of atmospheric CO2 profiles were used to derive the expected CO2 column values, and when compared to the MFLL measurements over desert and vegetated surfaces, the MFLL measurements were found to agree with the in situ-derived CO2 columns to within an average of 0.17% or approximately 0.65 ppmv with a standard deviation of 0.44% or approximately 1.7 ppmv. Initial results demonstrating ranging capability using a swept modulation technique are also presented.

Supercritical carbon dioxide extracted extracellular matrix material from adipose tissue.

PubMed

Wang, Jun Kit; Luo, Baiwen; Guneta, Vipra; Li, Liang; Foo, Selin Ee Min; Dai, Yun; Tan, Timothy Thatt Yang; Tan, Nguan Soon; Choong, Cleo; Wong, Marcus Thien Chong

2017-06-01

Adipose tissue is a rich source of extracellular matrix (ECM) material that can be isolated by delipidating and decellularizing the tissue. However, the current delipidation and decellularization methods either involve tedious and lengthy processes or require toxic chemicals, which may result in the elimination of vital proteins and growth factors found in the ECM. Hence, an alternative delipidation and decellularization method for adipose tissue was developed using supercritical carbon dioxide (SC-CO 2 ) that eliminates the need of any harsh chemicals and also reduces the amount of processing time required. The resultant SC-CO 2 -treated ECM material showed an absence of nuclear content but the preservation of key proteins such as collagen Type I, collagen Type III, collagen Type IV, elastin, fibronectin and laminin. In addition, other biological factors such as glycosaminoglycans (GAGs) and growth factors such as basic fibroblast growth factor (bFGF) and vascular endothelial growth factor (VEGF) were also retained. Subsequently, the resulting SC-CO 2 -treated ECM material was used as a bioactive coating on tissue culture plastic (TCP). Four different cell types including adipose tissue-derived mesenchymal stem cells (ASCs), human umbilical vein endothelial cells (HUVECs), immortalized human keratinocyte (HaCaT) cells and human monocytic leukemia cells (THP-1) were used in this study to show that the SC-CO 2 -treated ECM coating can be potentially used for various biomedical applications. The SC-CO 2 -treated ECM material showed improved cell-material interactions for all cell types tested. In addition, in vitro scratch wound assay using HaCaT cells showed that the presence of SC-CO 2 -treated ECM material enhanced keratinocyte migration whilst the in vitro cellular studies using THP-1-derived macrophages showed that the SC-CO 2 -treated ECM material did not evoke pro-inflammatory responses from the THP-1-derived macrophages. Overall, this study shows the efficacy of SC-CO 2 method for delipidation and decellularization of adipose tissue whilst retaining its ECM and its subsequent utilization as a bioactive surface coating material for soft tissue engineering, angiogenesis and wound healing applications. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

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

2013-05-01

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

Photosynthetic conversion of CO2 to farnesyl diphosphate-derived phytochemicals (amorpha-4,11-diene and squalene) by engineered cyanobacteria.

PubMed

Choi, Sun Young; Lee, Hyun Jeong; Choi, Jaeyeon; Kim, Jiye; Sim, Sang Jun; Um, Youngsoon; Kim, Yunje; Lee, Taek Soon; Keasling, Jay D; Woo, Han Min

2016-01-01

Metabolic engineering of cyanobacteria has enabled photosynthetic conversion of CO2 to value-added chemicals as bio-solar cell factories. However, the production levels of isoprenoids in engineered cyanobacteria were quite low, compared to other microbial hosts. Therefore, modular optimization of multiple gene expressions for metabolic engineering of cyanobacteria is required for the production of farnesyl diphosphate-derived isoprenoids from CO2. Here, we engineered Synechococcus elongatus PCC 7942 with modular metabolic pathways consisting of the methylerythritol phosphate pathway enzymes and the amorphadiene synthase for production of amorpha-4,11-diene, resulting in significantly increased levels (23-fold) of amorpha-4,11-diene (19.8 mg/L) in the best strain relative to a parental strain. Replacing amorphadiene synthase with squalene synthase led to the synthesis of a high amount of squalene (4.98 mg/L/OD730). Overexpression of farnesyl diphosphate synthase is the most critical factor for the significant production, whereas overexpression of 1-deoxy-d-xylulose 5-phosphate reductase is detrimental to the cell growth and the production. Additionally, the cyanobacterial growth inhibition was alleviated by expressing a terpene synthase in S. elongatus PCC 7942 strain with the optimized MEP pathway only (SeHL33). This is the first demonstration of photosynthetic production of amorpha-4,11-diene from CO2 in cyanobacteria and production of squalene in S. elongatus PCC 7942. Our optimized modular OverMEP strain (SeHL33) with either co-expression of ADS or SQS demonstrated the highest production levels of amorpha-4,11-diene and squalene, which could expand the list of farnesyl diphosphate-derived isoprenoids from CO2 as bio-solar cell factories.

Active-Site Models for the Nickel-Iron Hydrogenases: Effects of Ligands on Reactivity and Catalytic Properties

PubMed Central

Carroll, Maria E.; Barton, Bryan E.; Gray, Danielle L.; Mack, Amanda E.; Rauchfuss, Thomas B.

2011-01-01

Described are new derivatives of the type [HNiFe(SR)2(diphosphine)(CO)3]+, which feature a Ni(diphosphine) group linked to a Fe(CO)3 group via two bridging thiolate ligands. Previous work had described [HNiFe(pdt)(dppe)(CO)3]+ ([1H]+) and its activity as a catalyst for the reduction of protons. Work described in this paper focused on the effects of the diphosphine attached to nickel as well as the dithiolate bridge, 1,3-propanedithiolate (pdt) vs 1,2-ethanedithiolate (edt). A new synthetic route to these Ni-Fe dithiolates is described, involving reaction of Ni(SR)2(diphosphine) with FeI2(CO)4 followed by in situ reduction with cobaltocene. Evidence is presented that this route proceeds via metastable μ-iodo derivatives. Attempted isolation of such species led to the crystallization of NiFe(Me2pdt)(dppe)I2, which features tetrahedral Fe(II) and square planar Ni(II) centers (Me2pdt = 2,2-dimethylpropanedithiol). The new tricarbonyls prepared in this work are NiFe(pdt)(dcpe)(CO)3 (2, dcpe = 1,2-bis(dicyclohexylphosphino)ethane), NiFe(edt)(dppe)(CO)3 (3), and NiFe(edt)(dcpe)(CO)3 (4). Attempted preparation of a phenylthiolate-bridged complex via the FeI2(CO)4 + Ni(SPh)2(dppe) route gave the tetrametallic species [(CO)2Fe(SPh)2Ni(CO)]2(μ-dppe)2. Crystallographic analysis of the edt-dcpe compund [2H]BF4 and the edt-dppe compound [3H]BF4 verified their close resemblance. Each features pseudo-octahedral Fe and square pyramidal Ni centers. Starting from [4H]BF4 we prepared the PPh3 derivative [HNiFe(edt)(dppe)(PPh3)(CO)2]BF4 ([5H]BF4), which was obtained as a ~2:1 mixture of unsymmetrical and symmetrical isomers. Acid-base measurements indicate that changing from Ni(dppe) to Ni(dcpe) decreases the acidity of the cationic hydride complexes by 2.5 pKaMeCN units, from ~11 to ~13.5 (previous work showed that substitution at Fe leads to more dramatic effects). The redox potentials are more strongly affected by the change from dppe to dcpe, for example the [2]0/+ couple occurs at E1/2 = −820 for [2]0/+ vs −574 mV (vs Fc+/0) for [1]0/+. Changes in the dithiolate do not affect the acidity or the reduction potentials of the hydrides. The acid-independent rate of reduction of CH2ClCO2H by [2H]+ is ca. 50 s−1 (25 °C), twice that of [1H]+. The edt-dppe complex [2H]+ proved to be the most active catalyst, with an acid-independent rate of 300 s−1. PMID:21866886

Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion

DOE PAGES

Nava, Matthew; Lopez, Nazario; Muller, Peter; ...

2015-10-14

The reactivity of peroxide dianion O 2 2– has been scarcely explored in organic media due to the lack of soluble sources of this reduced oxygen species. We now report the finding that the encapsulated peroxide cryptate, [O 2cmBDCA-5t-H 6] 2– (1), reacts with carbon monoxide in organic solvents at 40 °C to cleanly form an encapsulated carbonate. Characterization of the resulting hexacarboxamide carbonate cryptate by single crystal X-ray diffraction reveals that carbonate dianion forms nine complementary hydrogen bonds with the hexacarboxamide cryptand, [CO 3cmBDCA-5t-H 6] 2– (2), a conclusion that is supported by spectroscopic data. Labeling studies and 17Omore » solid-state NMR data confirm that two-thirds of the oxygen atoms in the encapsulated carbonate derive from peroxide dianion, while the carbon is derived from CO. Further evidence for the formation of a carbonate cryptate was obtained by three methods of independent synthesis: treatment of (i) free cryptand with K 2CO 3; (ii) monodeprotonated cryptand with PPN[HCO 3]; and (iii) free cryptand with TBA[OH] and atmospheric CO 2. This work demonstrates CO oxidation mediated by a hydrogen-bonding anion receptor, constituting an alternative to transition-metal catalysis.« less

3D-QSAR analysis of MCD inhibitors by CoMFA and CoMSIA.

PubMed

Pourbasheer, Eslam; Aalizadeh, Reza; Ebadi, Amin; Ganjali, Mohammad Reza

2015-01-01

Three-dimensional quantitative structure-activity relationship was developed for the series of compounds as malonyl-CoA decarboxylase antagonists (MCD) using the CoMFA and CoMSIA methods. The statistical parameters for CoMFA (q(2)=0.558, r(2)=0.841) and CoMSIA (q(2)= 0.615, r(2) = 0.870) models were derived based on 38 compounds as training set in the basis of the selected alignment. The external predictive abilities of the built models were evaluated by using the test set of nine compounds. From obtained results, the CoMSIA method was found to have highly predictive capability in comparison with CoMFA method. Based on the given results by CoMSIA and CoMFA contour maps, some features that can enhance the activity of compounds as MCD antagonists were introduced and used to design new compounds with better inhibition activity.

Direct synthesis and characterization of mixed-valent Li 0.5$-$δCoPO 4, a Li-deficient derivative of the Cmcm polymorph of LiCoPO 4

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

Ludwig, Jennifer; Alarcon-Suesca, Carlos; Geprags, Stephan

While the majority of research activities on LiCoPO 4 is focussed on the thermodynamically stable olivine-type Pnma polymorph, the metastable Pna2 1 and Cmcm modifications have recently attracted considerable attention due to their interesting material properties. In this study, we present the first Li-deficient structural derivative of the Cmcm modification with the nominal composition Li 0.5–δCoPO 4. As opposed to the substoichiometric olivine ( Pnma) phases Li xCoPO 4 (x = 0; 2/3), which are exclusively accessible by electrochemical or chemical Li extraction techniques, this is also the first time that a direct soft-chemical synthesis route towards a Li xCoPOmore » 4-type material is accomplished. X-ray and neutron diffraction studies indicate that Cmcm-type Li 0.5–δCoPO 4 shows vacancies on both the Li and Co sites, whereas X-ray absorption spectra demonstrate that the structure features heterovalent Co ions (+2/+3) to compensate for the Li deficit. Magnetic measurements reveal a long-range antiferromagnetic order below 10.5 K. A thorough investigation of the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and temperature-dependent in situ X-ray powder diffraction demonstrates that Li 0.5–δCoPO 4 is metastable and exhibits a complex, multi-step thermal decomposition mechanism. In the first step at 394 °C, it decomposes to α-Co 2P 2O 7 ( P2 1/c) and LiCoPO 4 ( Cmcm) upon O 2 release. The LiCoPO 4 ( Cmcm) intermediate is then irreversibly transformed to olivine-type LiCoPO 4 (Pnma) at 686 °C. Furthermore, the material properties of Li 0.5–δCoPO 4 are further compared to the fully lithiated, isostructural LiCoPO 4 ( Cmcm) phase, for which an improved structure solution as well as Co L 2,3-edge X-ray absorption spectra are reported for the first time.« less

Direct synthesis and characterization of mixed-valent Li 0.5$-$δCoPO 4, a Li-deficient derivative of the Cmcm polymorph of LiCoPO 4

DOE PAGES

Ludwig, Jennifer; Alarcon-Suesca, Carlos; Geprags, Stephan; ...

2017-05-26

While the majority of research activities on LiCoPO 4 is focussed on the thermodynamically stable olivine-type Pnma polymorph, the metastable Pna2 1 and Cmcm modifications have recently attracted considerable attention due to their interesting material properties. In this study, we present the first Li-deficient structural derivative of the Cmcm modification with the nominal composition Li 0.5–δCoPO 4. As opposed to the substoichiometric olivine ( Pnma) phases Li xCoPO 4 (x = 0; 2/3), which are exclusively accessible by electrochemical or chemical Li extraction techniques, this is also the first time that a direct soft-chemical synthesis route towards a Li xCoPOmore » 4-type material is accomplished. X-ray and neutron diffraction studies indicate that Cmcm-type Li 0.5–δCoPO 4 shows vacancies on both the Li and Co sites, whereas X-ray absorption spectra demonstrate that the structure features heterovalent Co ions (+2/+3) to compensate for the Li deficit. Magnetic measurements reveal a long-range antiferromagnetic order below 10.5 K. A thorough investigation of the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and temperature-dependent in situ X-ray powder diffraction demonstrates that Li 0.5–δCoPO 4 is metastable and exhibits a complex, multi-step thermal decomposition mechanism. In the first step at 394 °C, it decomposes to α-Co 2P 2O 7 ( P2 1/c) and LiCoPO 4 ( Cmcm) upon O 2 release. The LiCoPO 4 ( Cmcm) intermediate is then irreversibly transformed to olivine-type LiCoPO 4 (Pnma) at 686 °C. Furthermore, the material properties of Li 0.5–δCoPO 4 are further compared to the fully lithiated, isostructural LiCoPO 4 ( Cmcm) phase, for which an improved structure solution as well as Co L 2,3-edge X-ray absorption spectra are reported for the first time.« less

Factors and processes governing the C-14 content of carbonate in desert soils

NASA Technical Reports Server (NTRS)

Amundson, Ronald; Wang, Yang; Chadwick, Oliver; Trumbore, Susan; Mcfadden, Leslie; Mcdonald, Eric; Wells, Steven; Deniro, Michael

1994-01-01

A model is presented describing the factors and processes which determine the measured C-14 ages of soil calcium carbonate. Pedogenic carbonate forms in isotopic equilium with soil CO2. Carbon dioxide in soils is a mixture of CO2 derived from two biological sources: respiration by living plant roots and respiration of microorganisms decomposing soil humus. The relative proportion of these two CO2 sources can greatly affect the initial C-14 content of pedogenic carbonate: the greater the contribution of humus-derived CO2, the greater the initial C-14 age of the carbonate mineral. For any given mixture of CO2 sources, the steady-state (14)CO2 distribution vs. soil depth can be described by a production/diffusion model. As a soil ages, the C-14 age of soil humus increases, as does the steady-state C-14 age of soil CO2 and the initial C-14 age of any pedogenic carbonate which forms. The mean C-14 age of a complete pedogenic carbonate coating or nodule will underestimate the true age of the soil carbonate. This discrepancy increases the older a soil becomes. Partial removal of outer (and younger) carbonate coatings greatly improves the relationship between measured C-14 age and true age. Although the production/diffusion model qualitatively explains the C-14 age of pedogenic carbonate vs. soil depth in many soils, other factors, such as climate change, may contribute to the observed trends, particularily in soils older than the Holocene.

A method for examining the geospatial distribution of CO2 storage resources applied to the Pre-Punta Gorda Composite and Dollar Bay reservoirs of the South Florida Basin, U.S.A

USGS Publications Warehouse

Roberts-Ashby, Tina; Brandon N. Ashby,

2016-01-01

This paper demonstrates geospatial modification of the USGS methodology for assessing geologic CO2 storage resources, and was applied to the Pre-Punta Gorda Composite and Dollar Bay reservoirs of the South Florida Basin. The study provides detailed evaluation of porous intervals within these reservoirs and utilizes GIS to evaluate the potential spatial distribution of reservoir parameters and volume of CO2 that can be stored. This study also shows that incorporating spatial variation of parameters using detailed and robust datasets may improve estimates of storage resources when compared to applying uniform values across the study area derived from small datasets, like many assessment methodologies. Geospatially derived estimates of storage resources presented here (Pre-Punta Gorda Composite = 105,570 MtCO2; Dollar Bay = 24,760 MtCO2) were greater than previous assessments, which was largely attributed to the fact that detailed evaluation of these reservoirs resulted in higher estimates of porosity and net-porous thickness, and areas of high porosity and thick net-porous intervals were incorporated into the model, likely increasing the calculated volume of storage space available for CO2 sequestration. The geospatial method for evaluating CO2 storage resources also provides the ability to identify areas that potentially contain higher volumes of storage resources, as well as areas that might be less favorable.

Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction

DOE PAGES

Eilert, Andre; Cavalca, Filippo; Roberts, F. Sloan; ...

2016-12-16

Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO 2RR). Using in situ ambient pressure X-ray photoelectron spectroscopy and quasi in situ electron energy-loss spectroscopy in a transmission electron microscope, we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts but no residual copper oxide. On the basis of these findings in combination with density functional theory simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stablemore » under the strongly reducing conditions found in CO 2RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multicarbon compounds such as ethylene.« less

Pedagogical Reflections by Secondary Science Teachers at Different NOS Implementation Levels

NASA Astrophysics Data System (ADS)

Herman, Benjamin C.; Clough, Michael P.; Olson, Joanne K.

2017-02-01

This study investigated what 13 secondary science teachers at various nature of science (NOS) instruction implementation levels talked about when they reflected on their teaching. We then determined if differences exist in the quality of those reflections between high, medium, and low NOS implementers. This study sought to answer the following questions: (1) What do teachers talk about when asked general questions about their pedagogy and NOS pedagogy and (2) what qualitative differences, if any, exist within variables across teachers of varying NOS implementation levels? Evidence derived from these teachers' reflections indicated that self-efficacy and perceptions of general importance for NOS instruction were poor indicators of NOS implementation. However, several factors were associated with the extent that these teachers implemented NOS instruction, including the utility value they hold for NOS teaching, considerations of how people learn, understanding of NOS pedagogy, and their ability to accurately and deeply self-reflect about teaching. Notably, those teachers who effectively implemented the NOS at higher levels value NOS instruction for reasons that transcend immediate instructional objectives. That is, they value teaching NOS for achieving compelling ends realized long after formal schooling (e.g., lifelong socioscientific decision-making for civic reasons), and they deeply reflect about how to teach NOS by drawing from research about how people learn. Low NOS implementers' simplistic notions and reflections about teaching and learning appeared to be impeding factors to accurate and consistent NOS implementation. This study has implications for science teacher education efforts that promote NOS instruction.

Determination Co 2+ in vitamin B 12 based on enhancement of 2-(4-substituted-phenyl)-4,5-di(2-furyl) imidazole and H 2O 2 chemiluminescence reaction

NASA Astrophysics Data System (ADS)

Han, Lu; Zhang, Yumin; Kang, Jing; Tang, Jieli; Zhang, Yihua

2011-11-01

In this paper, three kinds of imidazole derivatives, 2-(4-methylphenyl)-4,5-di(2-furyl) imidazole (MDFI), 2-(4-nitrophenyl)-4,5-di(2-furyl) imidazole (NDFI), and 2-(4-tert-butylphenyl)-4,5-di(2-furyl) imidazole (t-BDFI) were synthesized. In an alkaline medium, the chemiluminescence (CL) reaction of imidazole derivatives with H 2O 2 has been investigated. It was also found that MDFI/H 2O 2 and t-BDFI/H 2O 2 systems gave strong CL. When Co 2+ was added into the two CL systems, the CL intensity was remarkably enhanced. In the optimum conditions, the CL intensity is linearly related to the logarithm of concentration of Co 2+. The linear ranges are 5 × 10 -9-2.5 × 10 -7 mol/L for MDFI/H 2O 2 system and 5 × 10 -9-2.5 × 10 -7 mol/L for t-BDFI/H 2O 2 system, and the corresponding detection limits are 1.2 × 10 -9 mol/L and 1.1 × 10 -9 mol/L, respectively. The method was applied to the determination of Co 2+ in vitamin B 12 injection. Furthermore, the CL mechanism was also discussed.

Short peptides derived from the interaction domain of SARS coronavirus nonstructural protein nsp10 can suppress the 2'-O-methyltransferase activity of nsp10/nsp16 complex.

PubMed

Ke, Min; Chen, Yu; Wu, Andong; Sun, Ying; Su, Ceyang; Wu, Hao; Jin, Xu; Tao, Jiali; Wang, Yi; Ma, Xiao; Pan, Ji-An; Guo, Deyin

2012-08-01

Coronaviruses are the etiological agents of respiratory and enteric diseases in humans and livestock, exemplified by the life-threatening severe acute respiratory syndrome (SARS) caused by SARS coronavirus (SARS-CoV). However, effective means for combating coronaviruses are still lacking. The interaction between nonstructural protein (nsp) 10 and nsp16 has been demonstrated and the crystal structure of SARS-CoV nsp16/10 complex has been revealed. As nsp10 acts as an essential trigger to activate the 2'-O-methyltransferase activity of nsp16, short peptides derived from nsp10 may have inhibitory effect on viral 2'-O-methyltransferase activity. In this study, we revealed that the domain of aa 65-107 of nsp10 was sufficient for its interaction with nsp16 and the region of aa 42-120 in nsp10, which is larger than the interaction domain, was needed for stimulating the nsp16 2'-O-methyltransferase activity. We further showed that two short peptides derived from the interaction domain of nsp10 could inhibit the 2'-O-methyltransferase activity of SARS-CoV nsp16/10 complex, thus providing a novel strategy and proof-of-principle study for developing peptide inhibitors against SARS-CoV. Copyright © 2012 Elsevier B.V. All rights reserved.

Influence of high-temperature steam on the reactivity of CaO sorbent for CO₂ capture.

PubMed

Donat, Felix; Florin, Nicholas H; Anthony, Edward J; Fennell, Paul S

2012-01-17

Calcium looping is a high-temperature CO(2) capture technology applicable to the postcombustion capture of CO(2) from power station flue gas, or integrated with fuel conversion in precombustion CO(2) capture schemes. The capture technology uses solid CaO sorbent derived from natural limestone and takes advantage of the reversible reaction between CaO and CO(2) to form CaCO(3); that is, to achieve the separation of CO(2) from flue or fuel gas, and produce a pure stream of CO(2) suitable for geological storage. An important characteristic of the sorbent, affecting the cost-efficiency of this technology, is the decay in reactivity of the sorbent over multiple CO(2) capture-and-release cycles. This work reports on the influence of high-temperature steam, which will be present in flue (about 5-10%) and fuel (∼20%) gases, on the reactivity of CaO sorbent derived from four natural limestones. A significant increase in the reactivity of these sorbents was found for 30 cycles in the presence of steam (from 1-20%). Steam influences the sorbent reactivity in two ways. Steam present during calcination promotes sintering that produces a sorbent morphology with most of the pore volume associated with larger pores of ∼50 nm in diameter, and which appears to be relatively more stable than the pore structure that evolves when no steam is present. The presence of steam during carbonation reduces the diffusion resistance during carbonation. We observed a synergistic effect, i.e., the highest reactivity was observed when steam was present for both calcination and carbonation.

3D hierarchical porous cobalt monoxide nanoplates with a book-like structure derived from Co(CO3)0.5(OH)·0.11H2O: two-steps oriented attachment and high-performance asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Xiao, Yuanhua; Zhao, Xiaobing; Jin, Qingxian; Su, Dangcheng; Wang, Xuezhao; Wu, Shide; Zhou, Liming; Fang, Shaoming

2017-10-01

3D Hierarchical porous cobalt monoxide (CoO) nanoplates with a book-like structure derive from Co(CO3)0.5(OH)·0.11H2O by a two-steps oriented attachment mechanism in the solvothermal process. Firstly, nanoplates are formed by oriented attachment of nanorods. Secondly, new nanoplates could be generated on the old nanoplates by a sloped oriented attachment of nanorods with the based nanoplates shape into a 3D hierarchical book-like structure. The CoO nanoplates show superior specific capacitance about 1221.7 F g-1 at 1 A g-1 to most of the Co-based supercapacitor materials up to date. An asymmetric supercapacitor (ASC) based on positive electrode CoO and negative electrode active carbon (AC) exhibits an excellent energy density of 50.1 Wh kg-1 at a power density of 589 W kg-1 and gets a satisfactory cycling stability (86.3% of its initial capacitance retention at 10 A g-1 over 10 000 cycles).

Adipose-derived stem cells cooperate with fractional carbon dioxide laser in antagonizing photoaging: a potential role of Wnt and β-catenin signaling.

PubMed

Xu, Xiao; Wang, Hong-Yi; Zhang, Yu; Liu, Yang; Li, Yan-Qi; Tao, Kai; Wu, Chu-Tse; Jin, Ji-de; Liu, Xiao-Yan

2014-01-01

It is well established that adipose-derived stem cells (ADSCs) produce and secrete cytokines/growth factors that antagonize UV-induced photoaging of skin. However, the exact molecular basis underlying the anti-photoaging effects exerted by ADSCs is not well understood, and whether ADSCs cooperate with fractional carbon dioxide (CO2) laser to facilitate photoaging skin healing process has not been explored. Here, we investigated the impacts of ADSCs on photoaging in a photoaging animal model, its associated mechanisms, and its functional cooperation with fractional CO2 laser in treatment of photoaging skin. We showed that ADSCs improved dermal thickness and activated the proliferation of dermal fibroblast. We further demonstrated that the combined treatment of ADSCs and fractional CO2 laser, the latter which is often used to resurface skin and treat wrinkles, had more beneficial effects on the photoaging skin compared with each individual treatment. In our prepared HDF photoaging model, flow cytometry showed that, after adipose derived stem cells conditioned medium (ADSC-CM) co-cultured HDF photoaging model, the cell proliferation rate is higher than UVB irradiation induced HDF modeling (p < 0.05). Additionally, the expressions of β-catenin and Wnt3a, which were up-regulated after the transplantation of ADSCs alone or in combination with fractional CO2 laser treatment. And the expression of wnt3a and β-catenin has the positive correlation with photoaging related protein TGF-β2 and COLI. We also verified these protein expressions in tissue level. In addition, after injected SFRP2 into ADSC-CM co-cultured HDF photoaging model, wnt3a inhibitor, compared with un-intervened group, wnt3a, β-catenin protein level significantly decreased. Both ADSCs and fractional CO2 laser improved photoaging skin at least partially via targeting dermal fibroblast activity which was increased in photoaging skin. The combinatorial use of ADSCs and fractional CO2 laser synergistically improved the healing process of photoaging skin. Thus, we provide a strong rationale for a combined use of ADSCs and fractional CO2 laser in treatment of photoaging skin in clinic in the future. Moreover, we provided evidence that the Wnt/β-catenin signaling pathway may contribute to the activation of dermal fibroblast by the transplantation of ADSCs in both vitro and vivo experiment.

Adipose-derived stem cells cooperate with fractional carbon dioxide laser in antagonizing photoaging: a potential role of Wnt and β-catenin signaling

PubMed Central

2014-01-01

Background It is well established that adipose-derived stem cells (ADSCs) produce and secrete cytokines/growth factors that antagonize UV-induced photoaging of skin. However, the exact molecular basis underlying the anti-photoaging effects exerted by ADSCs is not well understood, and whether ADSCs cooperate with fractional carbon dioxide (CO2) laser to facilitate photoaging skin healing process has not been explored. Here, we investigated the impacts of ADSCs on photoaging in a photoaging animal model, its associated mechanisms, and its functional cooperation with fractional CO2 laser in treatment of photoaging skin. Results We showed that ADSCs improved dermal thickness and activated the proliferation of dermal fibroblast. We further demonstrated that the combined treatment of ADSCs and fractional CO2 laser, the latter which is often used to resurface skin and treat wrinkles, had more beneficial effects on the photoaging skin compared with each individual treatment. In our prepared HDF photoaging model, flow cytometry showed that, after adipose derived stem cells conditioned medium (ADSC-CM) co-cultured HDF photoaging model, the cell proliferation rate is higher than UVB irradiation induced HDF modeling (p < 0.05). Additionally, the expressions of β-catenin and Wnt3a, which were up-regulated after the transplantation of ADSCs alone or in combination with fractional CO2 laser treatment. And the expression of wnt3a and β-catenin has the positive correlation with photoaging related protein TGF-β2 and COLI. We also verified these protein expressions in tissue level. In addition, after injected SFRP2 into ADSC-CM co-cultured HDF photoaging model, wnt3a inhibitor, compared with un-intervened group, wnt3a, β-catenin protein level significantly decreased. Conclusion Both ADSCs and fractional CO2 laser improved photoaging skin at least partially via targeting dermal fibroblast activity which was increased in photoaging skin. The combinatorial use of ADSCs and fractional CO2 laser synergistically improved the healing process of photoaging skin. Thus, we provide a strong rationale for a combined use of ADSCs and fractional CO2 laser in treatment of photoaging skin in clinic in the future. Moreover, we provided evidence that the Wnt/β-catenin signaling pathway may contribute to the activation of dermal fibroblast by the transplantation of ADSCs in both vitro and vivo experiment. PMID:24917925

Enhanced agarose and xylan degradation for production of polyhydroxyalkanoates by co-culture of marine bacterium, Saccharophagus degradans and its contaminant, Bacillus cereus

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

Sawant, Shailesh S.; Salunke, Bipinchandra K.; Taylor, II, Larry E.

Over reliance on energy or petroleum products has raised concerns both in regards to the depletion of their associated natural resources as well as their increasing costs. Bioplastics derived from microbes are emerging as promising alternatives to fossil fuel derived petroleum plastics. The development of a simple and eco-friendly strategy for bioplastic production with high productivity and yield, which is produced in a cost effective manner utilising abundantly available renewable carbon sources, would have the potential to result in an inexhaustible global energy source. Here we report the biosynthesis of bioplastic polyhydroxyalkanoates (PHAs) in pure cultures of marine bacterium, Saccharophagusmore » degradans 2-40 ( Sde 2-40), its contaminant, Bacillus cereus, and a co-culture of these bacteria ( Sde 2-40 and B. cereus) degrading plant and algae derived complex polysaccharides. Sde 2-40 degraded the complex polysaccharides agarose and xylan as sole carbon sources for biosynthesis of PHAs. The ability of Sde 2-40 to degrade agarose increased after co-culturing with B. cereus. The association of Sde 2-40 with B. cereus resulted in increased cell growth and higher PHA production (34.5% of dry cell weight) from xylan as a carbon source in comparison to Sde 2-40 alone (22.7% of dry cell weight). Lastly, the present study offers an innovative prototype for production of PHA through consolidated bioprocessing of complex carbon sources by pure and co-culture of microorganisms.« less

Enhanced agarose and xylan degradation for production of polyhydroxyalkanoates by co-culture of marine bacterium, Saccharophagus degradans and its contaminant, Bacillus cereus

DOE PAGES

Sawant, Shailesh S.; Salunke, Bipinchandra K.; Taylor, II, Larry E.; ...

2017-02-28

Over reliance on energy or petroleum products has raised concerns both in regards to the depletion of their associated natural resources as well as their increasing costs. Bioplastics derived from microbes are emerging as promising alternatives to fossil fuel derived petroleum plastics. The development of a simple and eco-friendly strategy for bioplastic production with high productivity and yield, which is produced in a cost effective manner utilising abundantly available renewable carbon sources, would have the potential to result in an inexhaustible global energy source. Here we report the biosynthesis of bioplastic polyhydroxyalkanoates (PHAs) in pure cultures of marine bacterium, Saccharophagusmore » degradans 2-40 ( Sde 2-40), its contaminant, Bacillus cereus, and a co-culture of these bacteria ( Sde 2-40 and B. cereus) degrading plant and algae derived complex polysaccharides. Sde 2-40 degraded the complex polysaccharides agarose and xylan as sole carbon sources for biosynthesis of PHAs. The ability of Sde 2-40 to degrade agarose increased after co-culturing with B. cereus. The association of Sde 2-40 with B. cereus resulted in increased cell growth and higher PHA production (34.5% of dry cell weight) from xylan as a carbon source in comparison to Sde 2-40 alone (22.7% of dry cell weight). Lastly, the present study offers an innovative prototype for production of PHA through consolidated bioprocessing of complex carbon sources by pure and co-culture of microorganisms.« less

Cross section data sets for electron collisions with H2, O2, CO, CO2, N2O and H2O

NASA Astrophysics Data System (ADS)

Anzai, K.; Kato, H.; Hoshino, M.; Tanaka, H.; Itikawa, Y.; Campbell, L.; Brunger, M. J.; Buckman, S. J.; Cho, H.; Blanco, F.; Garcia, G.; Limão-Vieira, P.; Ingólfsson, O.

2012-02-01

We review earlier cross section data sets for electron-collisions with H2, O2, CO, CO2, H2O and N2O, updated here by experimental results for their electronic states. Based on our recent measurements of differential cross sections for the electronic states of those molecules, integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis and then assessed against theory (BE f-scaling [Y.-K. Kim, J. Chem. Phys. 126, 064305 (2007)]). As they now represent benchmark electronic state cross sections, those ICSs for the above molecules are added into the original cross section sets taken from the data reviews for H2, O2, CO2 and H2O (the Itikawa group), and for CO and N2O (the Zecca group).

Electrochemical CO 2 Reduction on Oxide-Derived Cu Surface with Various Oxide Thicknesses

DOE PAGES

Liang, Zhixiu; Fu, Jie; Vukmirovic, Miomir B.; ...

2018-03-26

Here, cuprous oxide on copper foil electrodes prepared via electrochemical deposition and thermal annealing are investigated towards CO 2 electrochemical reduction at low overpotential. The thickness of the electrochemical deposited Cu 2O was controlled by varying the constant-current deposition time. The surface morphology and roughness were examined with SEM and CV respectively. The electrode fabricated by cuprous oxide deposited for 20 min demonstrated the best faradic efficiency (7.02%) and specific activity (0.123 mA/cm 2) towards format/formic acid formation at -0.5 V vs. RHE in CO 2 saturated 0.5 M K 2CO 3 among studied samples.

Electrochemical CO 2 Reduction on Oxide-Derived Cu Surface with Various Oxide Thicknesses

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

Liang, Zhixiu; Fu, Jie; Vukmirovic, Miomir B.

Here, cuprous oxide on copper foil electrodes prepared via electrochemical deposition and thermal annealing are investigated towards CO 2 electrochemical reduction at low overpotential. The thickness of the electrochemical deposited Cu 2O was controlled by varying the constant-current deposition time. The surface morphology and roughness were examined with SEM and CV respectively. The electrode fabricated by cuprous oxide deposited for 20 min demonstrated the best faradic efficiency (7.02%) and specific activity (0.123 mA/cm 2) towards format/formic acid formation at -0.5 V vs. RHE in CO 2 saturated 0.5 M K 2CO 3 among studied samples.

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

Shearer, J.; Callan, P; Amie, J

Nitrile hydratases (NHases) are non-heme Fe{sup III} or non-corrin Co{sup III} containing metalloenzymes that possess an N{sub 2}S{sub 3} ligand environment with nitrogen donors derived from amidates and sulfur donors derived from cysteinates. A closely related enzyme is thiocyanate hydrolase (SCNase), which possesses a nearly identical active-site coordination environment as CoNHase. These enzymes are redox inactive and perform hydrolytic reactions; SCNase hydrolyzes thiocyanate anions while NHase converts nitriles into amides. Herein an active CoNHase metallopeptide mimic, [Co{sup III}NHase-m1] (NHase-m1 = AcNH-CCDLP-CGVYD-PA-COOH), that contains Co{sup III} in a similar N{sub 2}S{sub 3} coordination environment as CoNHase is reported. [Co{sup III}NHase-m1] wasmore » characterized by electrospray ionization-mass spectrometry (ESI-MS), gel-permeation chromatography (GPC), Co K-edge X-ray absorption spectroscopy (Co-S: 2.21 {angstrom}; Co-N: 1.93 {angstrom}), vibrational, and optical spectroscopies. We find that [Co{sup III}NHase-m1] will perform the catalytic conversion of acrylonitrile into acrylamide with up to 58 turnovers observed after 18 h at 25 C (pH 8.0). FTIR data used in concert with calculated vibrational data (mPWPW91/aug-cc-TZVPP) demonstrates that the active form of [Co{sup III}NHase-m1] has a ligated SO{sub 2} (? = 1091 cm{sup -1}) moiety and a ligated protonated SO(H) (? = 928 cm{sup -1}) moiety; when only one oxygenated cysteinate ligand (i.e., a mono-SO{sub 2} coordination motif) or the bis-SO{sub 2} coordination motif are found within [Co{sup III}NHase-m1] no catalytic activity is observed. Calculations of the thermodynamics of ligand exchange (B3LYP/aug-cc-TZVPP) suggest that the reason for this is that the SO{sub 2}/SO(H) equatorial ligand motif promotes both water dissociation from the Co{sup III}-center and nitrile coordination to the Co{sup III}-center. In contrast, the under- or overoxidized motifs will either strongly favor a five coordinate Co{sup III}-center or strongly favor water binding to the Co{sup III}-center over nitrile binding.« less

Strong CO+ and {{\\rm{N}}}_{2}^{+} Emission in Comet C/2016 R2 (Pan-STARRS)

NASA Astrophysics Data System (ADS)

Cochran, Anita L.; McKay, Adam J.

2018-02-01

We report on imaging and spectroscopic observations of comet C/2016 R2 (Pan-STARRS) obtained with the 0.8 m and 2.7 m telescopes of McDonald Observatory in 2017 November and December, respectively. The comet was at a heliocentric distance greater than 3 au during both sets of observations. The images showed a well-developed tail with properties that suggested it was an ion tail. The spectra confirmed that we were observing well-developed bands of CO+ and {{{N}}}2+. The {{{N}}}2+ detection was unequivocally cometary and was one of the strongest bands of {{{N}}}2+ detected in a comet spectrum. We derived the ratio of these two ions and from that we were able to derive that N2/CO = 0.15. This is the highest such ratio reported for a comet. This Letter includes data taken at The McDonald Observatory of The University of Texas at Austin.

The role of soil microbes in the global carbon cycle: tracking the below-ground microbial processing of plant-derived carbon for manipulating carbon dynamics in agricultural systems

PubMed Central

Gougoulias, Christos; Clark, Joanna M; Shaw, Liz J

2014-01-01

It is well known that atmospheric concentrations of carbon dioxide (CO2) (and other greenhouse gases) have increased markedly as a result of human activity since the industrial revolution. It is perhaps less appreciated that natural and managed soils are an important source and sink for atmospheric CO2 and that, primarily as a result of the activities of soil microorganisms, there is a soil-derived respiratory flux of CO2 to the atmosphere that overshadows by tenfold the annual CO2 flux from fossil fuel emissions. Therefore small changes in the soil carbon cycle could have large impacts on atmospheric CO2 concentrations. Here we discuss the role of soil microbes in the global carbon cycle and review the main methods that have been used to identify the microorganisms responsible for the processing of plant photosynthetic carbon inputs to soil. We discuss whether application of these techniques can provide the information required to underpin the management of agro-ecosystems for carbon sequestration and increased agricultural sustainability. We conclude that, although crucial in enabling the identification of plant-derived carbon-utilising microbes, current technologies lack the high-throughput ability to quantitatively apportion carbon use by phylogentic groups and its use efficiency and destination within the microbial metabolome. It is this information that is required to inform rational manipulation of the plant–soil system to favour organisms or physiologies most important for promoting soil carbon storage in agricultural soil. PMID:24425529

Conversion of 4-Hydroxybutyrate to Acetyl Coenzyme A and Its Anapleurosis in the Metallosphaera sedula 3-Hydroxypropionate/4-Hydroxybutyrate Carbon Fixation Pathway

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

Hawkins, AB; Adams, MWW; Kelly, RM

2014-03-25

The extremely thermoacidophilic archaeon Metallosphaera sedula (optimum growth temperature, 73 degrees C, pH 2.0) grows chemolithoautotrophically on metal sulfides or molecular hydrogen by employing the 3-hydroxypropionate/4-hydroxybutyrate (3HP/4HB) carbon fixation cycle. This cycle adds two CO2 molecules to acetyl coenzyme A (acetyl-CoA) to generate 4HB, which is then rearranged and cleaved to form two acetyl-CoA molecules. Previous metabolic flux analysis showed that two-thirds of central carbon precursor molecules are derived from succinyl-CoA, which is oxidized to malate and oxaloacetate. The remaining one-third is apparently derived from acetyl-CoA. As such, the steps beyond succinyl-CoA are essential for completing the carbon fixation cyclemore » and for anapleurosis of acetyl-CoA. Here, the final four enzymes of the 3HP/4HB cycle, 4-hydroxybutyrate-CoA ligase (AMP forming) (Msed_0406), 4-hydroxybutyryl-CoA dehydratase (Msed_1321), crotonyl-CoA hydratase/(S)-3-hydroxybutyryl-CoA dehydrogenase (Msed_0399), and acetoacetyl-CoA beta-ketothiolase (Msed_0656), were produced recombinantly in Escherichia coli, combined in vitro, and shown to convert 4HB to acetyl-CoA. Metabolic pathways connecting CO2 fixation and central metabolism were examined using a gas-intensive bioreactor system in which M. sedula was grown under autotrophic (CO2-limited) and heterotrophic conditions. Transcriptomic analysis revealed the importance of the 3HP/4HB pathway in supplying acetyl-CoA to anabolic pathways generating intermediates in M. sedula metabolism. The results indicated that flux between the succinate and acetyl-CoA branches in the 3HP/4HB pathway is governed by 4-hydroxybutyrate-CoA ligase, possibly regulated posttranslationally by the protein acetyltransferase (Pat)/Sir2-dependent system. Taken together, this work confirms the final four steps of the 3HP/4HB pathway, thereby providing the framework for examining connections between CO2 fixation and central metabolism in M. sedula.« less

CoMFA analyses of C-2 position salvinorin A analogs at the kappa-opioid receptor provides insights into epimer selectivity.

PubMed

McGovern, Donna L; Mosier, Philip D; Roth, Bryan L; Westkaemper, Richard B

2010-04-01

The highly potent and kappa-opioid (KOP) receptor-selective hallucinogen Salvinorin A and selected analogs have been analyzed using the 3D quantitative structure-affinity relationship technique Comparative Molecular Field Analysis (CoMFA) in an effort to derive a statistically significant and predictive model of salvinorin affinity at the KOP receptor and to provide additional statistical support for the validity of previously proposed structure-based interaction models. Two CoMFA models of Salvinorin A analogs substituted at the C-2 position are presented. Separate models were developed based on the radioligand used in the kappa-opioid binding assay, [(3)H]diprenorphine or [(125)I]6 beta-iodo-3,14-dihydroxy-17-cyclopropylmethyl-4,5 alpha-epoxymorphinan ([(125)I]IOXY). For each dataset, three methods of alignment were employed: a receptor-docked alignment derived from the structure-based docking algorithm GOLD, another from the ligand-based alignment algorithm FlexS, and a rigid realignment of the poses from the receptor-docked alignment. The receptor-docked alignment produced statistically superior results compared to either the FlexS alignment or the realignment in both datasets. The [(125)I]IOXY set (Model 1) and [(3)H]diprenorphine set (Model 2) gave q(2) values of 0.592 and 0.620, respectively, using the receptor-docked alignment, and both models produced similar CoMFA contour maps that reflected the stereoelectronic features of the receptor model from which they were derived. Each model gave significantly predictive CoMFA statistics (Model 1 PSET r(2)=0.833; Model 2 PSET r(2)=0.813). Based on the CoMFA contour maps, a binding mode was proposed for amine-containing Salvinorin A analogs that provides a rationale for the observation that the beta-epimers (R-configuration) of protonated amines at the C-2 position have a higher affinity than the corresponding alpha-epimers (S-configuration). (c) 2010. Published by Elsevier Inc.

Kinetic temperature of massive star forming molecular clumps measured with formaldehyde

NASA Astrophysics Data System (ADS)

Tang, X. D.; Henkel, C.; Menten, K. M.; Zheng, X. W.; Esimbek, J.; Zhou, J. J.; Yeh, C. C.; König, C.; Yuan, Y.; He, Y. X.; Li, D. L.

2017-02-01

Context. For a general understanding of the physics involved in the star formation process, measurements of physical parameters such as temperature and density are indispensable. The chemical and physical properties of dense clumps of molecular clouds are strongly affected by the kinetic temperature. Therefore, this parameter is essential for a better understanding of the interstellar medium. Formaldehyde, a molecule which traces the entire dense molecular gas, appears to be the most reliable tracer to directly measure the gas kinetic temperature. Aims: We aim to determine the kinetic temperature with spectral lines from formaldehyde and to compare the results with those obtained from ammonia lines for a large number of massive clumps. Methods: Three 218 GHz transitions (JKAKC = 303-202, 322-221, and 321-220) of para-H2CO were observed with the 15 m James Clerk Maxwell Telescope (JCMT) toward 30 massive clumps of the Galactic disk at various stages of high-mass star formation. Using the RADEX non-LTE model, we derive the gas kinetic temperature modeling the measured para-H2CO 322-221/303-202 and 321-220/303-202 ratios. Results: The gas kinetic temperatures derived from the para-H2CO (321-220/303-202) line ratios range from 30 to 61 K with an average of 46 ± 9 K. A comparison of kinetic temperature derived from para-H2CO, NH3, and the dust emission indicates that in many cases para-H2CO traces a similar kinetic temperature to the NH3 (2, 2)/(1, 1) transitions and the dust associated with the HII regions. Distinctly higher temperatures are probed by para-H2CO in the clumps associated with outflows/shocks. Kinetic temperatures obtained from para-H2CO trace turbulence to a higher degree than NH3 (2, 2)/(1, 1) in the massive clumps. The non-thermal velocity dispersions of para-H2CO lines are positively correlated with the gas kinetic temperature. The massive clumps are significantly influenced by supersonic non-thermal motions. The reduced spectra (FITS files) are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/598/A30

Wide-field 12CO (J=2-1) and 13CO (J=2-1) Observations toward the Aquila Rift and Serpens Molecular Cloud Complexes. I. Molecular Clouds and Their Physical Properties

NASA Astrophysics Data System (ADS)

Nakamura, Fumitaka; Dobashi, Kazuhito; Shimoikura, Tomomi; Tanaka, Tomohiro; Onishi, Toshikazu

2017-03-01

We present the results of wide-field 12CO (J=2{--}1) and 13CO (J=2{--}1) observations toward the Aquila Rift and Serpens molecular cloud complexes (25^\\circ < l< 33^\\circ and 1^\\circ < b< 6^\\circ ) at an angular resolution of 3.‧4 (≈ 0.25 pc) and at a velocity resolution of 0.079 km s-1 with velocity coverage of -5 {km} {{{s}}}-1< {V}{LSR}< 35 {km} {{{s}}}-1. We found that the 13CO emission better traces the structures seen in the extinction map, and derived the {X}{13{CO}}-factor of this region. Applying SCIMES to the 13CO data cube, we identified 61 clouds and derived their mass, radii, and line widths. The line width-radius relation of the identified clouds basically follows those of nearby molecular clouds. The majority of the identified clouds are close to virial equilibrium, although the dispersion is large. By inspecting the 12CO channel maps by eye, we found several arcs that are spatially extended to 0.°2-3° in length. In the longitude-velocity diagrams of 12CO, we also found two spatially extended components that appear to converge toward Serpens South and the W40 region. The existence of two components with different velocities and arcs suggests that large-scale expanding bubbles and/or flows play a role in the formation and evolution of the Serpens South and W40 cloud.

Abundant carbon in the mantle beneath Hawai`i

USGS Publications Warehouse

Anderson, Kyle R.; Poland, Michael

2017-01-01

Estimates of carbon concentrations in Earth’s mantle vary over more than an order of magnitude, hindering our ability to understand mantle structure and mineralogy, partial melting, and the carbon cycle. CO2 concentrations in mantle-derived magmas supplying hotspot ocean island volcanoes yield our most direct constraints on mantle carbon, but are extensively modified by degassing during ascent. Here we show that undegassed magmatic and mantle carbon concentrations may be estimated in a Bayesian framework using diverse geologic information at an ocean island volcano. Our CO2 concentration estimates do not rely upon complex degassing models, geochemical tracer elements, assumed magma supply rates, or rare undegassed rock samples. Rather, we couple volcanic CO2 emission rates with probabilistic magma supply rates, which are obtained indirectly from magma storage and eruption rates. We estimate that the CO2content of mantle-derived magma supplying Hawai‘i’s active volcanoes is 0.97−0.19+0.25 wt%—roughly 40% higher than previously believed—and is supplied from a mantle source region with a carbon concentration of 263−62+81 ppm. Our results suggest that mantle plumes and ocean island basalts are carbon-rich. Our data also shed light on helium isotope abundances, CO2/Nb ratios, and may imply higher CO2 emission rates from ocean island volcanoes.

Solvent-Free Synthesis of Uniform MOF Shell-Derived Carbon Confined SnO2 /Co Nanocubes for Highly Reversible Lithium Storage.

PubMed

He, Qiu; Liu, Jinshuai; Li, Zhaohuai; Li, Qi; Xu, Lin; Zhang, Baoxuan; Meng, Jiashen; Wu, Yuzhu; Mai, Liqiang

2017-10-01

Tin dioxide (SnO 2 ) has attracted much attention in lithium-ion batteries (LIBs) due to its abundant source, low cost, and high theoretical capacity. However, the large volume variation, irreversible conversion reaction limit its further practical application in next-generation LIBs. Here, a novel solvent-free approach to construct uniform metal-organic framework (MOF) shell-derived carbon confined SnO 2 /Co (SnO 2 /Co@C) nanocubes via a two-step heat treatment is developed. In particular, MOF-coated CoSnO 3 hollow nanocubes are for the first time synthesized as the intermediate product by an extremely simple thermal solid-phase reaction, which is further developed as a general strategy to successfully obtain other uniform MOF-coated metal oxides. The as-synthesized SnO 2 /Co@C nanocubes, when tested as LIB anodes, exhibit a highly reversible discharge capacity of 800 mAh g -1 after 100 cycles at 200 mA g -1 and excellent cycling stability with a retained capacity of 400 mAh g -1 after 1800 cycles at 5 A g -1 . The experimental analyses demonstrate that these excellent performances are mainly ascribed to the delicate structure and a synergistic effect between Co and SnO 2 . This facile synthetic approach will greatly contribute to the development of functional metal oxide-based and MOF-assisted nanostructures in many frontier applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gluon tomography from deeply virtual Compton scattering at small x

DOE PAGES

Hatta, Yoshitaka; Xiao, Bo-Wen; Yuan, Feng

2017-06-29

We present a full evaluation of the deeply virtual Compton scattering cross section in the dipole framework in the small-x region. The result features the cosφ and cos2φ azimuthal angular correlations, which have been missing in previous studies based on the dipole model. In particular, the cos2φ term is generated by the elliptic gluon Wigner distribution of which the measurement at the planned electron-ion collider provides important information about the gluon tomography at small x. Here, we also show the consistency with the standard collinear factorization approach based on the quark and gluon generalized parton distributions.

Variability of Atmospheric CO2 over the western North Pacific: Influence of Asian outflow during March-April 2001

NASA Astrophysics Data System (ADS)

Vay, S. A.; Woo, J.; Anderson, B. E.; Thornhill, K. L.; Kiley, C.; Avery, M. A.; Sachse, G. W.; Blake, D. R.; Streets, D. G.; Nolf, S. R.

2002-12-01

We report here tropospheric CO2 measurements made as part of the airborne component of NASA's Transport and Chemical Evolution over the Pacific (TRACE-P) Mission during March and April in 2001. CO2 mixing ratios, sampled in the subtropics (23.5-45.5° N) west of 150° E, exhibited a decreasing trend with height (0.5-12 km), were highly correlated with latitude showing a distinct north to south gradient, and peaked between 35-40° N within the planetary boundary layer. Near the Asian continent, discrete plumes encountered below 4 km contained up to 393.6 ppmv CO2 and were augmented with the combustion and industrial tracers CO, C2H6, C3H8, CH3Cl, C2Cl4, and C6H6. A chemically based air mass classification scheme using the combustion products CO and C2H2 as tracers of continental source emissions was employed in this analysis. Results show an excellent positive correlation for CO2 (r2=0.98) with respect to this ratio in the lower to mid free troposphere (4-8 km) providing evidence of continental outflow. South of the Tropic of Cancer, mean and median CO2 values derived from samples obtained below 8 km are less than those calculated for the subtropics. However, within the upper troposphere (UT) of both regions, similar values were determined and enhancements in combustion-derived species in the 8-12 km altitude range were observed. The relationship revealed between CO2 and the C2H2/CO ratio, particularly for the tropics, suggests recent inputs from the surface to the UT. In order to elucidate the processes determining the variations of CO2 in the Asian Pacific rim region during TRACE-P, a CO2 emissions data base developed for Asia was examined in conjunction with the chemistry and 5 day backward trajectories in an attempt to link CO2 enhancements observed in pollution plumes to source regions. From these data acquired downwind of the Asian continent when CO2 concentrations at the surface were approaching their seasonal maximum, we estimate a net export flux on the order of 20 Tg C day-1 attributable to both anthropogenic emissions and the respiration of the terrestrial biosphere, animals, and humans.

Porous carbon derived via KOH activation of a hypercrosslinked porous organic polymer for efficient CO{sub 2}, CH{sub 4}, H{sub 2} adsorptions and high CO{sub 2}/N{sub 2} selectivity

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

Modak, Arindam; Bhaumik, Asim, E-mail: msab@iacs.res.in

2015-12-15

Microporous carbon having Brunauer-Emmett-Teller (BET) surface area of 2186 m{sup 2} g{sup −1} and micropore volume of 0.85 cm{sup 3} g{sup −1} has been synthesized via KOH induced high temperature carbonization of a non-conjugated hypercrosslinked organic polymer. Owing to the templating and activation by KOH, we have succeeded in making a microporous carbon from this porous polymer and the resultant carbon material showed high uptake for CO{sub 2} (7.6 mmol g{sup −1}) and CH{sub 4} (2.4 mmol g{sup −1}) at 1 atm, 273 K together with very good selectivity for the CO{sub 2}/N{sub 2} (30.2) separation. Furthermore, low pressure (1more » atm) H{sub 2} (2.6 wt%, 77 K) and water uptake (57.4 wt%, 298 K) ability of this polymer derived porous activated carbon is noteworthy. - Graphical abstract: Microporous carbon with BET surface area of 2186 m{sup 2} g{sup −1} has been synthesized via KOH activation of a porous organic polymer and it showed high uptake for CO{sub 2} (7.6 mmol g{sup −1}), CH{sub 4} (2.4 mmol g{sup −1}) and H{sub 2} (2.6 wt%) at 1 atm together with very good selectivity for CO{sub 2}. - Highlights: • Porous carbon from hypercrosslinked organic polymer. • KOH activated carbon with BET surface area 2186 m{sup 2} g{sup −1}. • High CO2 uptake (7.6 mmol g{sup −1}) and CO{sub 2}/N{sub 2} selectivity (30.2). • Porous carbon also showed high H{sub 2} (2.6 wt%) and H{sub 2}O (57.4 wt%) uptakes.« less

Hydrogenation of Organic Matter as a Terminal Electron Sink Sustains High CO 2 :CH 4 Production Ratios During Anaerobic Decomposition

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

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO 2 and CH 4 for each molecule of organic matter degraded. However, CO 2:CH 4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO 2 has an oxidationmore » state of +4, if CH 4 (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO 2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO 2:CH 4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. In conclusion, this mechanism for CO 2 generation without concomitant CH 4 production has the potential to regulate the global warming potential of peatlands by elevating CO 2:CH 4 production ratios.« less

Hydrogenation of Organic Matter as a Terminal Electron Sink Sustains High CO 2 :CH 4 Production Ratios During Anaerobic Decomposition

DOE PAGES

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.; ...

2017-07-03

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO 2 and CH 4 for each molecule of organic matter degraded. However, CO 2:CH 4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO 2 has an oxidationmore » state of +4, if CH 4 (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO 2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO 2:CH 4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. In conclusion, this mechanism for CO 2 generation without concomitant CH 4 production has the potential to regulate the global warming potential of peatlands by elevating CO 2:CH 4 production ratios.« less

Hydrogenation of organic matter as a terminal electron sink sustains high CO 2 :CH 4 production ratios during anaerobic decomposition

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

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO2 and CH4 for each molecule of organic matter degraded. However, CO2:CH4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO2 has an oxidation state of +4, if CH4more » (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO2:CH4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. This mechanism for CO2 generation without concomitant CH4 production has the potential to regulate the global warming potential of peatlands by elevating CO2:CH4 production ratios.« less

Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

NASA Technical Reports Server (NTRS)

Fu, Qi; Socki, R. A.; Niles, Paul B.

2011-01-01

Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets.

Longitudinal target-spin asymmetries for deeply virtual Compton scattering

DOE PAGES

Seder, E.; Biselli, A.; Pisano, S.; ...

2015-01-22

A measurement of the electroproduction of photons off protons in the deeply inelastic regime was performed at Jefferson Lab using a nearly 6-GeV electron beam, a longitudinally polarized proton target and the CEBAF Large Acceptance Spectrometer. Target-spin asymmetries for ep → e'p'y events, which arise from the interference of the deeply virtual Compton scattering and the Bethe-Heitler processes, were extracted over the widest kinematics in Q 2, x B, t and Φ, for 166 four-dimensional bins. In the framework of Generalized Parton Distributions (GPDs), at leading twist the t dependence of these asymmetries provides insight on the spatial distribution ofmore » the axial charge of the proton, which appears to be concentrated in its center. In conclusion, these results bring important and necessary constraints for the existing parametrizations of chiral-even GPDs.« less

Hydrophilic Conjugated Polymers with Large Bandgaps and Deep-Lying HOMO Levels as an Efficient Cathode Interlayer in Inverted Polymer Solar Cells.

PubMed

Kan, Yuanyuan; Zhu, Yongxiang; Liu, Zhulin; Zhang, Lianjie; Chen, Junwu; Cao, Yong

2015-08-01

Two hydrophilic conjugated polymers, PmP-NOH and PmP36F-NOH, with polar diethanol-amine on the side chains and main chain structures of poly(meta-phenylene) and poly(meta-phenylene-alt-3,6-fluorene), respectively, are successfully synthesized. The films of PmP-NOH and PmP36F-NOH show absorption edges at 340 and 343 nm, respectively. The calculated optical bandgaps of the two polymers are 3.65 and 3.62 eV, respectively, the largest ones so far reported for hydrophilic conjugated polymers. PmP-NOH and PmP36F-NOH also possess deep-lying highest occupied molecular orbital levels of -6.19 and -6.15 eV, respectively. Inserting PmP-NOH and PmP36F-NOH as a cathode interlayer in inverted polymer solar cells with a PTB7/PC71 BM blend as the active layer, high power conversion efficiencies of 8.58% and 8.33%, respectively, are achieved, demonstrating that the two hydrophilic polymers are excellent interlayers for efficient inverted polymer solar cells. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Initial assessment of multi-scale measures of C02 and H20 flux in the Siberian taiga

Treesearch

D.Y. Hollinger; F.M. Kelliher; E.-D. Schulze; N.N. Vygodskaya; A. Varlagin; I. Milukova; J.N. Byers; A. Sogachov; J.E. Hunt; T.M. McSeveny; K.I. Kobak; G. Bauer; A. Arneth

1995-01-01

We measured CO2 and H2O fluxes between undisturbed Larix gmelinii forest and the atmosphere at a remote Eastern Siberian site in July 1993. Scaled-up leaf-level porometer measurements agreed with those derived from the eddy correlation technique for the canopy fluxes of CO2 and H...

A comparison of top-down and bottom-up carbon dioxide fluxes in the UK using a multi-platform measurement network.

NASA Astrophysics Data System (ADS)

White, Emily; Rigby, Matt; O'Doherty, Simon; Stavert, Ann; Lunt, Mark; Nemitz, Eiko; Helfter, Carole; Allen, Grant; Pitt, Joe; Bauguitte, Stéphane; Levy, Pete; van Oijen, Marcel; Williams, Mat; Smallman, Luke; Palmer, Paul

2016-04-01

Having a comprehensive understanding, on a countrywide scale, of both biogenic and anthropogenic CO2 emissions is essential for knowing how best to reduce anthropogenic emissions and for understanding how the terrestrial biosphere is responding to global fossil fuel emissions. Whilst anthropogenic CO2 flux estimates are fairly well constrained, fluxes from biogenic sources are not. This work will help to verify existing anthropogenic emissions inventories and give a better understanding of biosphere - atmosphere CO2 exchange. Using an innovative top-down inversion scheme; a hierarchical Bayesian Markov Chain Monte Carlo approach with reversible jump "trans-dimensional" basis function selection, we aim to find emissions estimates for biogenic and anthropogenic sources simultaneously. Our approach allows flux uncertainties to be derived more comprehensively than previous methods, and allows the resolved spatial scales in the solution to be determined using the data. We use atmospheric CO2 mole fraction data from the UK Deriving Emissions related to Climate Change (DECC) and Greenhouse gAs UK and Global Emissions (GAUGE) projects. The network comprises of 6 tall tower sites, flight campaigns and a ferry transect along the east coast, and enables us to derive high-resolution monthly flux estimates across the UK and Ireland for the period 2013-2015. We have derived UK total fluxes of 675 PIC 78 Tg/yr during January 2014 (seasonal maximum) and 23 PIC 96 Tg/yr during May 2014 (seasonal minimum). Our disaggregated anthropogenic and biogenic flux estimates are compared to a new high-resolution time resolved anthropogenic inventory that will underpin future UNFCCC reports by the UK, and to DALEC carbon cycle model. This allows us to identify where significant differences exist between these "bottom-up" and "top-down" flux estimates and suggest reasons for discrepancies. We will highlight the strengths and limitations of the UK's CO2 emissions verification infrastructure at present and outline improvements that could be made in the future.

N/S Co-doped Carbon Derived From Cotton as High Performance Anode Materials for Lithium Ion Batteries.

PubMed

Xiong, Jiawen; Pan, Qichang; Zheng, Fenghua; Xiong, Xunhui; Yang, Chenghao; Hu, Dongli; Huang, Chunlai

2018-01-01

Highly porous carbon with large surface areas is prepared using cotton as carbon sources which derived from discard cotton balls. Subsequently, the sulfur-nitrogen co-doped carbon was obtained by heat treatment the carbon in presence of thiourea and evaluated as Lithium-ion batteries anode. Benefiting from the S, N co-doping, the obtained S, N co-doped carbon exhibits excellent electrochemical performance. As a result, the as-prepared S, N co-doped carbon can deliver a high reversible capacity of 1,101.1 mA h g -1 after 150 cycles at 0.2 A g -1 , and a high capacity of 531.2 mA h g -1 can be observed even after 5,000 cycles at 10.0 A g -1 . Moreover, excellently rate capability also can be observed, a high capacity of 689 mA h g -1 can be obtained at 5.0 A g -1 . This superior lithium storage performance of S, N co-doped carbon make it as a promising low-cost and sustainable anode for high performance lithium ion batteries.

N/S co-doped carbon derived from Cotton as high performance anode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Xiong, Jiawen; Pan, Qichang; Zheng, Fenghua; Xiong, Xunhui; Yang, Chenghao; Hu, Dongli; Huang, Chunlai

2018-04-01

Highly porous carbon with large surface areas is prepared using cotton as carbon sources which derived from discard cotton balls. Subsequently, the sulfur-nitrogen co-doped carbon was obtained by heat treatment the carbon in presence of thiourea and evaluated as Lithium-ion batteries anode. Benefiting from the S, N co-doping, the obtained S, N co-doped carbon exhibits excellent electrochemical performance. As a result, the as-prepared S, N co-doped carbon can deliver a high reversible capacity of 1101.1 mA h g-1 after 150 cycles at 0.2 A g-1, and a high capacity of 531.2 mA h g-1 can be observed even after 5000 cycles at 10.0 A g-1. Moreover, excellently rate capability also can be observed, a high capacity of 689 mA h g-1 can be obtained at 5.0 A g-1. This superior lithium storage performance of S, N co-doped carbon make it as a promising low-cost and sustainable anode for high performance lithium ion batteries.

Metal organic framework-derived CoPS/N-doped carbon for efficient electrocatalytic hydrogen evolution.

PubMed

Li, Yuzhi; Niu, Siqi; Rakov, Dmitrii; Wang, Ying; Cabán-Acevedo, Miguel; Zheng, Shijian; Song, Bo; Xu, Ping

2018-04-19

Electrocatalytic hydrogen evolution has attracted a great deal of attention due to the urgent need for clean energy. Herein, we demonstrate the synthesis of ternary pyrite-type cobalt phosphosulphide (CoPS) nanoparticles supported on a nitrogen-doped carbon matrix, CoPS/N-C, through carbonization and subsequent phosphosulfurization of Co-based zeolitic imidazolate frameworks (ZIF-67), as promising hydrogen evolution reaction (HER) electrocatalysts in both acidic and alkaline solutions. The polyhedral structure of ZIF-67 can be well maintained in the as-prepared CoPS/N-C nanocomposites. In particular, CoPS/N-C provides a geometric catalytic current density of -10 mA cm-2 at overpotentials of -80 and -148 mV vs. a reversible hydrogen electrode (RHE) and a Tafel slope of 68 and 78 mV dec-1 in 0.5 M H2SO4 and 1 M KOH, respectively, which is superior to most of the transition metal phosphosulfide materials. This MOF-derived synthesis of a transition metal phosphosulfide supported heteroatom-doped carbon matrix provides a promising opportunity for the development of highly efficient electrocatalysts for renewable energy devices.

N/S Co-doped Carbon Derived From Cotton as High Performance Anode Materials for Lithium Ion Batteries

PubMed Central

Xiong, Jiawen; Pan, Qichang; Zheng, Fenghua; Xiong, Xunhui; Yang, Chenghao; Hu, Dongli; Huang, Chunlai

2018-01-01

Highly porous carbon with large surface areas is prepared using cotton as carbon sources which derived from discard cotton balls. Subsequently, the sulfur-nitrogen co-doped carbon was obtained by heat treatment the carbon in presence of thiourea and evaluated as Lithium-ion batteries anode. Benefiting from the S, N co-doping, the obtained S, N co-doped carbon exhibits excellent electrochemical performance. As a result, the as-prepared S, N co-doped carbon can deliver a high reversible capacity of 1,101.1 mA h g−1 after 150 cycles at 0.2 A g−1, and a high capacity of 531.2 mA h g−1 can be observed even after 5,000 cycles at 10.0 A g−1. Moreover, excellently rate capability also can be observed, a high capacity of 689 mA h g−1 can be obtained at 5.0 A g−1. This superior lithium storage performance of S, N co-doped carbon make it as a promising low-cost and sustainable anode for high performance lithium ion batteries. PMID:29755966

Year-round Regional CO2 Fluxes from Boreal and Tundra Ecosystems in Alaska

NASA Astrophysics Data System (ADS)

Commane, R.; Lindaas, J.; Benmergui, J. S.; Luus, K. A.; Chang, R. Y. W.; Daube, B. C.; Euskirchen, E. S.; Henderson, J.; Karion, A.; Miller, J. B.; Miller, S. M.; Parazoo, N.; Randerson, J. T.; Sweeney, C.; Tans, P. P.; Thoning, K. W.; Veraverbeke, S.; Miller, C. E.; Wofsy, S. C.

2016-12-01

High-latitude ecosystems could release large amounts of carbon dioxide (CO2) to the atmosphere in a warmer climate. We derive temporally and spatially resolved year-round CO2 fluxes in Alaska from a synthesis of airborne and tower CO2 observations in 2012-2014. We find that tundra ecosystems were net sources of atmospheric CO2. We discuss these flux estimates in the context of long-term CO2 measurements at Barrow, AK, to asses the long term trend in carbon fluxes in the Arctic. Many Earth System Models incorrectly simulate net carbon uptake in Alaska presently. Our results imply that annual net emission of CO2 to the atmosphere may have increased markedly in this region of the Arctic in response to warming climate, supporting the view that climate-carbon feedback is strongly positive in the high Arctic.

The Role of Sub- and Supercritical CO2 as "Processing Solvent" for the Recycling and Sample Preparation of Lithium Ion Battery Electrolytes.

PubMed

Nowak, Sascha; Winter, Martin

2017-03-06

Quantitative electrolyte extraction from lithium ion batteries (LIB) is of great interest for recycling processes. Following the generally valid EU legal guidelines for the recycling of batteries, 50 wt % of a LIB cell has to be recovered, which cannot be achieved without the electrolyte; hence, the electrolyte represents a target component for the recycling of LIBs. Additionally, fluoride or fluorinated compounds, as inevitably present in LIB electrolytes, can hamper or even damage recycling processes in industry and have to be removed from the solid LIB parts, as well. Finally, extraction is a necessary tool for LIB electrolyte aging analysis as well as for post-mortem investigations in general, because a qualitative overview can already be achieved after a few minutes of extraction for well-aged, apparently "dry" LIB cells, where the electrolyte is deeply penetrated or even gellified in the solid battery materials.

Developing the Precision Magnetic Field for the E989 Muon g{2 Experiment

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

Smith, Matthias W.

The experimental value ofmore » $$(g\\hbox{--}2)_\\mu$$ historically has been and contemporarily remains an important probe into the Standard Model and proposed extensions. Previous measurements of $$(g\\hbox{--}2)_\\mu$$ exhibit a persistent statistical tension with calculations using the Standard Model implying that the theory may be incomplete and constraining possible extensions. The Fermilab Muon g-2 experiment, E989, endeavors to increase the precision over previous experiments by a factor of four and probe more deeply into the tension with the Standard Model. The $$(g\\hbox{--}2)_\\mu$$ experimental implementation measures two spin precession frequencies defined by the magnetic field, proton precession and muon precession. The value of $$(g\\hbox{--}2)_\\mu$$ is derived from a relationship between the two frequencies. The precision of magnetic field measurements and the overall magnetic field uniformity achieved over the muon storage volume are then two undeniably important aspects of the e xperiment in minimizing uncertainty. The current thesis details the methods employed to achieve magnetic field goals and results of the effort.« less

Chronic liver injury promotes hepatocarcinoma cells seeding and growth, associated with the infiltration by macrophages.

PubMed

Delire, Bénédicte; Henriet, Patrick; Lemoine, Pascale; Leclercq, Isabelle A; Stärkel, Peter

2018-05-04

Ninety percent of hepatocarcinoma (HCC) develop in a chronically damaged liver. The interactions between non tumor stromal components, especially macrophages, and the cancer cells are still incompletely understood. Our aim was to determine whether a chronically injured liver represents a favorable environment for the seeding and growth of HCC cells, and to evaluate the potential roles of macrophages infiltrated within the tumor. HCC cells were injected into the liver in healthy mice (healthy liver group-HL) and in mice chronically treated with CCl 4 for 7 weeks (CCl 4 7w group). Livers were examined for the presence of tumor 2 weeks post injection. Tumor and non tumor tissues were analyzed for macrophages infiltration, origin (monocytes-derived vs resident macrophages) and polarization state, and matrix metalloproteinases (MMPs) production. Fifty-three percent of mice developed neoplastic lesion in the HL group while a tumor lesion was found in all livers in the CCl 4 7w group. Macrophages infiltrated more deeply the tumors of the CCl 4 7weeks group. Evaluation of factors involved in the recruitment of macrophages and of markers of their polarization state was in favor of prominent infiltration of M2 pro-tumor monocytes-derived macrophages inside the tumors developing in a chronically injured liver. MMP-2 and -9 production, attributed to M2 pro-tumor macrophages, was significantly higher in the tumors of the CCl 4 7w group. Chronic liver damage promotes cancer development in our model. Our results suggest that an injured background favors the infiltration of M2 pro-tumor monocytes-derived macrophages. These secrete MMP-2 and MMP-9 that promote tumor progression. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Brainstem response patterns in deeply-sedated critically-ill patients predict 28-day mortality.

PubMed

Rohaut, Benjamin; Porcher, Raphael; Hissem, Tarik; Heming, Nicholas; Chillet, Patrick; Djedaini, Kamel; Moneger, Guy; Kandelman, Stanislas; Allary, Jeremy; Cariou, Alain; Sonneville, Romain; Polito, Andréa; Antona, Marion; Azabou, Eric; Annane, Djillali; Siami, Shidasp; Chrétien, Fabrice; Mantz, Jean; Sharshar, Tarek

2017-01-01

Deep sedation is associated with acute brain dysfunction and increased mortality. We had previously shown that early-assessed brainstem reflexes may predict outcome in deeply sedated patients. The primary objective was to determine whether patterns of brainstem reflexes might predict mortality in deeply sedated patients. The secondary objective was to generate a score predicting mortality in these patients. Observational prospective multicenter cohort study of 148 non-brain injured deeply sedated patients, defined by a Richmond Assessment sedation Scale (RASS) <-3. Brainstem reflexes and Glasgow Coma Scale were assessed within 24 hours of sedation and categorized using latent class analysis. The Full Outline Of Unresponsiveness score (FOUR) was also assessed. Primary outcome measure was 28-day mortality. A "Brainstem Responses Assessment Sedation Score" (BRASS) was generated. Two distinct sub-phenotypes referred as homogeneous and heterogeneous brainstem reactivity were identified (accounting for respectively 54.6% and 45.4% of patients). Homogeneous brainstem reactivity was characterized by preserved reactivity to nociceptive stimuli and a partial and topographically homogenous depression of brainstem reflexes. Heterogeneous brainstem reactivity was characterized by a loss of reactivity to nociceptive stimuli associated with heterogeneous brainstem reflexes depression. Heterogeneous sub-phenotype was a predictor of increased risk of 28-day mortality after adjustment to Simplified Acute Physiology Score-II (SAPS-II) and RASS (Odds Ratio [95% confidence interval] = 6.44 [2.63-15.8]; p<0.0001) or Sequential Organ Failure Assessment (SOFA) and RASS (OR [95%CI] = 5.02 [2.01-12.5]; p = 0.0005). The BRASS (and marginally the FOUR) predicted 28-day mortality (c-index [95%CI] = 0.69 [0.54-0.84] and 0.65 [0.49-0.80] respectively). In this prospective cohort study, around half of all deeply sedated critically ill patients displayed an early particular neurological sub-phenotype predicting 28-day mortality, which may reflect a dysfunction of the brainstem.

Detailed Study of the Formation of Sugar Derivatives Produced from the UV Irradiation of Astrophysical Ice Analogs

NASA Technical Reports Server (NTRS)

Nuevo, Michel; Cooper, George; Saunders, John; Buffo, Christina E.; Materese, Christopher K.; Sandford, Scott A.

2018-01-01

Carbonaceous meteorites such as Murchison contain a large variety of organic compounds of astrobiological interest such as amino acids, other amphiphilic compounds, functionalized nitrogen heterocycles (including nucleobases), functionalized polycylic aromatic hydro-carbons (including quinones), and sugar derivatives. The presence of such a broad variety of organics in meteorites strongly suggests that molecules essential to life can form abiotically under astrophysical conditions. This hypothesis is strongly supported by laboratory studies in which astrophysical ice analogs (i.e., mixtures of H2O, CO, CO2, CH3OH, CH4, NH3, etc.) are subjected to ultraviolet (UV) irradiation at low temperature (less than 15 K) to simulate cold interstellar environments. These studies have shown that the organic residues recovered at room temperature after irradiation contain organic compounds that are very similar to those found in meteorites. No systematic search for the presence of sugar derivatives in laboratory residues had been carried out until the recent detection of ribose, the sugar of RNA, as well as other sugars, sugar alcohols, and sugar acids in one residue produced from the UV irradiation of an ice mixture containing H2O, CH3OH, and NH3 at 80 K. In this work, we present a detailed study of the formation of sugar derivatives contained in organic residues that are produced from the UV irradiation of ice mixtures of different starting compositions (H2O, CH3OH, CO, CO2, and/or NH3) at less than 15 K. While the presence of sugar alcohols, sugars, and sugar acids-in some cases with up to 6 carbon atoms-could be confirmed in all these residues, their distribution was shown to vary with the composition of the starting ices. In particular, only a few ices result in the formation of sugar derivatives displaying a distribution that resembles that of meteorites, in which sugar alcohols and sugar acids are very abundant while sugars are mostly absent.

Two-Dimensional Layered Double Hydroxides for Reactions of Methanation and Methane Reforming in C1 Chemistry

PubMed Central

Li, Panpan; Altaf, Naveed; Zhu, Mingyuan; Li, Jiangbing; Dai, Bin; Wang, Qiang

2018-01-01

CH4 as the paramount ingredient of natural gas plays an eminent role in C1 chemistry. CH4 catalytically converted to syngas is a significant route to transmute methane into high value-added chemicals. Moreover, the CO/CO2 methanation reaction is one of the potent technologies for CO2 valorization and the coal-derived natural gas production process. Due to the high thermal stability and high extent of dispersion of metallic particles, two-dimensional mixed metal oxides through calcined layered double hydroxides (LDHs) precursors are considered as the suitable supports or catalysts for both the reaction of methanation and methane reforming. The LDHs displayed compositional flexibility, small crystal sizes, high surface area and excellent basic properties. In this paper, we review previous works of LDHs applied in the reaction of both methanation and methane reforming, focus on the LDH-derived catalysts, which exhibit better catalytic performance and thermal stability than conventional catalysts prepared by impregnation method and also discuss the anti-coke ability and anti-sintering ability of LDH-derived catalysts. We believe that LDH-derived catalysts are promising materials in the heterogeneous catalytic field and provide new insight for the design of advance LDH-derived catalysts worthy of future research. PMID:29385064

Substrate-Controlled Product Divergence: Conversion of CO2 into Heterocyclic Products.

PubMed

Rintjema, Jeroen; Epping, Roel; Fiorani, Giulia; Martín, Eddy; Escudero-Adán, Eduardo C; Kleij, Arjan W

2016-03-14

Substituted epoxy alcohols and amines allow substrate-controlled conversion of CO2 into a wide range of heterocyclic structures through different mechanistic manifolds. This new approach results in an unusual scope of CO2-derived products by initial activation of CO2 through either the amine or alcohol unit, thus providing nucleophiles for intramolecular epoxy ring opening under mild reaction conditions. Control experiments support the crucial role of the amine/alcohol fragment in this process with the nucleophile-assisted ring-opening step following an SN i pathway, and a 5-exo-tet cyclization, thus leading to heterocyclic scaffolds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Global CO2 Distributions over Land from the Greenhouse Gases Observing Satellite (GOSAT)

NASA Technical Reports Server (NTRS)

Hammerling, Dorit M.; Michalak, Anna M.; O'Dell, Christopher; Kawa, Randolph S.

2012-01-01

January 2009 saw the successful launch of the first space-based mission specifically designed for measuring greenhouse gases, the Japanese Greenhouse gases Observing SATellite (GOSAT). We present global land maps (Level 3 data) of column-averaged CO2 concentrations (X(sub CO2)) derived using observations from the GOSAT ACOS retrieval algorithm, for July through December 2009. The applied geostatistical mapping approach makes it possible to generate maps at high spatial and temporal resolutions that include uncertainty measures and that are derived directly from the Level 2 observations, without invoking an atmospheric transport model or estimates of CO2 uptake and emissions. As such, they are particularly well suited for comparison studies. Results show that the Level 3 maps for July to December 2009 on a lO x 1.250 grid, at six-day resolution capture much of the synoptic scale and regional variability of X(sub CO2), in addition to its overall seasonality. The uncertainty estimates, which reflect local data coverage, X(sub CO2) variability, and retrieval errors, indicate that the Southern latitudes are relatively well-constrained, while the Sahara Desert and the high Northern latitudes are weakly-constrained. A probabilistic comparison to the PCTM/GEOS-5/CASA-GFED model reveals that the most statistically significant discrepancies occur in South America in July and August, and central Asia in September to December. While still preliminary, these results illustrate the usefulness of a high spatiotemporal resolution, data-driven Level 3 data product for direct interpretation and comparison of satellite observations of highly dynamic parameters such as atmospheric CO2.

Synthesis and structure of an extended cluster lead(II) carboxylate, [Pb((CO){sub 9}Co{sub 3}({mu}{sub 3}-CCO{sub 2})){sub 2}]{sub n}. Role of core metals in cluster-derived hydrogenation catalysts

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

Xinjian Lei; Maoyu Shang; Fehlner, T.P.

The reaction of lead acetate with (CO){sub 9}Co{sub 3}({mu}{sub 3}-CCOOH) leads to the formation of [Pb((CO){sub 9}Co{sub 3}({mu}{sub 3}-CCO{sub 2})){sub 2}]{sub n}, I, in high yield. The structure of I exhibits unusual six-coordinate Pb(II) centers with two asymmetrical chelating cluster carboxylates (C{sub 22}Co{sub 6}PbO{sub 22}; triclinic P1; a = 8.119(1), b = 14.346(2), c = 14.660(2) {Angstrom}; {alpha} = 102.18(1), {beta} = 99.01(1), {gamma} = 97.30(1){degrees}; Z = 2). One oxygen of each cluster carboxylate ligand bridges between adjacent lead atoms such that a chainlike extended structure is found in the solid state without the presence of solvent or water.more » I is converted stepwide on pyrolysis into two metastable forms of solid materials (designated LT and HT), each of which has been characterized spectroscopically. The hydrogenation of 2-butenal as a test reaction shows that the LT catalyst exhibits selectivities similar to previous LT materials derived from other cobalt cluster metal carboxylates and that the HT material is totally inactive. The observed release of the lead core metal under HT activation conditions totally inactivates the catalyst and demonstrates exposure of the core metal in the HT form of these novel catalysts.« less

Ag-doped Co3O4 catalyst derived from heterometallic MOF for syngas production by electrocatalytic reduction of CO2 in water

NASA Astrophysics Data System (ADS)

Zhang, Shi-Yuan; Yang, Yuan-Yuan; Zheng, Yue-Qing; Zhu, Hong-Lin

2018-07-01

Electrocatalytic reduction of CO2 to useful fuels or chemicals is a promising path for carbon recycling. In this study, a novel mixed-metallic MOF [Ag4Co2(pyz)PDC4][Ag2Co(pyz)2PDC2] was synthesized, and it transformed into Ag doped Co3O4 catalyst, which exhibits excellent electro-catalytic performance for reduction of CO2 in water to syngas (H2 + CO). The as-prepared Ag/Co3O4 material exhibits a high selectivity of CO in 0.1 M KHCO3 aqueous solution (CO2 saturated) with the corresponding faradaic efficiency up to 55.6%. Compared with the Ag/Co3O4 electrode, the maximum faradaic efficiency (FE) of CO of pure Co3O4 is 21.3% at - 1.8 V vs. SCE. The results show that the presence of Ag can improve the efficiency of CO significantly, thereby inhibiting the production of H2. The stability of the samples can be maintained for more than 10 h at - 1.8 V vs. SCE. The ratio of production between H2 and CO can be controlled by varying the potential values.

Local induction of calcium phosphate formation on TiO2 coatings on titanium via surface treatment with a CO2 laser.

PubMed

Moritz, N; Jokinen, M; Peltola, T; Areva, S; Yli-Urpo, A

2003-04-01

Sol-gel-derived TiO(2) coatings are known to promote bonelike hydroxyapatite formation on their surfaces in vitro and in vivo. Hydroxyapatite integrates into bone tissue. In some clinical applications, the surface of an implant is simultaneously interfaced with soft and hard tissues, so it should match the properties of both. A new method is introduced for treating the coatings locally in a controlled manner. The local densification of sol-gel-derived titania coatings on titanium substrates with a CO(2) laser was studied in terms of the in vitro calcium phosphate-inducting properties. CO(2)-laser-treated multilayer coatings were compared with furnace-fired coatings prepared with the same recipe and previously shown to be bioactive. Additionally, local areas of furnace-fired multilayer coatings (previously shown to be bioactive in vitro) were further laser-treated to achieve various properties in the same implant. Topological surface properties were examined with atomic force microscopy. The formation of hydroxyapatite was studied with Fourier transform infrared and scanning electron microscopy energy-dispersive X-ray analysis. The results show that calcium phosphate formation can be adjusted locally by laser treatment. Calcium phosphate is a bonelike hydroxyapatite. The local treatment of sol-gel-derived coatings with a CO(2) laser is a promising technique for creating implants with various properties to interface different tissues and a possible way of coating implants that do not tolerate furnace firing. Copyright 2003 Wiley Periodicals, Inc.

Reactive Transport of Slab-Derived Carbonatitic Melts in the Deep Upper Mantle and Generation of Kimberlites

NASA Astrophysics Data System (ADS)

Sun, C.; Dasgupta, R.

2017-12-01

Kimberlite is a diamond-bearing CO2-rich ultramafic magma from the mantle at depths of >200 km, featured by enrichment of incompatible elements [1]. It has been considered significant for understanding mantle geochemistry and particularly for providing information of deep carbon cycle. Recent experimental studies suggested that partial melts of carbonated peridotites at high pressures and temperatures could resemble the MgO (>20 wt%) and enriched incompatible elements in kimberlites only when the source experienced refertilization with perhaps prior depletion (e.g., [2]). Although addition of CO2 and incompatible elements in the deep mantle is often linked to subducted components, partial melts directly from carbonated oceanic crusts do not have high enough MgO (e.g., ≤8.2 wt%; [3]). A crucial question is how slab-derived CO2-rich melt evolves in reaction with ambient mantle, which may provide a feasible mechanism for kimberlite generation. To investigate the fate of slab-derived carbonatitic melt in the deep ambient mantle, we have performed multi-anvil experiments at 7-10 GPa and 1400-1450 °C. The starting compositions were synthesized by mixing a fertile peridotite composition, KLB-1, with variable proportions (0-45 wt.%) of Ca-rich carbonatitic melt similar to those derived from a carbonated ocean crust at 13-21 GPa [3]. Experiments were performed in Pt, Pt/Gr, Au-Pd and Au-Pd/Gr capsules, and the experimental phases include olivine ± opx + cpx + majoritic garnet ± carbonated silicate melt. With the increase of melt-rock ratios, experimental melts become progressively enriched in CaO (13.0-23.1 wt%) and CO2 (14.2-38.7 wt%) but depleted in MgO (28.9-19.9 wt%), SiO2 (33.1-7.9 wt%), and Al2O3 (2.7-0.2 wt%). The net flux of melt increases with the increase of infiltrating carbonatitic melt proportion and with the decrease of pressure. Kimberlite melts were produced from experiments with 5-25 wt% infiltrating carbonatitic melts by dissolution of olivine and orthopyroxene and precipitation of clinopyroxene. Thus, a localized influx of slab-derived CO2-rich melts can enlarge the mantle porosity, enhance melt focusing, and initiate a channelized flow of kimberlite melts. [1] Becker & Le Roex (2006) J. Pet. 47: 673-703; [2] Brey et al. (2008) J. Pet. 49: 797-821; [3] Thomson et al. (2016) Nature 529: 76-79.

Dielectric recovery mechanism of pressurized carbon dioxide at liquid and supercritical phases

NASA Astrophysics Data System (ADS)

Tanoue, Hiroyuki; Furusato, Tomohiro; Imamichi, Takahiro; Ota, Miyuki; Katsuki, Sunao; Akiyama, Hidenori

2015-09-01

Estimates of dielectric recovery rates of supercritical (SC) and liquid carbon dioxide (CO2) were derived with focus on highly-repetitive pulsed power switching mediums. Calculated results suggest that recovery time of SC and liquid CO2 are approximately 50 times shorter than that of water and oils. Prior to 10 µs after breakdown, recovery rates in neither SC nor liquid CO2 reached 100%, though the recovery rate in SC CO2 was higher than that of liquid CO2. To examine causes of recovery rate differences, each dielectric recovery process in SC and liquid CO2 was observed by laser shadowgraph technique. These shadowgraph images suggest two factors explaining dielectric recovery rate differences between these medium conditions: 1) thermodynamic property differences between medium conditions, and 2) differences in the low density region recovery mechanism.

Contribution of various carbon sources toward isoprene biosynthesis in poplar leaves mediated by altered atmospheric CO2 concentrations.

PubMed

Trowbridge, Amy M; Asensio, Dolores; Eller, Allyson S D; Way, Danielle A; Wilkinson, Michael J; Schnitzler, Jörg-Peter; Jackson, Robert B; Monson, Russell K

2012-01-01

Biogenically released isoprene plays important roles in both tropospheric photochemistry and plant metabolism. We performed a (13)CO(2)-labeling study using proton-transfer-reaction mass spectrometry (PTR-MS) to examine the kinetics of recently assimilated photosynthate into isoprene emitted from poplar (Populus × canescens) trees grown and measured at different atmospheric CO(2) concentrations. This is the first study to explicitly consider the effects of altered atmospheric CO(2) concentration on carbon partitioning to isoprene biosynthesis. We studied changes in the proportion of labeled carbon as a function of time in two mass fragments, M41(+), which represents, in part, substrate derived from pyruvate, and M69(+), which represents the whole unlabeled isoprene molecule. We observed a trend of slower (13)C incorporation into isoprene carbon derived from pyruvate, consistent with the previously hypothesized origin of chloroplastic pyruvate from cytosolic phosphenolpyruvate (PEP). Trees grown under sub-ambient CO(2) (190 ppmv) had rates of isoprene emission and rates of labeling of M41(+) and M69(+) that were nearly twice those observed in trees grown under elevated CO(2) (590 ppmv). However, they also demonstrated the lowest proportion of completely labeled isoprene molecules. These results suggest that under reduced atmospheric CO(2) availability, more carbon from stored/older carbon sources is involved in isoprene biosynthesis, and this carbon most likely enters the isoprene biosynthesis pathway through the pyruvate substrate. We offer direct evidence that extra-chloroplastic rather than chloroplastic carbon sources are mobilized to increase the availability of pyruvate required to up-regulate the isoprene biosynthesis pathway when trees are grown under sub-ambient CO(2).

Contribution of Various Carbon Sources Toward Isoprene Biosynthesis in Poplar Leaves Mediated by Altered Atmospheric CO2 Concentrations

PubMed Central

Trowbridge, Amy M.; Asensio, Dolores; Eller, Allyson S. D.; Way, Danielle A.; Wilkinson, Michael J.; Schnitzler, Jörg-Peter; Jackson, Robert B.; Monson, Russell K.

2012-01-01

Biogenically released isoprene plays important roles in both tropospheric photochemistry and plant metabolism. We performed a 13CO2-labeling study using proton-transfer-reaction mass spectrometry (PTR-MS) to examine the kinetics of recently assimilated photosynthate into isoprene emitted from poplar (Populus × canescens) trees grown and measured at different atmospheric CO2 concentrations. This is the first study to explicitly consider the effects of altered atmospheric CO2 concentration on carbon partitioning to isoprene biosynthesis. We studied changes in the proportion of labeled carbon as a function of time in two mass fragments, M41+, which represents, in part, substrate derived from pyruvate, and M69+, which represents the whole unlabeled isoprene molecule. We observed a trend of slower 13C incorporation into isoprene carbon derived from pyruvate, consistent with the previously hypothesized origin of chloroplastic pyruvate from cytosolic phosphenolpyruvate (PEP). Trees grown under sub-ambient CO2 (190 ppmv) had rates of isoprene emission and rates of labeling of M41+ and M69+ that were nearly twice those observed in trees grown under elevated CO2 (590 ppmv). However, they also demonstrated the lowest proportion of completely labeled isoprene molecules. These results suggest that under reduced atmospheric CO2 availability, more carbon from stored/older carbon sources is involved in isoprene biosynthesis, and this carbon most likely enters the isoprene biosynthesis pathway through the pyruvate substrate. We offer direct evidence that extra-chloroplastic rather than chloroplastic carbon sources are mobilized to increase the availability of pyruvate required to up-regulate the isoprene biosynthesis pathway when trees are grown under sub-ambient CO2. PMID:22384238

Magma-derived CO2 emissions in the Tengchong volcanic field, SE Tibet: Implications for deep carbon cycle at intra-continent subduction zone

NASA Astrophysics Data System (ADS)

Zhang, Maoliang; Guo, Zhengfu; Sano, Yuji; Zhang, Lihong; Sun, Yutao; Cheng, Zhihui; Yang, Tsanyao Frank

2016-09-01

Active volcanoes at oceanic subduction zone have long been regard as important pathways for deep carbon degassed from Earth's interior, whereas those at continental subduction zone remain poorly constrained. Large-scale active volcanoes, together with significant modern hydrothermal activities, are widely distributed in the Tengchong volcanic field (TVF) on convergent boundary between the Indian and Eurasian plates. They provide an important opportunity for studying deep carbon cycle at the ongoing intra-continent subduction zone. Soil microseepage survey based on accumulation chamber method reveals an average soil CO2 flux of ca. 280 g m-2 d-1 in wet season for the Rehai geothermal park (RGP). Combined with average soil CO2 flux in dry season (ca. 875 g m-2 d-1), total soil CO2 output of the RGP and adjacent region (ca. 3 km2) would be about 6.30 × 105 t a-1. Additionally, we conclude that total flux of outgassing CO2 from the TVF would range in (4.48-7.05) × 106 t a-1, if CO2 fluxes from hot springs and soil in literature are taken into account. Both hot spring and soil gases from the TVF exhibit enrichment in CO2 (>85%) and remarkable contribution from mantle components, as indicated by their elevated 3He/4He ratios (1.85-5.30 RA) and δ13C-CO2 values (-9.00‰ to -2.07‰). He-C isotope coupling model suggests involvement of recycled organic metasediments and limestones from subducted Indian continental lithosphere in formation of the enriched mantle wedge (EMW), which has been recognized as source region of the TVF parental magmas. Contamination by crustal limestone is the first-order control on variations in He-CO2 systematics of volatiles released by the EMW-derived melts. Depleted mantle and recycled crustal materials from subducted Indian continental lithosphere contribute about 45-85% of the total carbon inventory, while the rest carbon (about 15-55%) is accounted by limestones in continental crust. As indicated by origin and evolution of the TVF volatiles, mantle-derived magmas at continental subduction zone can act as important triggers for liberation of carbon stored in crustal carbonate rocks, which has the potential to be a complement to volatile recycling mechanism at subduction zones. Variations in He-Nd-Sr isotopes of magmas and volatiles from different types of plate boundaries suggest higher amounts of recycled materials for mantle wedge enrichment of continental subduction zone relative to that of oceanic subduction zone.

Curcumin-induced heme oxygenase-1 expression prevents H2O2-induced cell death in wild type and heme oxygenase-2 knockout adipose-derived mesenchymal stem cells.

PubMed

Cremers, Niels A J; Lundvig, Ditte M S; van Dalen, Stephanie C M; Schelbergen, Rik F; van Lent, Peter L E M; Szarek, Walter A; Regan, Raymond F; Carels, Carine E; Wagener, Frank A D T G

2014-10-08

Mesenchymal stem cell (MSC) administration is a promising adjuvant therapy to treat tissue injury. However, MSC survival after administration is often hampered by oxidative stress at the site of injury. Heme oxygenase (HO) generates the cytoprotective effector molecules biliverdin/bilirubin, carbon monoxide (CO) and iron/ferritin by breaking down heme. Since HO-activity mediates anti-apoptotic, anti-inflammatory, and anti-oxidative effects, we hypothesized that modulation of the HO-system affects MSC survival. Adipose-derived MSCs (ASCs) from wild type (WT) and HO-2 knockout (KO) mice were isolated and characterized with respect to ASC marker expression. In order to analyze potential modulatory effects of the HO-system on ASC survival, WT and HO-2 KO ASCs were pre-treated with HO-activity modulators, or downstream effector molecules biliverdin, bilirubin, and CO before co-exposure of ASCs to a toxic dose of H2O2. Surprisingly, sensitivity to H2O2-mediated cell death was similar in WT and HO-2 KO ASCs. However, pre-induction of HO-1 expression using curcumin increased ASC survival after H2O2 exposure in both WT and HO-2 KO ASCs. Simultaneous inhibition of HO-activity resulted in loss of curcumin-mediated protection. Co-treatment with glutathione precursor N-Acetylcysteine promoted ASC survival. However, co-incubation with HO-effector molecules bilirubin and biliverdin did not rescue from H2O2-mediated cell death, whereas co-exposure to CO-releasing molecules-2 (CORM-2) significantly increased cell survival, independently from HO-2 expression. Summarizing, our results show that curcumin protects via an HO-1 dependent mechanism against H2O2-mediated apoptosis, and likely through the generation of CO. HO-1 pre-induction or administration of CORMs may thus form an attractive strategy to improve MSC therapy.

Vertical changes of the Co and Mn speciation along a lateritic regolith developed on peridotites (New Caledonia)

DOE PAGES

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica; ...

2017-07-21

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopymore » at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. Finally, this latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.« less

Vertical changes of the Co and Mn speciation along a lateritic regolith developed on peridotites (New Caledonia)

NASA Astrophysics Data System (ADS)

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica; Noël, Vincent; Fritsch, Emmanuel; Proux, Olivier; Olivi, Luca; Ploquin, Florian; Morin, Guillaume

2017-11-01

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopy at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. This latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.

Simultaneous adsorption of CO2 and H2O under Mars-like conditions and application to the evolution of the Martian climate

NASA Technical Reports Server (NTRS)

Zent, Aaron P.; Quinn, Richard

1994-01-01

The Martian regolith is the most substantial volatile reservoir on the planet; it holds CO2 as adsorbate, and can exchange that CO2 with the atmosphere-cap system over timescales of 10(exp 5) to 10(exp 6) years. The climatic response to insolation changes caused by obliquity and eccentricity variations depends in part on the total reservoir of adsorbed CO2. Previous estimates of the adsorbate inventory have been made by measuring the adsorptive behavior of one or more Mars-analyog materials, and deriving an empirical equation that described that adsorption as a function of the partial pressure of CO2 and the temperature of the regolith. The current CO2 inventory is that which satisfies adsorptive equilibrium, observed atmospheric pressure, and no permanent CO2 caps. There is laboratory evidence that H2O poisons the CO2 adsorptive capacity of most materials. No consideration of CO2 - H2O co-adsorption was given in previous estimates of the Martian CO2 inventory, although H2O is present in the vapor phase, and so as adsorbate, throughout the regolith.

An Excel tool for deriving key photosynthetic parameters from combined gas exchange and chlorophyll fluorescence: theory and practice.

PubMed

Bellasio, Chandra; Beerling, David J; Griffiths, Howard

2016-06-01

Combined photosynthetic gas exchange and modulated fluorometres are widely used to evaluate physiological characteristics associated with phenotypic and genotypic variation, whether in response to genetic manipulation or resource limitation in natural vegetation or crops. After describing relatively simple experimental procedures, we present the theoretical background to the derivation of photosynthetic parameters, and provide a freely available Excel-based fitting tool (EFT) that will be of use to specialists and non-specialists alike. We use data acquired in concurrent variable fluorescence-gas exchange experiments, where A/Ci and light-response curves have been measured under ambient and low oxygen. From these data, the EFT derives light respiration, initial PSII (photosystem II) photochemical yield, initial quantum yield for CO2 fixation, fraction of incident light harvested by PSII, initial quantum yield for electron transport, electron transport rate, rate of photorespiration, stomatal limitation, Rubisco (ribulose 1·5-bisphosphate carboxylase/oxygenase) rate of carboxylation and oxygenation, Rubisco specificity factor, mesophyll conductance to CO2 diffusion, light and CO2 compensation point, Rubisco apparent Michaelis-Menten constant, and Rubisco CO2 -saturated carboxylation rate. As an example, a complete analysis of gas exchange data on tobacco plants is provided. We also discuss potential measurement problems and pitfalls, and suggest how such empirical data could subsequently be used to parameterize predictive photosynthetic models. © 2015 John Wiley & Sons Ltd.

From Mixed-Metal MOFs to Carbon-Coated Core-Shell Metal Alloy@Metal Oxide Solid Solutions: Transformation of Co/Ni-MOF-74 to CoxNi1-x@CoyNi1-yO@C for the Oxygen Evolution Reaction.

PubMed

Sun, Dengrong; Ye, Lin; Sun, Fangxiang; García, Hermenegildo; Li, Zhaohui

2017-05-01

Calcination of the mixed-metal species Co/Ni-MOF-74 leads to the formation of carbon-coated Co x Ni 1-x @Co y Ni 1-y O with a metal core diameter of ∼3.2 nm and a metal oxide shell thickness of ∼2.4 nm embedded uniformly in the ligand-derived carbon matrix. The close proximity of Co and Ni in the mixed-metal Co/Ni-MOF-74 promotes the metal alloying and the formation of a solid solution of metal oxide during the calcination process. The presence of the tightly coated carbon shell prohibits particle agglomeration and stabilizes the Co x Ni 1-x @Co y Ni 1-y O nanoparticles in small size. The Co x Ni 1-x @Co y Ni 1-y O@C derived from Co/Ni-MOF-74 nanocomposites show superior performance for the oxygen evolution reaction (OER). The use of mixed-metal MOFs as precursors represents a powerful strategy for the fabrication of metal alloy@metal oxide solid solution nanoparticles in small size. This method also holds great promise in the development of multifunctional carbon-coated complex core-shell metal/metal oxides owing to the diversified MOF structures and their flexible chemistry.

Origin of mitochondrial DNA diversity of domestic yaks

PubMed Central

Guo, Songchang; Savolainen, Peter; Su, Jianping; Zhang, Qian; Qi, Delin; Zhou, Jie; Zhong, Yang; Zhao, Xinquan; Liu, Jianquan

2006-01-01

Background The domestication of plants and animals was extremely important anthropologically. Previous studies have revealed a general tendency for populations of livestock species to include deeply divergent maternal lineages, indicating that they were domesticated in multiple, independent events from genetically discrete wild populations. However, in water buffalo, there are suggestions that a similar deep maternal bifurcation may have originated from a single population. These hypotheses have rarely been rigorously tested because of a lack of sufficient wild samples. To investigate the origin of the domestic yak (Poephagus grunnies), we analyzed 637 bp of maternal inherited mtDNA from 13 wild yaks (including eight wild yaks from a small population in west Qinghai) and 250 domesticated yaks from major herding regions. Results The domestic yak populations had two deeply divergent phylogenetic groups with a divergence time of > 100,000 yrs BP. We here show that haplotypes clustering with two deeply divergent maternal lineages in domesticated yaks occur in a single, small, wild population. This finding suggests that all domestic yaks are derived from a single wild gene pool. However, there is no clear correlation of the mtDNA phylogenetic clades and the 10 morphological types of sampled yaks indicating that the latter diversified recently. Relatively high diversity was found in Qinghai and Tibet around the current wild distribution, in accordance with previous suggestions that the earliest domestications occurred in this region. Conventional molecular clock estimation led to an unrealistic early dating of the start of the domestication. However, Bayesian estimation of the coalescence time allowing a relaxation of the mutation rate are better in agreement with a domestication during the Holocene as supported by archeological records. Conclusion The information gathered here and the previous studies of other animals show that the demographic histories of domestication of livestock species were highly diverse despite the common general feature of deeply divergent maternal lineages. The results further suggest that domestication of local wild prey ungulate animals was a common occurrence during the development of human civilization following the postglacial colonization in different locations of the world, including the high, arid Qinghai-Tibetan Plateau. PMID:16995938

Carbon isotopic compositions of organic matter across continental Cretaceous-Tertiary (K-T) boundary sections: Implications for paleoenvironment after the K-T impact event

USGS Publications Warehouse

Maruoka, T.; Koeberl, C.; Bohor, B.F.

2007-01-01

To assess the environmental perturbation induced by the impact event that marks the Cretaceous-Tertiary (K-T) boundary, concentrations and isotopic compositions of bulk organic carbon were determined in sedimentary rocks that span the terrestrial K-T boundary at Dogie Creek, Montana, and Brownie Butte, Wyoming in the Western Interior of the United States. The boundary clays at both sites are not bounded by coals. Although coals consist mainly of organic matter derived from plant tissue, siliceous sedimentary rocks, such as shale and clay, may contain organic matter derived from microbiota as well as plants. Coals record ??13C values of plant-derived organic matter, reflecting the ??13C value of atmospheric CO2, whereas siliceous sedimentary rocks record the ??13C values of organic matter derived from plants and microbiota. The microbiota ??13C value reflects not only the ??13C value of atmospheric CO2, but also biological productivity. Therefore, the siliceous rocks from these sites yields information that differs from that obtained previously from coal beds. Across the freshwater K-T boundary at Brownie Butte, the ??13C values decrease by 2.6??? (from - 26.15??? below the boundary clay to - 28.78??? above the boundary clay), similar to the trend in carbonate at marine K-T sites. This means that the organic ??13C values reflect the variation of ??13C of atmospheric CO2, which is in equilibrium with carbon isotopes at the ocean surface. Although a decrease in ??13C values is observed across the K-T boundary at Dogie Creek (from - 25.32??? below the boundary clay to - 26.11??? above the boundary clay), the degree of ??13C-decrease at Dogie Creek is smaller than that at Brownie Butte and that for marine carbonate. About 2??? decrease in ??13C of atmospheric CO2 was expected from the ??13C variation of marine carbonate at the K-T boundary. This ??13C-decrease of atmospheric CO2 should affect the ??13C values of organic matter derived from plant tissue. As such a decrease in ??13C value was not observed at Dogie Creek, a process that compensates the ??13C-decrease of atmospheric CO2 should be involved. For example, the enhanced contribution of 13C-enriched organic matter derived from algae in a high-productivity environment could be responsible. The ??13C values of algal organic matter become higher than, and thus distinguishable from, those of plant organic matter in situations with high productivity, where dissolved HCO3- becomes an important carbon source, as well as dissolved CO2. As the ??13C-decrease of atmospheric CO2 reflected a reduction of marine productivity, the compensation of the ??13C decrease by the enhanced activity of the terrestrial microbiota means that the microbiota at freshwater environment recovered more rapidly than those in the marine environment. A distinct positive ??13C excursion of 2??? in the K-T boundary clays is superimposed on the overall decreasing trend at Dogie Creek; this coincides with an increase in the content of organic carbon. We conclude that the K-T boundary clays include 13C-enriched organic matter derived from highly productive algae. Such a high biological productivity was induced by phenomena resulting from the K-T impact, such as nitrogen fertilization and/or eutrophication induced by enhanced sulfide formation. The high productivity recorded in the K-T boundary clays means that the freshwater environments (in contrast to marine environments) recovered rapidly enough to almost immediately (within 10??yr) respond to the impact-related environmental perturbations. ?? 2006 Elsevier B.V. All rights reserved.

Single-component and binary CO2 and H2O adsorption of amine-functionalized cellulose.

PubMed

Gebald, Christoph; Wurzbacher, Jan A; Borgschulte, Andreas; Zimmermann, Tanja; Steinfeld, Aldo

2014-02-18

A fundamental analysis of single-component and binary CO2 and H2O adsorption of amine-functionalized nanofibrillated cellulose is carried out in the temperature range of 283-353 K and at CO2 partial pressures in the range of 0.02-105 kPa, where the ultralow partial pressure range is relevant for the direct capture of CO2 from atmospheric air. Single-component CO2 and H2O adsorption experimental data are fitted to the Toth and Guggenheim-Anderson-de Boer models, respectively. Corresponding heats of adsorption, derived from explicit solutions of the van't Hoff equation, are -50 kJ/mol CO2 and -48.8 kJ/mol H2O. Binary CO2/H2O adsorption measurements for humid air reveal that the presence of H2O at 2.55 kPa enhances CO2 adsorption, while the presence of CO2 at 0.045 kPa does not influence H2O adsorption. The energy demand of the temperature-vacuum-swing adsorption/desorption cycle for delivering pure CO2 from air increases significantly with H2O adsorption and indicates the need to reduce the hygroscopicity of the adsorbent.

H2, CO, and dust absorption through cold molecular clouds

NASA Astrophysics Data System (ADS)

Lacy, John H.; Sneden, Chris; Kim, Hwihyun; Jaffe, Daniel Thomas

2017-06-01

We have made observations with IGRINS on the Harlan J. Smith telescope at McDonald Observatory of near-infrared absorption by H2, CO, and dust toward stars behind molecular clouds, primarily the TMC. Prior to these observations, the abundance of H2 in molecular clouds, relative to the commonly used tracer CO, had only been measured toward a few embedded stars, which may be surrounded by atypical gas. The new observations provide a representative sample of these molecules in cold molecular gas. We find N(H2)/Av ~ 0.9e+21, N(CO)/Av ~ 1.6e+17, and H2/CO ~ 6000. The measured H2/CO ratio is consistent with that measured toward embedded stars in various molecular clouds, but half that derived from mm-wave observations of CO emission and star counts or other determinations of Av.

Multishelled CaO Microspheres Stabilized by Atomic Layer Deposition of Al2 O3 for Enhanced CO2 Capture Performance.

PubMed

Armutlulu, Andac; Naeem, Muhammad Awais; Liu, Hsueh-Ju; Kim, Sung Min; Kierzkowska, Agnieszka; Fedorov, Alexey; Müller, Christoph R

2017-11-01

CO 2 capture and storage is a promising concept to reduce anthropogenic CO 2 emissions. The most established technology for capturing CO 2 relies on amine scrubbing that is, however, associated with high costs. Technoeconomic studies show that using CaO as a high-temperature CO 2 sorbent can significantly reduce the costs of CO 2 capture. A serious disadvantage of CaO derived from earth-abundant precursors, e.g., limestone, is the rapid, sintering-induced decay of its cyclic CO 2 uptake. Here, a template-assisted hydrothermal approach to develop CaO-based sorbents exhibiting a very high and cyclically stable CO 2 uptake is exploited. The morphological characteristics of these sorbents, i.e., a porous shell comprised of CaO nanoparticles coated by a thin layer of Al 2 O 3 (<3 nm) containing a central void, ensure (i) minimal diffusion limitations, (ii) space to accompany the substantial volumetric changes during CO 2 capture and release, and (iii) a minimal quantity of Al 2 O 3 for structural stabilization, thus maximizing the fraction of CO 2 -capture-active CaO. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intramolecular B/N frustrated Lewis pairs and the hydrogenation of carbon dioxide.

PubMed

Courtemanche, Marc-André; Pulis, Alexander P; Rochette, Étienne; Légaré, Marc-André; Stephan, Douglas W; Fontaine, Frédéric-Georges

2015-06-18

The FLP species 1-BR2-2-NMe2-C6H4 (R = 2,4,6-Me3C6H2, 2,4,5-Me3C6H2) reacts with H2 in sequential hydrogen activation and protodeborylation reactions to give (1-BH2-2-NMe2-C6H4)2. While reacts with H2/CO2 to give formyl, acetal and methoxy-derivatives, reacts with H2/CO2 to give C6H4(NMe2)(B(2,4,5-Me3C6H2)O)2CH2. The mechanism of CO2 reduction is considered.

Effects of elevated CO2 on soil organic matter turnover and plant nitrogen uptake: First results from a dual labeling mesocosm experiment

NASA Astrophysics Data System (ADS)

Eder, Lucia Muriel; Weber, Enrico; Schrumpf, Marion; Zaehle, Sönke

2017-04-01

The response of plant growth to elevated concentrations of CO2 (eCO2) is often constrained by plant nitrogen (N) uptake. To overcome potential N limitation, plants may invest photosynthetically fixed carbon (C) into N acquiring strategies, including fine root biomass, root exudation, or C allocation to mycorrhizal fungi. In turn, these strategies may affect the decomposition of soil organic matter, leading to uncertainties in net effects of eCO2 on C storage. To gain more insight into these plant-soil C-N-interactions, we combined C and N stable isotope labeling in a mesocosm experiment. Saplings of Fagus sylvatica L. were exposed to a 13CO2 enriched atmosphere at near ambient (380 ppm) or elevated (550 ppm) CO2 concentrations for four months of the vegetation period in 2016. Aboveground and belowground net CO2 fluxes were measured separately and the 13C label enabled partitioning of total soil CO2 efflux into old, soil derived and new, plant-derived C. We used ingrowth cores to assess effects of eCO2on belowground C allocation and plant N uptake in more detail and in particular we evaluated the relative importance of ectomycorrhizal associations. In the soil of each sapling, ingrowth cores with different mesh sizes allowed fine roots or only mycorrhizal hyphae to penetrate. In one type of ingrowth core each, we incorporated fine root litter that was enriched in 15N. Additionally, total N uptake was estimated by using 15N enriched saplings and unlabeled control plants. We found that eCO2 increased aboveground net CO2 exchange rates by 19% and total soil respiration by 11%. The eCO2 effect for GPP and also for NPP was positive (+23% and +11%, respectively). By combining gaseous C fluxes with data on new and old C stocks in bulk soil and plants through destructive harvesting in late autumn 2016, we will be able to infer net effects of eCO2 on the fate of C in these mesocosms. Biomass allocation patterns can reveal physiological responses to high C availability under potentially constrained N availability. Together with data on biomass production within the ingrowth cores these results elucidate mechanisms affecting soil C storage and plant N uptake under eCO2.

Composition and physical properties of Enceladus' surface

USGS Publications Warehouse

Brown, R.H.; Clark, R.N.; Buratti, B.J.; Cruikshank, D.P.; Barnes, J.W.; Mastrapa, R.M.E.; Bauer, J.; Newman, S.; Momary, T.; Baines, K.H.; Bellucci, G.; Capaccioni, F.; Cerroni, P.; Combes, M.; Coradini, A.; Drossart, P.; Formisano, V.; Jaumann, R.; Langavin, Y.; Matson, D.L.; McCord, T.B.; Nelson, R.M.; Nicholson, P.D.; Sicardy, B.; Sotin, Christophe

2006-01-01

Observations of Saturn's satellite Enceladus using Cassini's Visual and Infrared Mapping Spectrometer instrument were obtained during three flybys of Enceladus in 2005. Enceladus' surface is composed mostly of nearly pure water ice except near its south pole, where there are light organics, CO2, and amorphous and crystalline water ice, particularly in the region dubbed the "tiger stripes." An upper limit of 5 precipitable nanometers is derived for CO in the atmospheric column above Enceladus, and 2% for NH 3 in global surface deposits. Upper limits of 140 kelvin (for a filled pixel) are derived for the temperatures in the tiger stripes.

Several novel N-donor tridentate ligands formed in chemical studies of new fac-Re(CO)3 complexes relevant to fac-99mTc(CO)3 radiopharmaceuticals: attack of a terminal amine on coordinated acetonitrile.

PubMed

Perera, Theshini; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G

2010-03-01

To evaluate syntheses of fac-[Re(CO)(3)L](+) complexes in organic solvents, we treated fac-[Re(CO)(3)(CH(3)CN)(3)]PF(6)/BF(4) in acetonitrile with triamine ligands (L). When L had two primary or two tertiary terminal amine groups, the expected fac-[Re(CO)(3)L](+) complexes formed. In contrast, N,N-dimethyldiethylenetriamine (N,N-Me(2)dien) formed an unusual compound, fac-[Re(CO)(3)(DAE)]BF(4) {DAE = (Z)-N'-(2-(2-(dimethylamino)ethylamino)ethyl)acetimidamide = (Me(2)NCH(2)CH(2))NH(CH(2)CH(2)N=C(NH(2))Me)}. DAE is formed by addition of acetonitrile to the N,N-Me(2)dien terminal primary amine, converting this sp(3) nitrogen to an sp(2) nitrogen with a double bond to the original acetonitrile sp carbon. The three Ns bound to Re derive from N,N-Me(2)dien. The pathway to fac-[Re(CO)(3)(DAE)]BF(4) is suggested by a second unusual compound, fac-[Re(CO)(3)(MAE)]PF(6) {MAE = N-methyl-N-(2-(methyl-(2-(methylamino)ethyl)amino)ethyl)acetimidamide = MeN(H)-CH(2)CH(2)-N(Me)-CH(2)CH(2)-N(Me)-C(Me)=NH}, isolated after treating fac-[Re(CO)(3)(CH(3)CN)(3)]PF(6) with N,N',N''-trimethyldiethylenetriamine (N,N',N''-Me(3)dien). MAE chelates via a terminal and a central sp(3) N from N,N',N''-Me(3)dien and via one sp(2) NH in a C(Me)=NH group. This group is derived from acetonitrile by addition of the other N,N',N''-Me(3)dien terminal amine to the nitrile carbon. This addition creates an endocyclic NMe group within a seven-membered chelate ring. The structure and other properties of fac-[Re(CO)(3)(MAE)]PF(6) allow us to propose a reaction scheme for the formation of the unprecedented DAE ligand. The new compounds advance our understanding of the spectral and structural properties of Re analogues of (99m)Tc radiopharmaceuticals.

Electronic Structure and Multisite Basicity of the Pyramidal Phosphinidene-Bridged Dimolybdenum Complex [Mo2(η(5)-C5H5)(μ-κ(1):κ(1),η(5)-PC5H4)(η(6)-C6H3(t)Bu3)(CO)2(PMe3)].

PubMed

Albuerne, Isabel G; Alvarez, M Angeles; García, M Esther; García-Vivó, Daniel; Ruiz, Miguel A

2015-10-19

The title phosphinidene complex could be sequentially protonated with HBF4·OEt2 or [H(OEt2)2](BAr'4) to give the phosphido-bridged derivatives [Mo2Cp(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X and then the hydrides [Mo2Cp(H)(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X2 (X = BF4, BAr'4; Ar' = 3,5-C6H3(CF3)2; Mes* = 2,4,6-C6H2(t)Bu3). Density functional theory (DFT) calculations revealed that the most favored site for initial electrophilic attack is the metallocene Mo atom, but attachment of the electrophile to the phosphinidene P atom gives more stable products. This was in agreement with all other reactions investigated, which invariably involved the attachment of the added electrophile at the P site. Thus, the title compound reacted with S8 at 223 K to give the thiophosphinidene-bridged complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(S)C5H4}(η(6)-HMes*)(CO)2(PMe3)], a poorly stable molecule which reacted with MeI at room temperature to give the corresponding thiolatophosphido derivative, isolated as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(SMe)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4) (P-S = 2.128(4) Å) after anion exchange with Na(BAr'4). Reaction of the title compound with MeI proceeded smoothly to give the corresponding methylphosphido derivative, isolated analogously as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4). The related complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe2Ph)](BAr'4) (P-C(Me) = 1.841(5) Å) could be prepared analogously from the neutral precursor [Mo2Cp{μ-κ(1):κ(1),η(5)-PC5H4}(η(6)-HMes*)(CO)2(PMe2Ph)]. In contrast, reaction of the title complex with ethylene sulfide involved opening of the C2S ring and formation of new P-C and Mo-S bonds (1.886(7) and 2.493(2) Å, respectively), with displacement of the PMe3 ligand, to give the phosphido-thiolato complex [Mo2Cp{μ-κ(2)(P,S):κ(1)P,η(5)-P(C2H4S)C5H4}(η(6)-HMes*)(CO)2]. All these derivatives of the title complex displayed an unusual trigonal pyramidal-like environment around the bridging P atom, with the added electrophile placed in the Mo2P plane as a result of the directionality of the relevant frontier orbital of the phosphinidene complex, according to DFT calculations.

Bolide impacts and the oxidation state of carbon in the earth's early atmosphere

NASA Technical Reports Server (NTRS)

Kasting, James F.

1990-01-01

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean.

Oxygen and nitrogen co-doped porous carbon nanosheets derived from Perilla frutescens for high volumetric performance supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Bei; Liu, Yijiang; Chen, Hongbiao; Yang, Mei; Li, Huaming

2017-02-01

Biomass-derived O/N-co-doped porous carbons have become the most competitive electrode materials for supercapacitors because of their renewability and sustainability. We herein present a simple approach to fabricate O/N-co-doped porous carbon nanosheets by the direct pyrolysis of Perilla frutescens (PF) leaves. Under optimum pyrolysis temperature (700 °C), the PF leaf-derived carbon nanosheets (PFC-700) having O, N contents of 18.76 at.% and 1.70 at.%, respectively, exhibit a hierarchical pore structure with a moderate BET surface area (655 m2 g-1) and a relatively low pore volume (0.44 cm3 g-1). Such O/N-co-doped porous carbon nanosheets display both high gravimetric capacitance (270 F g-1 at 0.5 A g-1) and high volumetric capacitance (287 F cm-3 at 0.5 A g-1). In addition, the PFC-700-based symmetric supercapacitor offers a high volumetric energy density (14.8 Wh L-1 at 490 W L-1) as well as a high stability (about 96.1% of capacitance retention after 10000 cycles at 2 A g-1).

Far-infrared-light shadowgraphy for high extraction efficiency of extreme ultraviolet light from a CO2-laser-generated tin plasma

NASA Astrophysics Data System (ADS)

Matsukuma, Hiraku; Hosoda, Tatsuya; Suzuki, Yosuke; Yogo, Akifumi; Yanagida, Tatsuya; Kodama, Takeshi; Nishimura, Hiroaki

2016-08-01

The two-color, double-pulse method is an efficient scheme to generate extreme ultraviolet light for fabricating the next generation semiconductor microchips. In this method, a Nd:YAG laser pulse is used to expand a several-tens-of-micrometers-scale tin droplet, and a CO2 laser pulse is subsequently directed at the expanded tin vapor after an appropriate delay time. We propose the use of shadowgraphy with a CO2 laser probe-pulse scheme to optimize the CO2 main-drive laser. The distribution of absorption coefficients is derived from the experiment, and the results are converted to a practical absorption rate for the CO2 main-drive laser.

Modeling for CO poisoning of a fuel cell anode

NASA Technical Reports Server (NTRS)

Dhar, H. P.; Kush, A. K.; Patel, D. N.; Christner, L. G.

1986-01-01

Poisoning losses in a half-cell in the 110-190 C temperature range have been measured in 100 wt pct H3PO4 for various mixtures of H2, CO, and CO2 gases in order to investigate the polarization loss due to poisoning by CO of a porous fuel cell Pt anode. At a fixed current density, the poisoning loss was found to vary linearly with ln of the CO/H2 concentration ratio, although deviations from linearity were noted at lower temperatures and higher current densities for high CO/H2 concentration ratios. The surface coverages of CO were also found to vary linearly with ln of the CO/H2 concentration ratio. A general adsorption relationship is derived. Standard free energies for CO adsorption were found to vary from -14.5 to -12.1 kcal/mol in the 130-190 C temperature range. The standard entropy for CO adsorption was found to be -39 cal/mol per deg K.

Helium isotopic and chemical composition of gases from volcanic-hydrothermal systems in the Philippines

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

Giggenbach, W.F.; Poreda, R.J.

1993-10-01

Relative {sup 3}He, {sup 4}He, Ne, Ar, N{sub 2} and CO{sub 2} contents of gases collected from high temperature geothermal systems associated with active subduction zones in the Philippines, (Cagua, Alto Peak, Mahagnao, Mambucal and Mount Apo) correspond to {sup 3}He/{sup 4}He ratios of 6.9 to 7.6 R{sub A}, CO{sub 2}/{sup 3}He ratios of 10 to 50 {times} 10{sup 9} and N{sub 2}/Ar ratios of 200 to 500. The data suggest that He is essentially of upper mantle origin and that CO{sub 2} and N{sub 2} are predominantly derived from subducted sediments. Highest CO{sub 2}/He ratios are observed for systemsmore » along the centerline between major zones of active subduction to the E and W of the Philippine islands. The high values may tentatively be explained in terms of derivation from an especially CO{sub 2}-rich magmatic environment created by the supply of volatiles from two subduction systems. The low {sup 3}He/{sup 4}He ratios of 0.4 and 0.6 R{sub A} for two springs on the island of Palawan indicate that the thermal waters there are the result of only residual geothermal activity associated with an, at present, inactive subduction zone.« less

Stable isotopes of carbon dioxide in soil gas over massive sulfide mineralization at Crandon, Wisconsin

USGS Publications Warehouse

Alpers, Charles N.; Dettman, D.L.; Lohmann, K.C.; Brabec, D.

1990-01-01

Stable isotope ratios of oxygen and carbon were determined for CO2 in soil gas in the vicinity of the massive sulfide deposit at Crandon, Wisconsin with the objective of determining the source of anomalously high CO2 concentrations detected previously by McCarthy et al. (1986). Values of ??13C in soil gas CO2 from depths between 0.5 and 1.0 m were found to range from -12.68??? to -20.03??? (PDB). Organic carbon from the uppermost meter of soil has ??13C between -24.1 and -25.8??? (PDB), indicating derivation from plant species with the C3 (Calvin) type of photosynthetic pathway. Microbial decomposition of the organic carbon and root respiration from C3 and C4 (Hatch-Slack) plants, together with atmospheric CO2 are the likely sources of carbon in soil gas CO2. Values of ??18O in soil-gas CO2 range from 32 to 38??? (SMOW). These ??18O values are intermediate between that calculated for CO2 gas in isotopic equilibrium with local groundwaters and that for atmospheric CO2. The ??18O data indicate that atmospheric CO2 has been incorporated by mixing or diffusion. Any CO2 generated by microbial oxidation of organic matter has equilibrated its oxygen isotopes with the local groundwaters. The isotopic composition of soil-gas CO2 taken from directly above the massive sulfide deposit was not distinguishable from that of background samples taken 1 to 2 km away. No enrichment of the ??13C value of soil-gas CO2 was observed, contrary to what would be expected if the anomalous CO2 were derived from the dissolution of Proterozoic marine limestone country rock or of Paleozoic limestone clasts in glacial till. Therefore, it is inferred that root respiration and decay of C3 plant material were responsible for most CO2 generation both in the vicinity of the massive sulfide and in the "background" area, on the occasion of our sampling. Interpretation of our data is complicated by the effects of rainfall, which significantly reduced the magnitude of the CO2 anomaly. Therefore, we cannot rule out the possible mechanism of carbonate dissolution driven by pyrite oxidation, as proposed by Lovell et al. (1983) and McCarthy et al. (1986). Further work is needed on seasonal and daily variations of CO2 concentrations and stable isotope ratios in various hydrogeologic and ecologic settings so that more effective sampling strategies can be developed for mineral exploration using soil gases. ?? 1990.

Origin and transport of CH4 in two maar lakes fed by mantle-derived volatiles (Mt. Vulture volcano, Italy)

NASA Astrophysics Data System (ADS)

Caracausi, Antonio; Cosenza, Paolo; Favara, Rocco; Foresta Martin, Luigi; Galli, Nunzio; Grassa, Fausto; Nuccio, Pasquale Mario; Paternoster, Michele; Riccobono, Giuseppe

2014-05-01

It has been assessed that lakes contribute 6 to 16% to global CH4 emission in atmosphere. Accumulation of CH4 in the water is strongly dependent on the input of gas and the dynamic of the lake's water. Lakes located on tectonically and volcanically active areas (e.g., Kivu, Nyos) generally contain relevant amount of mantle-derived volatiles. This generated an open debate on the origin of CO2 and CH4 in volcanic lakes because the complex bio-geological cycling of these two gases. This study is a part of larger investigation carried out on two maar lakes (LPM and LGM) formed about 140.000 years ago during the last eruption of Mt. Vulture (Italy). In spite of it generally is considered to be extinct, both lakes are characterized by an active inflow of mantle-derived fluids (Caracausi et al., 2013). Although the two lakes are only 150 m apart, their respective dynamics are different being LPM a meromictic lake, while LGM a monomictic one (Caracausi et al., 2013). The stagnant waters of LPM are enriched in CO2 and CH4 but the total gas pressure is below the hydrostatic pressure, so that the transfer of gas towards the surface doesn't occur via bubbles. Vertical profiles at LPM reveal a marked decrease of the dissolved CH4 content in the shallower layers due to aerated water. The amount of CH4 dissolved in LGM water column shows seasonal variations: in autumn it is comparable to that of LPM at the same depth; in winter CH4 is fully released into atmosphere through overturn of waters. C and H isotopes of CH4 clearly indicate in both lakes an active production both by acetoclastic methanogenesis and by CO2 reduction although with different proportions. Historical reports describe intense episodic releases of gases from both lakes occurred up to about 200 years ago. Caracausi et al. (2013) highlight that these events could be caused by a release of mantle-derived CO2 accumulated in the crust or directly linked to magma degassing. In the present study the knowledge gained from previous limnological-geochemical investigations has been joined with isotope signature of gas (CH4 and CO2) collected from sediments at the bottom of LPM, by means of a specially designed robot called "Muddy". Muddy is also able to perform vertical profiles both of pH and of temperature in the water column and in the sediments as well. The obtained results lead us: 1) to assess the production ratio of CH4 through acetoclastic methanogenesis and CO2 reduction in the sediments; 2) to determinate CH4 oxidation; 3) to detect the origin of CO2 involved in methanogenic processes, evaluating the contribution organic-CO2 and the sink of mantle-derived CO2.;4) to discuss the differences in CH4 sources in the water and sediments; 5) to properly define gas hazards assessment. A. Caracausi, M. Nicolosi, P.M. Nuccio, R. Favara, M. Paternoster, A. Rosciglione (2013) Geochemical insight into differences in the physical structures and dynamics of two adjacent maar lakes at Mt. Vulture volcano (southern Italy), G. Cubed, doi: 10.1002/ggge.2011

Crustal CO2 liberation during the 2006 eruption and earthquake events at Merapi volcano, Indonesia

NASA Astrophysics Data System (ADS)

Troll, Valentin R.; Hilton, David R.; Jolis, Ester M.; Chadwick, Jane P.; Blythe, Lara S.; Deegan, Frances M.; Schwarzkopf, Lothar M.; Zimmer, Martin

2012-06-01

High-temperature volcanic gas is widely considered to originate from ascending, mantle-derived magma. In volcanic arc systems, crustal inputs to magmatic gases mainly occur via subducted sediments in the mantle source region. Our data from Merapi volcano, Indonesia imply, however, that during the April-October 2006 eruption significant quantities of CO2 were added from shallow crustal sources. We show that prior to the 2006 events, summit fumarole gas δ13C(CO2) is virtually constant (δ13C1994-2005 = -4.1 ± 0.3‰), but during the 2006 eruption and after the shallow Yogyakarta earthquake of late May, 2006 (M6.4; hypocentres at 10-15 km depth), carbon isotope ratios increased to -2.4 ± 0.2‰. This rise in δ13C is consistent with considerable addition of crustal CO2 and coincided with an increase in eruptive intensity by a factor of ˜3 to 5. We postulate that this shallow crustal volatile input supplemented the mantle-derived volatile flux at Merapi, intensifying and sustaining the 2006 eruption. Late-stage volatile additions from crustal contamination may thus provide a trigger for explosive eruptions independently of conventional magmatic processes.

The ETHANOL-CO_2 Dimer is AN Electron Donor-Acceptor Complex

NASA Astrophysics Data System (ADS)

McGuire, Brett A.; Martin-Drumel, Marie-Aline; McCarthy, Michael C.

2017-06-01

Supercritical (sc) CO_2 is a common industrial solvent for the extraction of caffeine, nicotine, petrochemicals, and natural products. The ability of apolar scCO_2 to dissolve polar solutes is greatly enhanced by the addition of a polar co-solvent, often methanol or ethanol. Experimental and theoretical work show that methanol interactions in scCO_2 are predominantly hydrogen bonding, while the gas-phase complex is an electron donor-acceptor (EDA) configuration. Ethanol, meanwhile, is predicted to form EDA complexes both in scCO_2 and in the gas phase, but there have been no experimental measurements to support this conclusion. Here, we report a combined chirped-pulse and cavity FTMW study of the ethanol-CO_2 complex. Comparison with theory indicates the EDA complex is dominant under our experimental conditions. We confirm the structure with isotopic substitution, and derive a semi-experimental equilibrium structure. Our results are consistent with theoretical predictions that the linearity of the CO_2 subgroup is broken by the complexation interaction.

Retrieval of CO2 and N2 in the Martian thermosphere using dayglow observations by IUVS on MAVEN

NASA Astrophysics Data System (ADS)

Evans, J. S.; Stevens, M. H.; Lumpe, J. D.; Schneider, N. M.; Stewart, A. I. F.; Deighan, J.; Jain, S. K.; Chaffin, M. S.; Crismani, M.; Stiepen, A.; McClintock, W. E.; Holsclaw, G. M.; Lefèvre, F.; Lo, D. Y.; Clarke, J. T.; Eparvier, F. G.; Thiemann, E. M. B.; Chamberlin, P. C.; Bougher, S. W.; Bell, J. M.; Jakosky, B. M.

2015-11-01

We present direct number density retrievals of carbon dioxide (CO2) and molecular nitrogen (N2) for the upper atmosphere of Mars using limb scan observations during October and November 2014 by the Imaging Ultraviolet Spectrograph on board NASA's Mars Atmosphere and Volatile EvolutioN (MAVEN) spacecraft. We use retrieved CO2 densities to derive temperature variability between 170 and 220 km. Analysis of the data shows (1) low-mid latitude northern hemisphere CO2 densities at 170 km vary by a factor of about 2.5, (2) on average, the N2/CO2 increases from 0.042 ± 0.017 at 130 km to 0.12 ± 0.06 at 200 km, and (3) the mean upper atmospheric temperature is 324 ± 22 K for local times near 14:00.

Effects of climate change on surface-water photochemistry: a review.

PubMed

De Laurentiis, Elisa; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

2014-10-01

Information concerning the link between surface-water photochemistry and climate is presently very scarce as only a few studies have been dedicated to the subject. On the basis of the limited knowledge that is currently available, the present inferences can be made as follows: (1) Warming can cause enhanced leaching of ionic solutes from the catchments to surface waters, including cations and more biologically labile anions such as sulphate. Preferential sulphate biodegradation followed by removal as organic sulphides in sediment could increase alkalinity, favouring the generation of the carbonate radical, CO3 (·-). However, this phenomenon would be easily offset by fluctuations of the dissolved organic carbon (DOC), which is strongly anticorrelated with CO3 (·-). Therefore, obtaining insight into DOC evolution is a key issue in understanding the link between photochemistry and climate. (2) Climate change could exacerbate water scarcity in the dry season in some regions. Fluctuations in the water column could deeply alter photochemistry that is usually favoured in shallower waters. However, the way water is lost would strongly affect the prevailing photoinduced processes. Water outflow without important changes in solute concentration would mostly favour reactions induced by the hydroxyl and carbonate radicals (·OH and CO3 (·-)). In contrast, evaporative concentration would enhance reactions mediated by singlet oxygen ((1)O2) and by the triplet states of chromophoric dissolved organic matter ((3)CDOM*). (3) In a warmer climate, the summer stratification period of lakes would last longer, thereby enhancing photochemical reactions in the epilimnion but at the same time keeping the hypolimnion water in the dark for longer periods.

Consequences of artichoke thistle invasion and removal on carbon and water cycling in a Mediterranean grassland

NASA Astrophysics Data System (ADS)

Potts, D. L.; Harpole, W. S.; Suding, K. N.; Goulden, M. L.

2006-12-01

Changes in vegetation structure and composition may interact with management activities to influence biosphere-atmosphere exchanges of mass and energy in unforeseen ways. Increases in the distribution and density of artichoke thistle (Cynara cardunculus), a perennial, non-native forb in Californian coastal grasslands, may alter seasonal dynamics of ecosystem C-assimilation and evapotranspiration (ET). During spring and summer 2006, we compared midday net ecosystem CO2 exchange (NEE) and ET among adjacent grassland plots where thistle was present and where it was absent. Estimates of NEE supported the prediction that deeply-rooted thistles increase ecosystem C-assimilation. Measurements of midday ecosystem respiration demonstrated that increases in ecosystem C-assimilation were associated with increased ecosystem photosynthesis rather than declines in respiration. Furthermore, the presence of C. cardunculus increased midday ET but did not influence shallow soil moisture or ecosystem water use efficiency. Following the initial sampling in late April, we removed C. cardunculus from half the thistle- containing plots with spot applications of herbicide. Three weeks later, fluxes in thistle-removal plots were indistinguishable from those in plots where thistles were never present, suggesting additive rather than interactive effects of thistles on grassland CO2 exchange and ET. Similar to woody-encroachment in some semi-arid ecosystems, C. cardunculus invasion in Californian grasslands increases ecosystem CO2 assimilation. Moreover, our results suggest that herbicide removal of C. cardunculus may be accompanied by few legacy effects. Future research should focus on the effects of C. cardunculus on early-growing season fluxes and belowground C-storage, and the interaction between the spread of non-native species and climate variability on biosphere-atmosphere exchanges of carbon and water.

Synthesis of terpene and steroid dimers and trimers having cyclobutadienyl-Co and aromatic tethers.

PubMed

Sierra, Miguel A; Torres, M Rosario; Torre, María C de la; Alvaro, Elsa

2007-05-25

The reaction of natural product derived propargylic alcohols with CpCo(CO)2 produces three new types of natural product hybrids having two or three terpene or steroid fragments. The tether joining the natural product subunits is built during the reaction. Type 1 hybrids have two terpene or steroid moieties joined by a CpCo-cyclobutadiene tether, with the two units disposed in a 1,2-arrangement (9, 14, 22). Type 2 hybrids have a Co-cyclopentadienone tether (10). Type 3 has three units of terpene or steroid joined to a benzene ring (11, 12, 15). An unusual Co-mediated beta-carbon elimination pathway of propargylic alcohols leading to ketones (an unknown process in this chemistry) has been observed.

Zwitterionic metal carboxylate complexes: In solid state

NASA Astrophysics Data System (ADS)

Nath, Bhaskar; Kalita, Dipjyoti; Baruah, Jubaraj B.

2012-07-01

A flexible dicarboxylic acid having composition [(CH(o-C5H4N)(p-C6H4OCH2CO2H)2] derived from corresponding bis-phenol reacts with various metal(II) acetates such as manganese(II), cobalt(II) and nickel(II) acetate leads to zwtterionic complexes with compositions [CH(o-C5H4N)(p-C6H4OCH2CO2){p-C6H4OCH2CO2M(H2O)5}].6H2O (where M = Mn, Co, Ni). The complexes are characterised by X-ray crystallography. These complexes have chiral center due to unsymmetric structure conferred to the ligand through coordination at only one carboxylate group of the ligand. In solid state these complexes are racemic.

Synthesis, spectroscopic, electrochemical and computational studies of rhenium(i) tricarbonyl complexes based on bidentate-coordinated 2,6-di(thiazol-2-yl)pyridine derivatives.

PubMed

Klemens, Tomasz; Czerwińska, Katarzyna; Szlapa-Kula, Agata; Kula, Slawomir; Switlicka, Anna; Kotowicz, Sonia; Siwy, Mariola; Bednarczyk, Katarzyna; Krompiec, Stanisław; Smolarek, Karolina; Maćkowski, Sebastian; Danikiewicz, Witold; Schab-Balcerzak, Ewa; Machura, Barbara

2017-07-25

Nine rhenium(i) complexes possessing three carbonyl groups together with a bidentate coordinated 2,6-di(thiazol-2-yl)pyridine derivative were synthesized to examine the impact of structure modification of the triimine ligand on the photophysical, thermal and electrochemical properties of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)]. The Re(i) complexes were fully characterized using IR, 1 H and 13 C, HRMS-ESI and single crystal X-ray analysis. Their thermal properties were evaluated using DSC and TGA measurements. Photoluminescence spectra of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)] were investigated in solution and in the solid state, at 298 and 77 K. Both emission wavelengths and quantum yields of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)] were found to be structure-related, demonstrating a crucial role of the substituent attached to the 2,6-di(thiazol-2-yl)pyridine skeleton. In order to fully understand the photophysical properties of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)], density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed. Furthermore, the complexes which showed appropriate solubility in chloroform were tested as an emissive active layer in OLED devices.

3D-QSAR studies and molecular docking on [5-(4-amino-1 H-benzoimidazol-2-yl)-furan-2-yl]-phosphonic acid derivatives as fructose-1,6-biphophatase inhibitors

NASA Astrophysics Data System (ADS)

Lan, Ping; Xie, Mei-Qi; Yao, Yue-Mei; Chen, Wan-Na; Chen, Wei-Min

2010-12-01

Fructose-1,6-biphophatase has been regarded as a novel therapeutic target for the treatment of type 2 diabetes mellitus (T2DM). 3D-QSAR and docking studies were performed on a series of [5-(4-amino-1 H-benzoimidazol-2-yl)-furan-2-yl]-phosphonic acid derivatives as fructose-1,6-biphophatase inhibitors. The CoMFA and CoMSIA models using thirty-seven molecules in the training set gave r cv 2 values of 0.614 and 0.598, r 2 values of 0.950 and 0.928, respectively. The external validation indicated that our CoMFA and CoMSIA models possessed high predictive powers with r 0 2 values of 0.994 and 0.994, r m 2 values of 0.751 and 0.690, respectively. Molecular docking studies revealed that a phosphonic group was essential for binding to the receptor, and some key features were also identified. A set of forty new analogues were designed by utilizing the results revealed in the present study, and were predicted with significantly improved potencies in the developed models. The findings can be quite useful to aid the designing of new fructose-1,6-biphophatase inhibitors with improved biological response.

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

Eilert, Andre; Cavalca, Filippo; Roberts, F. Sloan

Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO 2RR). Using in situ ambient pressure X-ray photoelectron spectroscopy and quasi in situ electron energy-loss spectroscopy in a transmission electron microscope, we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts but no residual copper oxide. On the basis of these findings in combination with density functional theory simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stablemore » under the strongly reducing conditions found in CO 2RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multicarbon compounds such as ethylene.« less

25 CFR 215.25 - Other minerals and deep-lying lead and zinc minerals.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 25 Indians 1 2014-04-01 2014-04-01 false Other minerals and deep-lying lead and zinc minerals. 215.25 Section 215.25 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR ENERGY AND MINERALS LEAD AND ZINC MINING OPERATIONS AND LEASES, QUAPAW AGENCY § 215.25 Other minerals and deep-lying lead...

25 CFR 215.25 - Other minerals and deep-lying lead and zinc minerals.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 25 Indians 1 2012-04-01 2011-04-01 true Other minerals and deep-lying lead and zinc minerals. 215.25 Section 215.25 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR ENERGY AND MINERALS LEAD AND ZINC MINING OPERATIONS AND LEASES, QUAPAW AGENCY § 215.25 Other minerals and deep-lying lead...

25 CFR 215.25 - Other minerals and deep-lying lead and zinc minerals.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 25 Indians 1 2013-04-01 2013-04-01 false Other minerals and deep-lying lead and zinc minerals. 215.25 Section 215.25 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR ENERGY AND MINERALS LEAD AND ZINC MINING OPERATIONS AND LEASES, QUAPAW AGENCY § 215.25 Other minerals and deep-lying lead...

Cobalt porphyrin-mediated oxygen transport in a polymer membrane. Effect of the cobalt porphyrin structure on the oxygen-binding reaction, oxygen-diffusion constants, and oxygen-transport efficiency

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

Nishide, Hiroyuki; Suzuki, Takayuki; Kawakami, Hiroyoshi

1994-05-12

New derivatives of (meso-[alpha],[alpha],[alpha],[alpha]-tetrakis(o-pivalamidophenyl)porphinato)cobalt (CoPs) were characterized by oxygen-binding equilibrium and rate constants of the cobalt centered in the porphyrins. They depended on the structure of the porphyrin; for example, the rate constants of oxygen binding and dissociation (k[sub on] and k[sub off]) for [alpha][sup 3][beta]-CoP[sub 4]P were 3 and 20 times as large as those for [alpha][sup 4]-CoB[sub 4]P, respectively. Oxygen transport through the polymer membranes containing CoPs as the fixed oxygen carriers was facilitated and was affected by the oxygen-binding character or the structure of CoPs. The logarithmically linear correlation of the oxygen-dissociation rate constant of CoPs (k[submore » off] = (3-66) x 10[sup 3] S[sup [minus]1]) with the diffusion constant of oxygen via CoPs fixed in the membranes (D[sub cc] = (3-140) x 10[sup [minus]9] cm[sup 2] s[sup [minus]1]) was given for those six CoP derivatives. 26 refs., 5 figs., 2 tabs.« less

Estimation of Surface Seawater Fugacity of Carbon Dioxide Using Satellite Data and Machine Learning

NASA Astrophysics Data System (ADS)

Jang, E.; Im, J.; Park, G.; Park, Y.

2016-12-01

The ocean controls the climate of Earth by absorbing and releasing CO2 through the carbon cycle. The amount of CO2 in the ocean has increased since the industrial revolution. High CO2 concentration in the ocean has a negative influence to marine organisms and reduces the ability of absorbing CO2 in the ocean. This study estimated surface seawater fugacity of CO2 (fCO2) in the East Sea of Korea using Geostationary Ocean Color Imager (GOCI) and Moderate Resolution Imaging Spectroradiometer (MODIS) satellite data, and Hybrid Coordinate Ocean Model (HYCOM) reanalysis data. GOCI is the world first geostationary ocean color observation satellite sensor, and it provides 8 images with 8 bands hourly per day from 9 am to 4 pm at 500m resolution. Two machine learning approaches (i.e., random forest and support vector regression) were used to model fCO2 in this study. While most of the existing studies used multiple linear regression to estimate the pressure of CO2 in the ocean, machine learning may handle more complex relationship between surface seawater fCO2 and ocean parameters in a dynamic spatiotemporal environment. Five ocean related parameters, colored dissolved organic matter (CDOM), chlorophyll-a (chla), sea surface temperature (SST), sea surface salinity (SSS), and mixed layer depth (MLD), were used as input variables. This study examined two schemes, one with GOCI-derived products and the other with MODIS-derived ones. Results show that random forest performed better than support vector regression regardless of satellite data used. The accuracy of GOCI-based estimation was higher than MODIS-based one, possibly thanks to the better spatiotemporal resolution of GOCI data. MLD was identified the most contributing parameter in estimating surface seawater fCO2 among the five ocean related parameters, which might be related with an active deep convection in the East Sea. The surface seawater fCO2 in summer was higher in general with some spatial variation than the other seasons because of higher SST.

Selectivity for CO2 over CH4 on a functionalized periodic mesoporous phenylene-silica explained by transition state theory

NASA Astrophysics Data System (ADS)

Kunkel, Christian; Viñes, Francesc; Lourenço, Mirtha A. O.; Ferreira, Paula; Gomes, José R. B.; Illas, Francesc

2017-03-01

Efficient separation of CO2/CH4 is critical in biogas upgrading, requiring highly selective adsorbents. Based on the adsorption energies of -0.30 and -0.14 eV, previously calculated by dispersion corrected density functional theory for adsorption/desorption of CO2 and CH4 on the functionalized periodic mesoporous phenylene-silica material APTMS@Ph-PMO, respectively, transition state theory rates were derived and used to simulate the adsorption/desorption rates of these two gases on APTMS@Ph-PMO. The latter yielded an estimation of initial CO2/CH4 selectivity at various temperatures. At T = 298 K, selectivity of 32.2 agrees to an experimental value of 26.1, which validates the method used for evaluating CO2/CH4 adsorption selectivities.

The reactivity of plant-derived organic matter and the potential importance of priming effects along the lower Amazon River

NASA Astrophysics Data System (ADS)

Ward, Nicholas D.; Bianchi, Thomas S.; Sawakuchi, Henrique O.; Gagne-Maynard, William; Cunha, Alan C.; Brito, Daimio C.; Neu, Vania; de Matos Valerio, Aline; da Silva, Rodrigo; Krusche, Alex V.; Richey, Jeffrey E.; Keil, Richard G.

2016-06-01

Here we present direct measurements of the biological breakdown of 13C-labeled substrates to CO2 at seven locations along the lower Amazon River, from Óbidos to the mouth. Dark incubation experiments were performed at high and low water periods using vanillin, a lignin phenol derived from vascular plants, and at the high water period using four different 13C-labeled plant litter leachates. Leachates derived from oak wood were degraded most slowly with vanillin monomers, macrophyte leaves, macrophyte stems, and whole grass leachates being converted to CO2 1.2, 1.3, 1.7, and 2.3 times faster, respectively, at the upstream boundary, Óbidos. Relative to Óbidos, the sum degradation rate of all four leachates was 3.3 and 2.6 times faster in the algae-rich Tapajós and Xingu Rivers, respectively. Likewise, the leachates were broken down 3.2 times more quickly at Óbidos when algal biomass from the Tapajós River was simultaneously added. Leachate reactivity similarly increased from Óbidos to the mouth with leachates breaking down 1.7 times more quickly at Almeirim (midway to the mouth) and 2.8 times more quickly across the river mouth. There was no discernible correlation between in situ nutrient levels and remineralization rates, suggesting that priming effects were an important factor controlling reactivity along the continuum. Further, continuous measurements of CO2, O2, and conductivity along the confluence of the Tapajós and Amazon Rivers and the Xingu and Jarauçu Rivers revealed in situ evidence for enhanced O2 drawdown and CO2 production along the mixing zone of these confluences.

Redox-Active Bis(phenolate) N-Heterocyclic Carbene [OCO] Pincer Ligands Support Cobalt Electron Transfer Series Spanning Four Oxidation States.

PubMed

Harris, Caleb F; Bayless, Michael B; van Leest, Nicolaas P; Bruch, Quinton J; Livesay, Brooke N; Bacsa, John; Hardcastle, Kenneth I; Shores, Matthew P; de Bruin, Bas; Soper, Jake D

2017-10-16

A new family of low-coordinate Co complexes supported by three redox-noninnocent tridentate [OCO] pincer-type bis(phenolate) N-heterocyclic carbene (NHC) ligands are described. Combined experimental and computational data suggest that the charge-neutral four-coordinate complexes are best formulated as Co(II) centers bound to closed-shell [OCO] 2- dianions, of the general formula [(OCO)Co II L] (where L is a solvent-derived MeCN or THF). Cyclic voltammograms of the [(OCO)Co II L] complexes reveal three oxidations accessible at potentials below 1.2 V vs Fc + /Fc, corresponding to generation of formally Co(V) species, but the true physical/spectroscopic oxidation states are much lower. Chemical oxidations afford the mono- and dications of the imidazoline NHC-derived complex, which were examined by computational and magnetic and spectroscopic methods, including single-crystal X-ray diffraction. The metal and ligand oxidation states of the monocationic complex are ambiguous; data are consistent with formulation as either [( S OCO)Co III (THF) 2 ] + containing a closed-shell [ S OCO] 2- diphenolate ligand bound to a S = 1 Co(III) center, or [( S OCO • )Co II (THF) 2 ] + with a low-spin Co(II) ion ferromagnetically coupled to monoanionic [ S OCO • ] - containing a single unpaired electron distributed across the [OCO] framework. The dication is best described as [( S OCO 0 )Co II (THF) 3 ] 2+ , with a single unpaired electron localized on the d 7 Co(II) center and a doubly oxidized, charge-neutral, closed-shell S OCO 0 ligand. The combined data provide for the first time unequivocal and structural evidence for [OCO] ligand redox activity. Notably, varying the degree of unsaturation in the NHC backbone shifts the ligand-based oxidation potentials by up to 400 mV. The possible chemical origins of this unexpected shift, along with the potential utility of the [OCO] pincer ligands for base-metal-mediated organometallic coupling catalysis, are discussed.

Synthesis and coordinating ability of an anionic cobaltabisdicarbollide ligand geometrically analogous to BINAP.

PubMed

Rojo, Isabel; Teixidor, Francesc; Viñas, Clara; Kivekäs, Raikko; Sillanpää, Reijo

2004-10-25

The anionic chelating ligand [1,1'-(PPh2)2-3,3'-Co(1,2-C2B9H10)2]- has been synthesized from [3,3'-Co(1,2-C2B9H11)2]- in very good yield in a one-pot process with an easy work-up procedure. The coordinating ability of this ligand has been studied with Group 11 metal ions (Ag, Au) and with transition-metal ions (Pd, Rh). The two dicarbollide halves of the [1,1'-(PPh2)2-3,3'-Co(1,2-C2B9H10)2]- ligand can swing about one axis in a manner analogous to the constituent parts of BINAP and ferrocenyl phosphine derivatives. All these ligands function as hinges, with the most important property in relation to the coordination requirements of the metal being the PP distance. [1,1'-(PPh2)2-3,3'-Co(1,2-C2B9H10)2]-, BINAP, ferrocenyl phosphine derivatives, and other hinge ligands present a range of different PP separations, and consequently different coordination spheres and dispositions around metal cations. To account for these differences, the equation Dphi2 = D02 + 4 R2cos2(90-phi/2) has been developed. It relates the PP distance (Dphi) in a complex with the minimum PP distance (D0) that is characteristic of the hinge-type ligand.

Laser diode absorption spectroscopy for accurate CO(2) line parameters at 2 microm: consequences for space-based DIAL measurements and potential biases.

PubMed

Joly, Lilian; Marnas, Fabien; Gibert, Fabien; Bruneau, Didier; Grouiez, Bruno; Flamant, Pierre H; Durry, Georges; Dumelie, Nicolas; Parvitte, Bertrand; Zéninari, Virginie

2009-10-10

Space-based active sensing of CO(2) concentration is a very promising technique for the derivation of CO(2) surface fluxes. There is a need for accurate spectroscopic parameters to enable accurate space-based measurements to address global climatic issues. New spectroscopic measurements using laser diode absorption spectroscopy are presented for the preselected R30 CO(2) absorption line ((20(0)1)(III)<--(000) band) and four others. The line strength, air-broadening halfwidth, and its temperature dependence have been investigated. The results exhibit significant improvement for the R30 CO(2) absorption line: 0.4% on the line strength, 0.15% on the air-broadening coefficient, and 0.45% on its temperature dependence. Analysis of potential biases of space-based DIAL CO(2) mixing ratio measurements associated to spectroscopic parameter uncertainties are presented.

An integrated appraisal of energy recovery options in the United Kingdom using solid recovered fuel derived from municipal solid waste.

PubMed

Garg, A; Smith, R; Hill, D; Longhurst, P J; Pollard, S J T; Simms, N J

2009-08-01

This paper reports an integrated appraisal of options for utilising solid recovered fuels (SRF) (derived from municipal solid waste, MSW) in energy intensive industries within the United Kingdom (UK). Four potential co-combustion scenarios have been identified following discussions with industry stakeholders. These scenarios have been evaluated using (a) an existing energy and mass flow framework model, (b) a semi-quantitative risk analysis, (c) an environmental assessment and (d) a financial assessment. A summary of results from these evaluations for the four different scenarios is presented. For the given ranges of assumptions; SRF co-combustion with coal in cement kilns was found to be the optimal scenario followed by co-combustion of SRF in coal-fired power plants. The biogenic fraction in SRF (ca. 70%) reduces greenhouse gas (GHG) emissions significantly ( approximately 2500 g CO(2) eqvt./kg DS SRF in co-fired cement kilns and approximately 1500 g CO(2) eqvt./kg DS SRF in co-fired power plants). Potential reductions in electricity or heat production occurred through using a lower calorific value (CV) fuel. This could be compensated for by savings in fuel costs (from SRF having a gate fee) and grants aimed at reducing GHG emission to encourage the use of fuels with high biomass fractions. Total revenues generated from coal-fired power plants appear to be the highest ( 95 pounds/t SRF) from the four scenarios. However overall, cement kilns appear to be the best option due to the low technological risks, environmental emissions and fuel cost. Additionally, cement kiln operators have good experience of handling waste derived fuels. The scenarios involving co-combustion of SRF with MSW and biomass were less favourable due to higher environmental risks and technical issues.

Asymmetric Supercapacitors Using 3D Nanoporous Carbon and Cobalt Oxide Electrodes Synthesized from a Single Metal-Organic Framework.

PubMed

Salunkhe, Rahul R; Tang, Jing; Kamachi, Yuichiro; Nakato, Teruyuki; Kim, Jung Ho; Yamauchi, Yusuke

2015-06-23

Nanoporous carbon and nanoporous cobalt oxide (Co3O4) materials have been selectively prepared from a single metal-organic framework (MOF) (zeolitic imidazolate framework, ZIF-67) by optimizing the annealing conditions. The resulting ZIF-derived carbon possesses highly graphitic walls and a high specific surface area of 350 m(2)·g(-1), while the resulting ZIF-derived nanoporous Co3O4 possesses a high specific surface area of 148 m(2)·g(-1) with much less carbon content (1.7 at%). When nanoporous carbon and nanoporous Co3O4 were tested as electrode materials for supercapacitor application, they showed high capacitance values (272 and 504 F·g(-1), respectively, at a scan rate of 5 mV·s(-1)). To further demonstrate the advantages of our ZIF-derived nanoporous materials, symmetric (SSCs) and asymmetric supercapacitors (ASCs) were also fabricated using nanoporous carbon and nanoporous Co3O4 electrodes. Improved capacitance performance was successfully realized for the ASC (Co3O4//carbon), better than those of the SSCs based on nanoporous carbon and nanoporous Co3O4 materials (i.e., carbon//carbon and Co3O4//Co3O4). The developed ASC with an optimal mass loading can be operated within a wide potential window of 0.0-1.6 V, which leads to a high specific energy of 36 W·h·kg(-1). More interestingly, this ASC also exhibits excellent rate capability (with the highest specific power of 8000 W·kg(-1) at a specific energy of 15 W·h·kg(-1)) combined with long-term stability up to 2000 cycles.

Synthesis and structural characterization of PHP[(C(5)Me(4))(2)], a monodentate chiral phosphine derived from intramolecular C-C coupling of tetramethylcyclopentadienyl groups: an evaluation of steric and electronic properties.

PubMed

Shin, J H; Bridgewater, B M; Churchill, D G; Parkin, G

2001-10-22

The chiral monodentate phosphine PhP[(C(5)Me(4))(2)] is readily obtained by oxidation of the lithium complex Li(2)[PhP(C(5)Me(4))(2)] with I(2), which couples the two cyclopentadienyl groups to form a five-membered heterocyclic ring. The steric and electronic properties of PhP[(C(5)Me(4))(2)] have been evaluated by X-ray diffraction and IR spectroscopic studies on a variety of derivatives, including Ph[(C(5)Me(4))(2)]PE (E = S, Se), Cp*MCl(4)[P[(C(5)Me(4))(2)]Ph] (M = Mo, Ta), Ir[P[(C(5)Me(4))(2)]Ph](2)(CO)Cl, and CpFe(CO)[PhP[(C(5)Me(4))(2)

Electrochemical and optical characterization of cobalt, copper and zinc phthalocyanine complexes.

PubMed

Lee, Jaehyun; Kim, Se Hun; Lee, Woosung; Lee, Jiwon; An, Byeong-Kwan; Oh, Se Young; Kim, Jae Pil; Park, Jongwook

2013-06-01

New phthalocyanine (Pc) derivatives that include the alkyl group in ligand were synthesized based on three core metals such as zinc (Zn), copper (Cu), and cobalt (Co). Electrochemical behaviors and optical properties of the new phthalocyanine derivatives with ligand and different core metal were investigated by using cyclic voltammetry, UV-Visible (UV-Vis) spectroscopy and photoluminescence (PL) spectroscopy. In UV-Vis data, maximum values of 2H, Co, Cu, and Zn complexes were 708 nm and 677 nm, 686 nm, 684 nm, respectively.

Hole and electron extraction layers based on graphene oxide derivatives for high-performance bulk heterojunction solar cells.

PubMed

Liu, Jun; Xue, Yuhua; Gao, Yunxiang; Yu, Dingshan; Durstock, Michael; Dai, Liming

2012-05-02

By charge neutralization of carboxylic acid groups in graphene oxide (GO) with Cs(2)CO(3) to afford Cesium-neutralized GO (GO-Cs), GO derivatives with appropriate modification are used as both hole- and electron-extraction layers for bulk heterojunction (BHJ) solar cells. The normal and inverted devices based on GO hole- and GO-Cs electron-extraction layers both outperform the corresponding standard BHJ solar cells. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantifying sources of methane using light alkanes in the Los Angeles basin, California

NASA Astrophysics Data System (ADS)

Peischl, J.; Ryerson, T. B.; Brioude, J.; Aikin, K. C.; Andrews, A. E.; Atlas, E.; Blake, D.; Daube, B. C.; de Gouw, J. A.; Dlugokencky, E.; Frost, G. J.; Gentner, D. R.; Gilman, J. B.; Goldstein, A. H.; Harley, R. A.; Holloway, J. S.; Kofler, J.; Kuster, W. C.; Lang, P. M.; Novelli, P. C.; Santoni, G. W.; Trainer, M.; Wofsy, S. C.; Parrish, D. D.

2013-05-01

Methane (CH4), carbon dioxide (CO2), carbon monoxide (CO), and C2-C5 alkanes were measured throughout the Los Angeles (L.A.) basin in May and June 2010. We use these data to show that the emission ratios of CH4/CO and CH4/CO2 in the L.A. basin are larger than expected from population-apportioned bottom-up state inventories, consistent with previously published work. We use experimentally determined CH4/CO and CH4/CO2 emission ratios in combination with annual State of California CO and CO2 inventories to derive a yearly emission rate of CH4 to the L.A. basin. We further use the airborne measurements to directly derive CH4 emission rates from dairy operations in Chino, and from the two largest landfills in the L.A. basin, and show these sources are accurately represented in the California Air Resources Board greenhouse gas inventory for CH4. We then use measurements of C2-C5 alkanes to quantify the relative contribution of other CH4 sources in the L.A. basin, with results differing from those of previous studies. The atmospheric data are consistent with the majority of CH4 emissions in the region coming from fugitive losses from natural gas in pipelines and urban distribution systems and/or geologic seeps, as well as landfills and dairies. The local oil and gas industry also provides a significant source of CH4 in the area. The addition of CH4 emissions from natural gas pipelines and urban distribution systems and/or geologic seeps and from the local oil and gas industry is sufficient to account for the differences between the top-down and bottom-up CH4 inventories identified in previously published work.

Evaluation of the pentose phosphate pathway from 14CO2 data. Fallibility of a classic equation when applied to non-homogeneous tissues.

PubMed

Larrabee, M G

1990-11-15

A classic equation that has frequently been used to estimate the fraction of glucose metabolized by the pentose phosphate pathway, using 14CO2 data, is more simply re-derived with careful consideration of the assumptions involved and the conditions under which it is applicable. The equation is shown to be unreliable for non-homogeneous tissues, depending on the fraction of triose phosphate converted to CO2. The formula in question is as follows: ([1]CO2/G-[6]CO2/G)/(1-[6]CO2/G) = 3Fmet./(1 + 2Fmet.) where [1]CO2 and [6]CO2 are output rates of carbons 1 and 6 of glucose respectively to CO2, G is the rate of glucose uptake and Fmet. is the fraction of the glucose that is metabolized to CO2 and triose phosphate by the pentose phosphate pathway, allowing for recycling of an appropriate fraction of the fructose-6-phosphate produced by the pathway. This analysis illustrates the importance of suitably testing any equation that assumes homogeneity before application to non-homogeneous tissues.

Three-dimensional quantitative structure-activity relationship study on anti-cancer activity of 3,4-dihydroquinazoline derivatives against human lung cancer A549 cells

NASA Astrophysics Data System (ADS)

Cho, Sehyeon; Choi, Min Ji; Kim, Minju; Lee, Sunhoe; Lee, Jinsung; Lee, Seok Joon; Cho, Haelim; Lee, Kyung-Tae; Lee, Jae Yeol

2015-03-01

A series of 3,4-dihydroquinazoline derivatives with anti-cancer activities against human lung cancer A549 cells were subjected to three-dimensional quantitative structure-activity relationship (3D-QSAR) studies using the comparative molecular similarity indices analysis (CoMSIA) approaches. The most potent compound, 1 was used to align the molecules. As a result, the best prediction was obtained with CoMSIA combined the steric, electrostatic, hydrophobic, hydrogen bond donor, and hydrogen bond acceptor fields (q2 = 0.720, r2 = 0.897). This model was validated by an external test set of 6 compounds giving satisfactory predictive r2 value of 0.923 as well as the scrambling stability test. This model would guide the design of potent 3,4-dihydroquinazoline derivatives as anti-cancer agent for the treatment of human lung cancer.

Synthesis and Structural Characterization of a Novel Indium Mercapto Derivative [clln(sch2(co)o)2]2-[(4-mepyh)2]2+

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K.; Duraj, Stan A.; Fanwick, Philip E.; Hepp, Aloysius F.; Martock, Robert A.

2004-01-01

The synthesis and structural characterization of a novel In(III) complex is described. The reaction between InCl3 with sodium mercapto-acetic acid, (NaSCH2(CO)OH) in 4-methylpyridine, (CH3(C5H5N), (4-Mepy)) at 25 C affords [ClIn(SCH2(CO)O)2]2- [(4-MepyH)2]2+. X-ray diffraction studies show it to have a distorted square pyramidal geometry, with the [(-SCH2(CO)CO-)] ligands in a trans conformation. The compound crystallizes in the P(raised dash) 1 (No. 2) space group with a = 7.8624 Angstrom, b = 9.950 Angstrom, c = 13.793 Angstrom, alpha = 107.60 degrees, beta= 90.336 degrees, gamma = 98.983 degrees, V = 1014.3 Angstroms (sup 3), R(F(raised circle)) = 0.037, and R(sub w) = 0.048.

Soft and Flexible Bilayer Thermoplastic Polyurethane Foam for Development of Bioinspired Artificial Skin.

PubMed

Li, Huan; Sinha, Tridib K; Oh, Jeong Seok; Kim, Jin Kuk

2018-04-25

Inspired by the epidermis-dermis composition of human skin, here we have simply developed a lightweight, robust, flexible, and biocompatible single-electrode triboelectric nanogenerator (S-TENG)-based prototype of bilayer artificial skin, by attaching one induction electrode with unfoamed skin layer of microcellular thermoplastic polyurethane (TPU) foam, which shows high-performance object manipulation [by responding differently toward different objects, viz., aluminum foil, balloon, cotton glove, human finger, glass, rubber glove, artificial leather, polyimide, poly(tetrafluoroethylene) (PTFE), paper, and wood], due to electrification and electrostatic induction during contact with the objects having different chemical functionalities. Comparative foaming behavior of ecofriendly supercritical fluids, viz., CO 2 over N 2 under variable temperatures (e.g., 130 and 150 °C) and constant pressure (15 MPa), have been examined here to pursue the soft and flexible triboelectric TPU foam. The foam derived by CO 2 foaming at 150 °C has been prioritized for development of S-TENG. Foam derived by CO 2 foaming at 130 °C did not respond as well due to the smaller cell size, higher hardness, and thicker skin. Inflexible N 2 -derived foam was not considered for S-TENG fabrication. Object manipulation performance has been visualized by principal component analysis (PCA), which shows good discrimination among responses to different objects.

Emissive polymeric materials for optoelectronic devices

DOEpatents

Shiang, Joseph John [Niskayuna, NY; Chichak, Kelly Scott [Clifton Park, NY; Cella, James Anthony [Clifton Park, NY; Lewis, Larry Neil [Scotia, NY; Janora, Kevin Henry [Schenectady, NY

2011-07-05

Polymers including at least one structural unit derived from a compound of formula I or including at least one pendant group of formula II may be used in optoelectronic devices ##STR00001## wherein R.sup.1, R.sup.3, R.sup.4 and R.sup.6 are independently hydrogen, alkyl, alkoxy, oxaalkyl, alkylaryl, aryl, arylalkyl, heteroaryl, substituted alkyl; substituted alkoxy, substituted oxaalkyl, substituted alkylaryl, substituted aryl, substituted arylalkyl, or substituted heteroaryl; R.sup.1a is hydrogen or alkyl; R.sup.2 is alkylene, substituted alkylene, oxaalkylene, CO, or CO.sub.2; R.sup.2a is alkylene; R.sup.5 is independently at each occurrence hydrogen, alkyl, alkylaryl, aryl, arylalkyl, alkoxy, carboxy, substituted alkyl; substituted alkylaryl, substituted aryl, substituted arylalkyl, or substituted alkoxy, X is halo, triflate, --B(OR.sup.1a).sub.2, or ##STR00002## located at the 2, 5- or 2, 7-positions; and L is derived from phenylpyridine, tolylpyridine, benzothienylpyridine, phenylisoquinoline, dibenzoquinozaline, fluorenylpyridine, ketopyrrole, 2-(1-naphthyl)benzoxazole)), 2-phenylbenzoxazole, 2-phenylbenzothiazole, coumarin, thienylpyridine, phenylpyridine, benzothienylpyridine, 3-methoxy-2-phenylpyridine, thienylpyridine, phenylimine, vinylpyridine, pyridylnaphthalene, pyridylpyrrole, pyridylimidazole, phenylindole, derivatives thereof or combinations thereof.

Shale gas development: a smart regulation framework.

PubMed

Konschnik, Katherine E; Boling, Mark K

2014-01-01

Advances in directional drilling and hydraulic fracturing have sparked a natural gas boom from shale formations in the United States. Regulators face a rapidly changing industry comprised of hundreds of players, operating tens of thousands of wells across 30 states. They are often challenged to respond by budget cuts, a brain drain to industry, regulations designed for conventional gas developments, insufficient information, and deeply polarized debates about hydraulic fracturing and its regulation. As a result, shale gas governance remains a halting patchwork of rules, undermining opportunities to effectively characterize and mitigate development risk. The situation is dynamic, with research and incremental regulatory advances underway. Into this mix, we offer the CO/RE framework--characterization of risk, optimization of mitigation strategies, regulation, and enforcement--to design tailored governance strategies. We then apply CO/RE to three types of shale gas risks, to illustrate its potential utility to regulators.

Can CO2 Turbulent Flux Be Measured by Lidar? A Preliminary Study

NASA Technical Reports Server (NTRS)

Gilbert, Fabien; Koch, Grady; Beyon, Jeffrey Y.; Hilton, Timothy W.; Davis, Kenneth J.; Andrews, Arlyn; Flamant, Pierre H.; Singh, Upendra N.

2011-01-01

The vertical profiling ofCO2 turbulent fluxes in the atmospheric boundary layer (ABL) is investigated using a coherent differential absorption lidar (CDIAL) operated nearby a tall tower in Wisconsin during June 2007. A CDIAL can perform simultaneous range-resolved CO2 DIAL and velocity measurements. The lidar eddy covariance technique is presented. The aims of the study are (i) an assessment of performance and current limitation of available CDIAL for CO2 turbulent fluxes and (ii) the derivation of instrument specifications to build a future CDIAL to perform accurate range-resolved CO2 fluxes. Experimental lidar CO2 mixing ratio and vertical velocity profiles are successfully compared with in situ sensors measurements. Time and space integral scales of turbulence in the ABL are addressed that result in limitation for time averaging and range accumulation. A first attempt to infer CO2 fluxes using an eddy covariance technique with currently available 2-mm CDIAL dataset is reported.

Large Uncertainty in Estimating pCO2 From Carbonate Equilibria in Lakes

NASA Astrophysics Data System (ADS)

Golub, Malgorzata; Desai, Ankur R.; McKinley, Galen A.; Remucal, Christina K.; Stanley, Emily H.

2017-11-01

Most estimates of carbon dioxide (CO2) evasion from freshwaters rely on calculating partial pressure of aquatic CO2 (pCO2) from two out of three CO2-related parameters using carbonate equilibria. However, the pCO2 uncertainty has not been systematically evaluated across multiple lake types and equilibria. We quantified random errors in pH, dissolved inorganic carbon, alkalinity, and temperature from the North Temperate Lakes Long-Term Ecological Research site in four lake groups across a broad gradient of chemical composition. These errors were propagated onto pCO2 calculated from three carbonate equilibria, and for overlapping observations, compared against uncertainties in directly measured pCO2. The empirical random errors in CO2-related parameters were mostly below 2% of their median values. Resulting random pCO2 errors ranged from ±3.7% to ±31.5% of the median depending on alkalinity group and choice of input parameter pairs. Temperature uncertainty had a negligible effect on pCO2. When compared with direct pCO2 measurements, all parameter combinations produced biased pCO2 estimates with less than one third of total uncertainty explained by random pCO2 errors, indicating that systematic uncertainty dominates over random error. Multidecadal trend of pCO2 was difficult to reconstruct from uncertain historical observations of CO2-related parameters. Given poor precision and accuracy of pCO2 estimates derived from virtually any combination of two CO2-related parameters, we recommend direct pCO2 measurements where possible. To achieve consistently robust estimates of CO2 emissions from freshwater components of terrestrial carbon balances, future efforts should focus on improving accuracy and precision of CO2-related parameters (including direct pCO2) measurements and associated pCO2 calculations.

Stable isotope and microbial analyses of methane-producing process in a geothermal aquifer associated with the subsurface of the accretionary prism, Japan

NASA Astrophysics Data System (ADS)

Hattori, S.; Kimura, H.; Nashimoto, H.; Koba, K.; Yamada, K.; Shimizu, M.; Watanabe, H.; Yoh, M.; Yoshida, N.

2009-04-01

The sedimentary layer in the southern part of Japan is accretionary prism which includes enriched organic materials derived from sediment on oceanic plate. There is geothermal aquifer in which a large amount of methane (CH4) dissolved. Since CH4 is important as a greenhouse gas and an important natural gas fuel, revealing CH4-producing process in subsurface environment is required. To understand the process of the CH4 production, we collected the groundwater from the aquifer of 1,189-1,489 m depth, and analyzed by using stable isotope and microbial analyses. 16S rRNA gene analysis showed a dominancy of hydrogenotrophic methanogens in domain Archaea and a dominancy of anaerobic heterotrophes to be known to produce H2 and CO2 by fermentation process in domain Bacteria. The anaerobic enrichment cultures with the groundwater amended with organic substrates showed that CH4 was produced by co-culture between the fermenters and hydrogenotrophic methanogens. On the other hand, conventional isotopic estimations for the origin of CH4 using δ13C-CH4 and δD-CH4 as well as δ13C-CH4and molecular ratio of C1/(C2+C3) indicated that CH4 was derived from thermogenic pathway. The values of δ13C-CO2, however, had higher values and carbon isotope fractionation factors between CH4 and CO2(α(CO2-CH4)) were approximately 1.05 to 1.06 indicating the possibility of biogenic CH4 production. Therefore, the origin of CH4 production was estimated as mixing both thermogenic and CO2 reduction from isotopic data. Furthermore, we incubated these enriched co-cultures and measure stable carbon isotope ratios of CH4 and CO2 and stable hydrogen isotope ratios of H2O and CH4. We revealed that concentration of H2 were kept lower by these co-cultures between fermenters and hydrogenotrophic methanogens and α(CO2-CH4) values were higher than that of cultures with the ground water amended with high concentration of H2+ CO2. Hydrogen isotope fractionation factor between H2O and CH4 by these co-culture increased (αH values decreased) with increasing H2 concentration.

Rapid transcriptional acclimation following transgenerational exposure of oysters to ocean acidification.

PubMed

Goncalves, Priscila; Anderson, Kelli; Thompson, Emma L; Melwani, Aroon; Parker, Laura M; Ross, Pauline M; Raftos, David A

2016-10-01

Marine organisms need to adapt in order to cope with the adverse effects of ocean acidification and warming. Transgenerational exposure to CO2 stress has been shown to enhance resilience to ocean acidification in offspring from a number of species. However, the molecular basis underlying such adaptive responses is currently unknown. Here, we compared the transcriptional profiles of two genetically distinct oyster breeding lines following transgenerational exposure to elevated CO2 in order to explore the molecular basis of acclimation or adaptation to ocean acidification in these organisms. The expression of key target genes associated with antioxidant defence, metabolism and the cytoskeleton was assessed in oysters exposed to elevated CO2 over three consecutive generations. This set of target genes was chosen specifically to test whether altered responsiveness of intracellular stress mechanisms contributes to the differential acclimation of oyster populations to climate stressors. Transgenerational exposure to elevated CO2 resulted in changes to both basal and inducible expression of those key target genes (e.g. ecSOD, catalase and peroxiredoxin 6), particularly in oysters derived from the disease-resistant, fast-growing B2 line. Exposure to CO2 stress over consecutive generations produced opposite and less evident effects on transcription in a second population that was derived from wild-type (nonselected) oysters. The analysis of key target genes revealed that the acute responses of oysters to CO2 stress appear to be affected by population-specific genetic and/or phenotypic traits and by the CO2 conditions to which their parents had been exposed. This supports the contention that the capacity for heritable change in response to ocean acidification varies between oyster breeding lines and is mediated by parental conditioning. © 2016 John Wiley & Sons Ltd.

CO2 laser increases the regenerative capacity of human adipose-derived stem cells by a mechanism involving the redox state and enhanced secretion of pro-angiogenic molecules.

PubMed

Constantin, Alina; Dumitrescu, Madalina; Mihai Corotchi, Maria Cristina; Jianu, Dana; Simionescu, Maya

2017-01-01

CO 2 laser has a beneficial effect on stem cells by mechanisms that are not clearly elucidated. We hypothesize that the effect of fractional CO 2 laser on human adipose-derived stem cells (ADSC) could be due to changes in redox homeostasis and secretion of factors contributing to cellular proliferation and angiogenic potential. ADSC incubated in medium containing 0.5 or 10 % FBS were exposed to a single irradiation of a 10,600-nm fractional CO 2 laser; non-irradiated ADSC were used as control. Viability/proliferation of ADSC was assessed by MTT assay; the intracellular reactive oxygen species (ROS) levels and the mitochondrial membrane potential (∆Ψ m ) were determined with DCFH-DA and JC-1 fluorescent probes, respectively. Molecules secreted by ADSC in the medium were determined by ELISA assay, and their capacity to support endothelial tube-like formation by the Matrigel assay. The results showed that compared to controls, ADSC kept in low FBS medium and irradiated with CO 2 laser at 9 W exhibited: (a) increased proliferation (∼20 %), (b) transient increase of mitochondrial ROS and the capacity to restore Δψ m after rotenone induced depolarization, and (c) augmented secretion in the conditioned medium of MMP-2 (twofold), MMP-9 (eightfold), VEGF (twofold), and adiponectin (∼50 %) that have the capacity to support angiogenesis of endothelial progenitor cells. In conclusion, the mechanisms underlying the benefic effect of CO 2 laser on ADSC are the activation of the redox pathways which increases cell proliferation and enhances secretion of angiogenic molecules. These results explain, in part, the mechanisms involved in the increased regenerative potential of CO 2 laser-exposed ADSC that could be exploited for clinical applications.

Fanconi anemia mesenchymal stromal cells-derived glycerophospholipids skew hematopoietic stem cell differentiation through Toll-like receptor signaling

PubMed Central

Amarachintha, Surya; Sertorio, Mathieu; Wilson, Andrew; Li, Xiaoli; Pang, Qishen

2015-01-01

Fanconi anemia (FA) patients develop bone marrow (BM) failure or leukemia. One standard care for these devastating complications is hematopoietic stem cell transplantation. We identified a group of mesenchymal stromal cells (MSCs)-derived metabolites, glycerophospholipids and their endogenous inhibitor, 5-(Tetradecyloxy)-2-furoic acid (TOFA), as regulators of donor hematopoietic stem and progenitor cells (HSPCs). We provided two pieces of evidence that TOFA could improve hematopoiesis-supporting function of FA MSCs: (1) limiting-dilution CAFC assay revealed that TOFA significantly increased cobblestone colonies in Fanca−/− or Fancd2−/− co-cultures compared to untreated co-cultures. (2) Competitive repopulating assay using output cells collected from co-cultures showed that TOFA greatly alleviated the abnormal expansion of the donor myeloid (CD45.2+Gr1+Mac1+) compartment in both peripheral blood and BM of recipient mice transplanted with cells from Fanca−/− or Fancd2−/− co-cultures. Further, mechanistic studies identified Tlr4 signaling as the responsible pathway mediating the effect of glycerophospholipids. Thus, targeting Glycerophospholipid biosynthesis in FA MSCs could be a therapeutic strategy to improve hematopoiesis and stem cell transplantation. PMID:26212365