Diffuse CO2 degassing at Vesuvio, Italy

NASA Astrophysics Data System (ADS)

Frondini, Francesco; Chiodini, Giovanni; Caliro, Stefano; Cardellini, Carlo; Granieri, Domenico; Ventura, Guido

2004-10-01

At Vesuvio, a significant fraction of the rising hydrothermal-volcanic fluids is subjected to a condensation and separation process producing a CO2-rich gas phase, mainly expulsed through soil diffuse degassing from well defined areas called diffuse degassing structures (DDS), and a liquid phase that flows towards the outer part of the volcanic cone. A large amount of thermal energy is associated with the steam condensation process and subsequent cooling of the liquid phase. The total amount of volcanic-hydrothermal CO2 discharged through diffuse degassing has been computed through a sequential Gaussian simulation (sGs) approach based on several hundred accumulation chamber measurements and, at the time of the survey, amounted to 151 t d-1. The steam associated with the CO2 output, computed assuming that the original H2O/CO2 ratio of hydrothermal fluids is preserved in fumarolic effluents, is 553 t d-1, and the energy produced by the steam condensation and cooling of the liquid phase is 1.47×1012 J d-1 (17 MW). The location of the CO2 and temperature anomalies show that most of the gas is discharged from the inner part of the crater and suggests that crater morphology and local stratigraphy exert strong control on CO2 degassing and subsurface steam condensation. The amounts of gas and energy released by Vesuvio are comparable to those released by other volcanic degassing areas of the world and their estimates, through periodic surveys of soil CO2 flux, can constitute a useful tool to monitor volcanic activity.

[CII] observations of H2 molecular layers in transition clouds

NASA Astrophysics Data System (ADS)

Velusamy, T.; Langer, W. D.; Pineda, J. L.; Goldsmith, P. F.; Li, D.; Yorke, H. W.

2010-10-01

We present the first results on the diffuse transition clouds observed in [CII] line emission at 158 μm (1.9 THz) towards Galactic longitudes near 340° (5 LOSs) & 20° (11 LOSs) as part of the HIFI tests and GOT C+ survey. Out of the total 146 [CII] velocity components detected by profile fitting we identify 53 as diffuse molecular clouds with associated 12CO emission but without 13CO emission and characterized by AV < 5 mag. We estimate the fraction of the [CII] emission in the diffuse HI layer in each cloud and then determine the [CII] emitted from the molecular layers in the cloud. We show that the excess [CII] intensities detected in a few clouds is indicative of a thick H2 layer around the CO core. The wide range of clouds in our sample with thin to thick H2 layers suggests that these are at various evolutionary states characterized by the formation of H2 and CO layers from HI and C+, respectively. In about 30% of the clouds the H2 column densities (“dark gas”) traced by the [CII] is 50% or more than that traced by 12CO emission. On the average ~25% of the total H2 in these clouds is in an H2 layer which is not traced by CO. We use the HI, [CII], and 12CO intensities in each cloud along with simple chemical models to obtain constraints on the FUV fields and cosmic ray ionization rates. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Intra-aggregate CO2 enrichment: a modelling approach for aerobic soils

NASA Astrophysics Data System (ADS)

Schlotter, D.; Schack-Kirchner, H.

2013-02-01

CO2 concentration gradients inside soil aggregates, caused by the respiration of soil microorganisms and fungal hyphae, might lead to variations in the soil solution chemistry on a mm-scale, and to an underestimation of the CO2 storage. But, up to now, there seems to be no feasible method for measuring CO2 inside natural aggregates with sufficient spatial resolution. We combined a one-dimensional model for gas diffusion in the inter-aggregate pore space with a cylinder diffusion model, simulating the consumption/production and diffusion of O2 and CO2 inside soil aggregates with air- and water-filled pores. Our model predicts that for aerobic respiration (respiratory quotient = 1) the intra-aggregate increase in the CO2 partial pressure can never be higher than 0.9 kPa for siliceous, and 0.1 kPa for calcaric aggregates, independent of the level of water-saturation. This suggests that only for siliceous aggregates CO2 produced by aerobic respiration might cause a high small-scale spatial variability in the soil solution chemistry. In calcaric aggregates, however, the contribution of carbonate species to the CO2 transport should lead to secondary carbonates on the aggregate surfaces. As regards the total CO2 storage in aerobic soils, both siliceous and calcaric, the effect of intra-aggregate CO2 gradients seems to be negligible. To assess the effect of anaerobic respiration on the intra-aggregate CO2 gradients, the development of a device for measuring CO2 on a mm-scale in soils is indispensable.

Cosmic-rays, gas, and dust in nearby anticentre clouds. II. Interstellar phase transitions and the dark neutral medium

NASA Astrophysics Data System (ADS)

Remy, Q.; Grenier, I. A.; Marshall, D. J.; Casandjian, J. M.

2018-03-01

Aim. H I 21-cm and 12CO 2.6-mm line emissions trace the atomic and molecular gas phases, respectively, but they miss most of the opaque H I and diffuse H2 present in the dark neutral medium (DNM) at the transition between the H I-bright and CO-bright regions. Jointly probing H I, CO, and DNM gas, we aim to constrain the threshold of the H I-H2 transition in visual extinction, AV, and in total hydrogen column densities, NHtot. We also aim to measure gas mass fractions in the different phases and to test their relation to cloud properties. Methods: We have used dust optical depth measurements at 353 GHz, γ-ray maps at GeV energies, and H I and CO line data to trace the gas column densities and map the DNM in nearby clouds toward the Galactic anticentre and Chamaeleon regions. We have selected a subset of 15 individual clouds, from diffuse to star-forming structures, in order to study the different phases across each cloud and to probe changes from cloud to cloud. Results: The atomic fraction of the total hydrogen column density is observed to decrease in the (0.6-1) × 1021 cm-2 range in NHtot (AV ≈ 0.4 mag) because of the formation of H2 molecules. The onset of detectable CO intensities varies by only a factor of 4 from cloud to cloud, between 0.6 × 1021 cm-2 and 2.5 × 1021 cm-2 in total gas column density. We observe larger H2 column densities than linearly inferred from the CO intensities at AV > 3 mag because of the large CO optical thickness; the additional H2 mass in this regime represents on average 20% of the CO-inferred molecular mass. In the DNM envelopes, we find that the fraction of diffuse CO-dark H2 in the molecular column densities decreases with increasing AV in a cloud. For a half molecular DNM, the fraction decreases from more than 80% at 0.4 mag to less than 20% beyond 2 mag. In mass, the DNM fraction varies with the cloud properties. Clouds with low peak CO intensities exhibit large CO-dark H2 fractions in molecular mass, in particular the diffuse clouds lying at high altitude above the Galactic plane. The mass present in the DNM envelopes appears to scale with the molecular mass seen in CO as MHDNM = 62 ± 7 MH2CO0.51 ± 0.02 across two decades in mass. Conclusions: The phase transitions in these clouds show both common trends and environmental differences. These findings will help support the theoretical modelling of H2 formation and the precise tracing of H2 in the interstellar medium.

CO Diffusion and Desorption Kinetics in CO2 Ices

NASA Astrophysics Data System (ADS)

Cooke, Ilsa R.; Öberg, Karin I.; Fayolle, Edith C.; Peeler, Zoe; Bergner, Jennifer B.

2018-01-01

The diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet, measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO2 ice at low temperatures (T = 11–23 K) using CO2 longitudinal optical phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick’s second law and find that the temperature-dependent diffusion coefficients are well fit by an Arrhenius equation, giving a diffusion barrier of 300 ± 40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO2 along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO2 ices deposited at 11–50 K by temperature programmed desorption and find that the desorption barrier ranges from 1240 ± 90 K to 1410 ± 70 K depending on the CO2 deposition temperature and resultant ice porosity. The measured CO–CO2 desorption barriers demonstrate that CO binds equally well to CO2 and H2O ices when both are compact. The CO–CO2 diffusion–desorption barrier ratio ranges from 0.21 to 0.24 dependent on the binding environment during diffusion. The diffusion–desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices.

Origin and z-distribution of Galactic diffuse [C II] emission

NASA Astrophysics Data System (ADS)

Velusamy, T.; Langer, W. D.

2014-12-01

Context. The [C ii] emission is an important probe of star formation in the Galaxy and in external galaxies. The GOT C+ survey and its follow up observations of spectrally resolved 1.9 THz [C ii] emission using Herschel HIFI provides the data needed to quantify the Galactic interstellar [C ii] gas components as tracers of star formation. Aims: We determine the source of the diffuse [C ii] emission by studying its spatial (radial and vertical) distributions by separating and evaluating the fractions of [C ii] and CO emissions in the Galactic ISM gas components. Methods: We used the HIFI [C ii] Galactic survey (GOT C+), along with ancillary H i, 12CO, 13CO, and C18O data toward 354 lines of sight, and several HIFI [C ii] and [C i] position-velocity maps. We quantified the emission in each spectral line profile by evaluating the intensities in 3 km s-1 wide velocity bins, "spaxels". Using the detection of [C ii] with CO or [C i], we separated the dense and diffuse gas components. We derived 2D Galactic disk maps using the spaxel velocities for kinematic distances. We separated the warm and cold H2 gases by comparing CO emissions with and without associated [C ii]. Results: We find evidence of widespread diffuse [C ii] emission with a z-scale distribution larger than that for the total [C ii] or CO. The diffuse [C ii] emission consists of (i) diffuse molecular (CO-faint) H2 clouds and (ii) diffuse H i clouds and/or WIM. In the inner Galaxy we find a lack of [C ii] detections in a majority (~62%) of H i spaxels and show that the diffuse component primarily comes from the WIM (~21%) and that the H i gas is not a major contributor to the diffuse component (~6%). The warm-H2 radial profile shows an excess in the range 4 to 7 kpc, consistent with enhanced star formation there. Conclusions: We derive, for the first time, the 2D [C ii] spatial distribution in the plane and the z-distributions of the individual [C ii] gas component. From the GOT C+ detections we estimate the fractional [C ii] emission tracing (i) H2 gas in dense and diffuse molecular clouds as ~48% and ~14%, respectively, (ii) in the H i gas ~18%, and (iii) in the WIM ~21%. Including non-detections from H i increases the [C ii] in H i to ~27%. The z-scale distributions FWHM from smallest to largest are [C ii] sources with CO, ~130 pc, (CO-faint) diffuse H2 gas, ~200 pc, and the diffuse H i and WIM, ~330 pc. When combined with [C ii], CO observations probe the warm-H2 gas, tracing star formation. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Diffuse Emission of Carbon Dioxide From Irazú Volcano, Costa Rica, Central America

NASA Astrophysics Data System (ADS)

Galindo, I.; Melian, G.; Ramirez, C.; Salazar, J.; Hernandez, P.; Perez, N.; Fernandez, M.; Notsu, K.

2001-12-01

Irazú (3,432 m) is a stratovolcano situated 50 Km east of San José, the capital of Costa Rica. Major geomorphological features at Irazú are five craters (Main Crater, Diego de La Haya, Playa Hermosa, La Laguna and El Piroclástico), and at least 10 satellitic cones which are located on its southern flank. Its eruptive history is known from 1723. Since then, have ocurred at least 23 eruptions. All known Holocene eruptions have been explosive. The focus of eruptions at the summit crater complex has migrated to the west towards the historically active crater from 1963 to 1965. Diffuse degassing studies are becoming an additional geochemical tool for volcanic surveillance. The purpose of this study is to evaluate the spatial distribution of diffuse CO2 emission as well as CO2 efflux from Irazú volcano. A soil CO2 flux survey of 201 sampling sites was carried out at the summit of Irazú volcano in March 2001. Sampling site distribution covered an area of 3.5 Km2. Soil CO2 efflux measurements were performed by means of a portable NDIR sensor LICOR-800. Soil CO2 efflux values ranged from non-detectable values to 316.1 gm-2d-1 Statistical-graphical analysis of the data showed three overlapping geochemical populations. The background mean is 3 gm-2d-1 and represents 91.3 % of the total data. Peak group showed a mean of 18 gm-2d-1 and represented 1.2 % of the data. Anomalous CO2 flux values are mainly detected in the South sector of the main crater, where landslides have previously occurred. Diffuse CO2 degassing rate of the study area yields 44.2 td-1.

Are closed landfills free of CH_{4} emissions? A case study of Arico's landfill, Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Barrancos, José; Cook, Jenny; Phillips, Victoria; Asensio-Ramos, María; Melián, Gladys; Hernández, Pedro A.; Pérez, Nemesio M.

2016-04-01

Landfills are authentic chemical and biological reactors that introduce in the environment a wide amount of gas pollutants (CO2, CH4, volatile organic compounds, etc.) and leachates. Even after years of being closed, a significant amount of landfill gas could be released to the atmosphere through the surface in a diffuse form, also known as non-controlled emission. The study of the spatial-temporal distribution of diffuse emissions provides information of how a landfill degassing takes place. The main objective of this study was to estimate the diffuse uncontrolled emission of CH4 into the atmosphere from the closed Arico's landfill (0.3 km2) in Tenerife Island, Spain. To do so, a non-controlled biogenic gas emission survey of nearly 450 sampling sites was carried out during August 2015. Surface gas sampling and surface landfill CO2 efflux measurements were carried out at each sampling site by means of a portable non-dispersive infrared spectrophotometer (NDIR) model LICOR Li800 following the accumulation chamber method. Landfill gases, CO2 and CH4, were analyzed using a double channel VARIAN 4900 micro-GC. The CH4 efflux was computed combining CO2 efflux and CH4/CO2 ratio in the landfill's surface gas. To quantify the total CH4 emission, CH4 efflux contour map was constructed using sequential Gaussian simulation (sGs) as interpolation method. The total diffuse CH4 emission was estimated in 2.2 t d-1, with CH4 efflux values ranging from 0-922 mg m-2 d-1. This type of studies provides knowledge of how a landfill degasses and serves to public and private entities to establish effective systems for extraction of biogas. This aims not only to achieve higher levels of controlled gas release from landfills resulting in a higher level of energy production but also will contribute to minimize air pollution caused by them.

Comparison of diffuse CO2 degassing at Miravalles and Rincón de la Vieja volcanoes (Guanacaste Province, Costa Rica)

NASA Astrophysics Data System (ADS)

Liegler, A.; Bakkar Hindeleh, H.; Deering, C. D.; Fentress, S. E.

2015-12-01

Volcanic gas emissions are a key component for monitoring volcanic activity, magmatic input of volatiles to the atmosphere and the assessment of geothermal potential in volcanic regions. Diffuse soil degassing has been shown to represent a major part of volcanic gas emissions. However, this type of gas emission has not yet been quantified in the Guanacaste province of Costa Rica; a region of the country with several large, active or dormant volcanoes. We conducted the first study of diffuse CO2 degassing at Rincón de la Vieja and Miravalles volcanoes, both located in Guanacaste. Diffuse degassing was measured using the accumulation chamber method to quantify CO2 flux in regions where hydrothermal surface features indicate anomalous activity. The total diffuse carbon dioxide flux estimated at Miravalles in two areas, together roughly 2 km2 in size, was 135 t/day and in several areas at Rincón de la Vieja a minimum of 4 t/day. Comparatively low flux values and a very local concentration (few m2) of CO2 flux were observed at the active Rincón de la Vieja volcano, compared to the dormant Miravalles volcano, where significant soil flux was found over extended areas, not only around vents. Our assessment of the origin of these differences leads to two possibilities depending on if the surface features on the two volcanoes are fed by a common hydrothermal system or two separate ones. In the former case, the different intensity of diffuse CO2 flux could indicate a different degassing behavior and stronger concentration of gas emissions at the active vent areas at Rincon de la Vieja. In the latter case, where the hydrothermal systems are not linked, the amount of CO2 degassed through the flanks of the volcanoes could indicate that different physical and chemical conditions are governing the degassing of the two systems.

Monitoring diffuse degassing in monogenetic volcanic field during seismic-volcanic unrest: the case of Tenerife North-West Rift Zone (NWRZ), Canary Islands, Spain

NASA Astrophysics Data System (ADS)

García, E.; Botelho, A. H.; Regnier, G. S. G.; Rodríguez, F.; Alonso Cótchico, M.; Melián, G.; Asensio-Ramos, M.; Padrón, E.; Hernández, P. A.; Pérez, N. M.

2017-12-01

Tenerife North-West Rift-Zone (NWRZ) is the most active volcano of the oceanic active volcanic island of Tenerife and the scenario of three historical eruptions (Boca Cangrejo S. XVI, Arenas Negras 1706 and Chinyero 1909). Since no visible degassing (fumaroles, etc.) at Tenerife NWRZ occurs, a geochemical monitoring program at Tenerife NWRZ was established mainly consisting on performing soil CO2 efflux surveys (50 surveys since 2000) to evaluate the temporal and spatial variations of soil CO2 efflux measurements and the diffuse CO2 emission rate. To do so, about 340 sampling sites were selected for each survey to obtain a homogeneous distribution after taking into consideration the local geology, structure, and accessibility. Measurements of soil CO2 efflux were performed in situ by means of a portable non-dispersive infrared sensor following the accumulation chamber method. The soil CO2 efflux values of the 2017 survey ranged from non-detectable to 46.6 g m-2 d-1. Statistical-graphical analysis of the 2017 data show two different geochemical populations; background (B) and peak (P) represented by 93.3% and 1.9% of the total data, respectively. The geometric means of the B and P populations are 2.4 and 19.1 g m-2 d-1, respectively. Most of the area showed B values while the P values were mainly observed at the N-W side of the volcanic rift. To estimate the diffuse CO2 emission in metric tons per day released from Tenerife NWRZ (75 km2) for the 2017 survey, we ran about 100 sGs simulations. The estimated 2017 diffuse CO2 output released to atmosphere by the Tenerife NWRZ volcano was 297 ± 13 t d-1. This 2017 diffuse CO2 emission rate value is relatively higher than the estimated background value (144 t d-1) and falls within the estimated background range (72 - 321 t d-1) observed for Tenerife NWRZ volcano during the 2000-2017 period. The observed temporal variation in the diffuse CO2 degassing output during this period does not seem to be driven by external factors and it shows a clear temporal correlation with the onsets of seismic activity (Hernández et al., 2017, Bull. Volcanol.). Monitoring the diffuse CO2 emission contributes to detect early warning signals of volcanic unrest at the Tenerife North-West Rift-Zone volcano.

Microstructure and Oxidation of a MAX Phase/Superalloy Hybrid Interface

NASA Technical Reports Server (NTRS)

Smialek, James L.; Garg, Anita

2014-01-01

Corrosion resistant, strain tolerant MAX phase coatings are of interest for turbine applications. Thin Cr2AlC MAX phase wafers were vacuum diffusion bonded to an advanced turbine disk alloy, LSHR, at 1100 C. The interface, examined by optical and scanning electron microscopy, revealed a primary diffusion zone consisting of 10 micrometers of beta-Ni(Co)Al, decorated with various NiCoCrAl, MC and M3B2 precipitates. On the Cr2AlC side, an additional 40 micrometers Al-depletion zone of Cr7C3 formed in an interconnected network with the beta-Ni(Co)Al. Oxidation of an exposed edge at 800 C for 100 h produced a fine-grained lenticular alumina scale over Cr2AlC and beta-Ni(Co)Al, with coarser chromia granules over the Cr7C3 regions. Subsequent growth of the diffusion layers was only 5 micrometers in total. A residual stress of 500 MPa was estimated for the MAX phase layer, but no interfacial damage was observed. Subsequent tests for 1000 h reveal similar results.

Solubility and diffusivity of N{sub 2}O and CO{sub 2} in (monoethanolamine + N-methyldiethanolamine + water) and in (monoethanolamine + 2-amino-2-methyl-1-propanol + water)

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

Li, M.H.; Lai, M.D.

1995-03-01

Solutions of amines are frequently used in gas-treating processes to remove acid gases, such as CO{sub 2} and H{sub 2}S, from gas streams in the natural gas and synthetic ammonia industries and petroleum chemical plants. The solubility and diffusivity of N{sub 2}O in (monoethanolamine + N-methyldiethanolamine + water) and in (monoethanolamine + 2-amino-2-methyl-l-propanol + water) were measured at 30, 35, and 40 C and at atmospheric pressure. Six (monoethanolamine + N-methyldiethanolamine + water) and five (monoethanolamine + 2-amino-2-methyl-l-propanol + water) systems were studied. The total amine mass percent in all cases was 30. The solubilities were measured by a solubilitymore » apparatus similar to that of Haimour and Sandall (1984). A wetted wall column absorber was used to obtain the diffusivity of N{sub 2}O in amines. The N{sub 2}O solubilities in amine solutions have been correlated on the basis of the excess Henry constant correlation of Wang et al. (1992). The N{sub 2}O analogy was used to estimate the solubility and diffusivity of CO{sub 2} in (monoethanolamine + N-methyldiethanolamine + water) and in (monoethanolamine + 2-amino-2-methyl-l-propanol + water).« less

Volatile emissions from the crater and flank of Oldoinyo Lengai volcano, Tanzania

USGS Publications Warehouse

Koepenick, K.W.; Brantley, S.L.; Thompson, J.M.; Rowe, G.L.; Nyblade, A.A.; Moshy, C.

1996-01-01

As a comparison to airborne infrared (IR) flux measurements, ground-based sampling of fumarole and soil gases was used to characterize the quiescent degassing of CO2 from Oldoinyo Lengai volcano. Aerial and ground-based measurements are in good agreement: ???75% of the aerially measured CO2 flux at Lengai (0.05-0.06 ?? 1012 mol yr-1 or 6000-7200 tonnes CO2 d-1) can be attributed to seven large crater vents. In contrast to Etna and Vulcano Island, where 15-50% of the total CO2 flux emanates diffusely through the volcanic flanks, diffuse emissions were measured only within 500 m of the crater rim at Lengai, contributing < 2% of the total flux. The lack of extensive flank emissions may reflect the dimensions of the magma chamber and/or the lack of a shallow fluid flow system. Thermodynamic restoration of fumarole analyses shows that gases are the most CO2-rich and H2O-poor reported for any volcano, containing 64-74% CO2, 24-34% H2O, 0.88-1.0% H2, 0.1-0.4% CO and < 0.1% H2S, HCl, HF, and CH4. Volatile emissions of S, Cl, and F at Oldoiyno Lengai are estimated as 4.5, 1.5, and 1.0 ?? 107 mol yr-1, respectively. Accuracy of the airborne technique was also assessed by measuring the C emission rate from a coal-burning power plant. CO2 fluxes were measured within ??10% near the plant; however, poor resolution at increased distances caused an underestimation of the flux by a factor of 2. The relatively large CO2 fluxes measured for alkaline volcanoes such as Oldoinyo Lengai or Etna may indicate that midplate volcanoes represent a large, yet relatively unknown, natural source of CO2.

Fumarole/plume and diffuse CO2 emission from Sierra Negra volcano, Galapagos archipelago

NASA Astrophysics Data System (ADS)

Padron, E.; Hernandez Perez, P. A.; Perez, N.; Theofilos, T.; Melian, G.; Barrancos, J.; Virgil, G.; Sumino, H.; Notsu, K.

2009-12-01

The active shield-volcano Sierra Negra is part of the Galapagos hotspot. Sierra Negra is the largest shield volcano of Isabela Island, hosting a 10 km diameter caldera. Ten historic eruptions have occurred and some involved a frequently visited east caldera rim fissure zone called Volcan Chico. The last volcanic event occurred in October 2005 and lasted for about a week, covering approximately twenty percent of the eastern caldera floor. Sierra Negra volcano has experienced some significant changes in the chemical composition of its volcanic gas discharges after the 2005 eruption. This volcanic event produced an important SO2 degassing that depleted the magmatic content of this gas. Not significant changes in the MORB and plume-type helium contribution were observed after the 2005 eruption, with a 65.5 % of MORB and 35.5 % of plume contribution. In 2006 a visible and diffuse gas emission study was performed at the summit of Sierra Negra volcano, Galapagos, to evaluate degassing rate from this volcanic system. Diffuse degassing at Sierra Negra was mainly confined in three different DDS: Volcan Chico, the southern inner margin of the caldera, and Mina Azufral. These areas showed also visible degassing, which indicates highly fractured areas where volcano-hydrothermal fluids migrate towards surface. A total fumarole/plume SO2 emission of 11 ± 2 td-1 was calculated by mini-DOAS ground-based measurements at Mina Azufral fumarolic area. Molar ratios of major volcanic gas components were also measured in-situ at Mina Azufral with a portable multisensor. The results showed H2S/SO2, CO2/SO2 and H2O/SO2 molar ratios of 0.41, 52.2 and 867.9, respectively. Multiplying the observed SO2 emission rate times the observed (gas)i/SO2 mass ratio we have estimated other volatiles emission rates. The results showed that H2O, CO2 and H2S emission rates from Sierra Negra are 562, 394, and 2.4 t d-1, respectively. The estimated total output of diffuse CO2 emission from the summit of Sierra Negra was 989 ± 85 t d-1. Estimated diffuse/plume CO2 emission ratio was 2.5.

Geochemical monitoring of the Tenerife North-East Rift Zone (NERZ) volcano (Canary Islands) by means of diffuse CO_{2} degassing surveys

NASA Astrophysics Data System (ADS)

Barrancos, José; O'Neill, Ryan; Gould, Catherine E.; Padilla, Germán; Rodríguez, Fátima; Amonte, Cecilia; Padrón, Eleazar; Pérez, Nemesio M.

2017-04-01

Tenerife is the largest of the Canary Islands (2100 km2) and the North East Rift (NERZ) volcano is one of the three active volcanic rift-zones of the island (210 km2). The last eruptive activity at NERZ volcano occurred in 1704 and 1705, with three volcanic eruptions: Siete Fuentes, Fasnia and Arafo. In order to provide a multidisciplinary approach to monitor potential volcanic activity changes at the NERZ volcano, diffuse CO2 emission surveys have been undertaken in a yearly basis since 2001. This study shows the results of the last soil CO2 efflux survey undertaken in summer 2016, with 600 soil gas sampling sites homogenously distributed. Soil CO2 efflux measurements were performed at the surface environment by means of a portable non-dispersive infrared spectrophotometer (NDIR) LICOR Li800 following the accumulation chamber method. Soil CO2 efflux values ranged from non-detectable (˜0.5 g m-2 d-1) up to 70 g m-2 d-1, with an average value of 8.8 g m-2 d-1. In order to distinguish the existence of different geochemical populations on the soil CO2 efflux data, a Sinclair graphical analysis was done. The average value of background population was 2.9 g m-2 d-1 and that of peak population was 67.8 g m-2 d-1, value that has been increasing since the year 2014. To quantify the total CO2 emission rate from the NERZ volcano a sequential Gaussian simulation (sGs) was used as interpolation method to construct soil CO2 emission contour maps. The diffuse CO2 emission rate for the studied area was estimated in 1,675 ± 47 t d-1. If we compare the 2016 results with those ones obtained in previous surveys since 2001, two main pulses on diffuse CO2 emission are identified, the first one in 2007 and the second one between during 2014 and 2016. This long-term variation on the diffuse CO2 emission doesn't seem to be masked by the external-meteorological variations. However, the first peak precedes the anomalous seismicity recorded in and around Tenerife Island between 2009 and 2011, suggesting changes in strain-stress at depth as a possible cause of the observed changes in the diffuse CO2 emission rate. On the other hand, the second peak seems to be related to later changes in the seismicity, such as the seismic activity that occurred in Tenerife at the end of 2016. Again, this study demonstrates the importance of studies of soil CO2 efflux at the NERZ volcano of Tenerife island as an effective volcanic monitoring tool.

Multi-scale observations of the variability of magmatic CO2 emissions, Mammoth Mountain, CA, USA

NASA Astrophysics Data System (ADS)

Lewicki, J. L.; Hilley, G. E.

2014-09-01

One of the primary indicators of volcanic unrest at Mammoth Mountain is diffuse emission of magmatic CO2, which can effectively track this unrest if its variability in space and time and relationship to near-surface meteorological and hydrologic phenomena versus those occurring at depth beneath the mountain are understood. In June-October 2013, we conducted accumulation chamber soil CO2 flux surveys and made half-hourly CO2 flux measurements with automated eddy covariance and accumulation chamber (auto-chamber) instrumentation at the largest area of diffuse CO2 degassing on Mammoth Mountain (Horseshoe Lake tree kill; HLTK). Estimated CO2 emission rates for HLTK based on 20 June, 30 July, and 24-25 October soil CO2 flux surveys were 165, 172, and 231 t d- 1, respectively. The average (June-October) CO2 emission rate estimated for this area was 123 t d- 1 based on an inversion of 4527 eddy covariance CO2 flux measurements and corresponding modeled source weight functions. Average daily eddy covariance and auto-chamber CO2 fluxes consistently declined over the four-month observation time. Wavelet analysis of auto-chamber CO2 flux and environmental parameter time series was used to evaluate the periodicity of, and local correlation between these variables in time-frequency space. Overall, CO2 emissions at HLTK were highly dynamic, displaying short-term (hourly to weekly) temporal variability related to meteorological and hydrologic changes, as well as long-term (monthly to multi-year) variations related to migration of CO2-rich magmatic fluids beneath the volcano. Accumulation chamber soil CO2 flux surveys were also conducted in the four additional areas of diffuse CO2 degassing on Mammoth Mountain in July-August 2013. Summing CO2 emission rates for all five areas yielded a total for the mountain of 311 t d- 1, which may suggest that emissions returned to 1998-2009 levels, following an increase from 2009 to 2011.

Multi-scale observations of the variability of magmatic CO2 emissions, Mammoth Mountain, CA, USA

USGS Publications Warehouse

Lewicki, Jennifer L.; Hilley, George E.

2014-01-01

One of the primary indicators of volcanic unrest at Mammoth Mountain is diffuse emission of magmatic CO2, which can effectively track this unrest if its variability in space and time and relationship to near-surface meteorological and hydrologic phenomena versus those occurring at depth beneath the mountain are understood. In June–October 2013, we conducted accumulation chamber soil CO2 flux surveys and made half-hourly CO2 flux measurements with automated eddy covariance and accumulation chamber (auto-chamber) instrumentation at the largest area of diffuse CO2 degassing on Mammoth Mountain (Horseshoe Lake tree kill; HLTK). Estimated CO2 emission rates for HLTK based on 20 June, 30 July, and 24–25 October soil CO2 flux surveys were 165, 172, and 231 t d− 1, respectively. The average (June–October) CO2 emission rate estimated for this area was 123 t d− 1 based on an inversion of 4527 eddy covariance CO2 flux measurements and corresponding modeled source weight functions. Average daily eddy covariance and auto-chamber CO2 fluxes consistently declined over the four-month observation time. Wavelet analysis of auto-chamber CO2 flux and environmental parameter time series was used to evaluate the periodicity of, and local correlation between these variables in time–frequency space. Overall, CO2 emissions at HLTK were highly dynamic, displaying short-term (hourly to weekly) temporal variability related to meteorological and hydrologic changes, as well as long-term (monthly to multi-year) variations related to migration of CO2-rich magmatic fluids beneath the volcano. Accumulation chamber soil CO2 flux surveys were also conducted in the four additional areas of diffuse CO2 degassing on Mammoth Mountain in July–August 2013. Summing CO2 emission rates for all five areas yielded a total for the mountain of 311 t d− 1, which may suggest that emissions returned to 1998–2009 levels, following an increase from 2009 to 2011.

Carbon dioxide emissions from the flat bottom and shallow Nam Theun 2 Reservoir: drawdown area as a neglected pathway to the atmosphere

NASA Astrophysics Data System (ADS)

Deshmukh, Chandrashekhar; Guérin, Frédéric; Vongkhamsao, Axay; Pighini, Sylvie; Oudone, Phetdala; Sopraseuth, Saysoulinthone; Godon, Arnaud; Rode, Wanidaporn; Guédant, Pierre; Oliva, Priscia; Audry, Stéphane; Zouiten, Cyril; Galy-Lacaux, Corinne; Robain, Henri; Ribolzi, Olivier; Kansal, Arun; Chanudet, Vincent; Descloux, Stéphane; Serça, Dominique

2018-03-01

Freshwater reservoirs are a significant source of CO2 to the atmosphere. CO2 is known to be emitted at the reservoir surface by diffusion at the air-water interface and downstream of dams or powerhouses by degassing and along the river course. In this study, we quantified total CO2 emissions from the Nam Theun 2 Reservoir (Lao PDR) in the Mekong River watershed. The study started in May 2009, less than a year after flooding and just a few months after the maximum level was first reached and lasted until the end of 2013. We tested the hypothesis that soils from the drawdown area would be a significant contributor to the total CO2 emissions.Total inorganic carbon, dissolved and particulate organic carbon and CO2 concentrations were measured in 4 pristine rivers of the Nam Theun watershed, at 9 stations in the reservoir (vertical profiles) and at 16 stations downstream of the monomictic reservoir on a weekly to monthly basis. CO2 bubbling was estimated during five field campaigns between 2009 and 2011 and on a weekly monitoring, covering water depths ranging from 0.4 to 16 m and various types of flooded ecosystems in 2012 and 2013. Three field campaigns in 2010, 2011 and 2013 were dedicated to the soils description in 21 plots and the quantification of soil CO2 emissions from the drawdown area. On this basis, we calculated total CO2 emissions from the reservoir and carbon inputs from the tributaries. We confirm the importance of the flooded stock of organic matter as a source of carbon (C) fuelling emissions. We show that the drawdown area contributes, depending on the year, from 40 to 75 % of total annual gross emissions in this flat and shallow reservoir. Since the CO2 emissions from the drawdown zone are almost constant throughout the years, the large interannual variations result from the significant decrease in diffusive fluxes and downstream emissions between 2010 and 2013. This overlooked pathway in terms of gross emissions would require an in-depth evaluation for the soil organic matter and vegetation dynamics to evaluate the actual contribution of this area in terms of net modification of gas exchange in the footprint of the reservoir, and how it could evolve in the future.

CO Diffusion into Amorphous H2O Ices

NASA Astrophysics Data System (ADS)

Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

2015-03-01

The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

The effect of nonlinear decompression history on H2O/CO2 vesiculation in rhyolitic magmas

NASA Astrophysics Data System (ADS)

Su, Yanqing; Huber, Christian

2017-04-01

Magma ascent rate is one of the key parameters that control volcanic eruption style, tephra dispersion, and volcanic atmospheric impact. Many methods have been employed to investigate the magma ascent rate in volcanic eruptions, and most rely on equilibrium thermodynamics. Combining the mixed H2O-CO2 solubility model with the diffusivities of both H2O and CO2 for normal rhyolitic melt, we model the kinetics of H2O and CO2 in rhyolitic eruptions that involve nonlinear decompression rates. Our study focuses on the effects of the total magma ascent time, the nonlinearity of decompression paths, and the influence of different initial CO2/H2O content on the posteruptive H2O and CO2 concentration profiles around bubbles within the melt. Our results show that, under most circumstances, volatile diffusion profiles do not constrain a unique solution for the decompression rate of magmas during an eruption, but, instead, provide a family of decompression paths with a well-defined trade-off between ascent time and nonlinearity. An important consequence of our analysis is that the common assumption of a constant decompression rate (averaged value) tends to underestimate the actual magma ascent time.

Molecular modeling of diffusion coefficient and ionic conductivity of CO2 in aqueous ionic solutions.

PubMed

Garcia-Ratés, Miquel; de Hemptinne, Jean-Charles; Bonet Avalos, Josep; Nieto-Draghi, Carlos

2012-03-08

Mass diffusion coefficients of CO(2)/brine mixtures under thermodynamic conditions of deep saline aquifers have been investigated by molecular simulation. The objective of this work is to provide estimates of the diffusion coefficient of CO(2) in salty water to compensate the lack of experimental data on this property. We analyzed the influence of temperature, CO(2) concentration,and salinity on the diffusion coefficient, the rotational diffusion, as well as the electrical conductivity. We observe an increase of the mass diffusion coefficient with the temperature, but no clear dependence is identified with the salinity or with the CO(2) mole fraction, if the system is overall dilute. In this case, we notice an important dispersion on the values of the diffusion coefficient which impairs any conclusive statement about the effect of the gas concentration on the mobility of CO(2) molecules. Rotational relaxation times for water and CO(2) increase by decreasing temperature or increasing the salt concentration. We propose a correlation for the self-diffusion coefficient of CO(2) in terms of the rotational relaxation time which can ultimately be used to estimate the mutual diffusion coefficient of CO(2) in brine. The electrical conductivity of the CO(2)-brine mixtures was also calculated under different thermodynamic conditions. Electrical conductivity tends to increase with the temperature and salt concentration. However, we do not observe any influence of this property with the CO(2) concentration at the studied regimes. Our results give a first evaluation of the variation of the CO(2)-brine mass diffusion coefficient, rotational relaxation times, and electrical conductivity under the thermodynamic conditions typically encountered in deep saline aquifers.

A Herschel [C ii] Galactic plane survey. II. CO-dark H2 in clouds

NASA Astrophysics Data System (ADS)

Langer, W. D.; Velusamy, T.; Pineda, J. L.; Willacy, K.; Goldsmith, P. F.

2014-01-01

Context. H i and CO large scale surveys of the Milky Way trace the diffuse atomic clouds and the dense shielded regions of molecular hydrogen clouds, respectively. However, until recently, we have not had spectrally resolved C+ surveys in sufficient lines of sight to characterize the ionized and photon dominated components of the interstellar medium, in particular, the H2 gas without CO, referred to as CO-dark H2, in a large sample of interstellar clouds. Aims: We use a sparse Galactic plane survey of the 1.9 THz (158 μm) [C ii] spectral line from the Herschel open time key programme, Galactic Observations of Terahertz C+ (GOT C+), to characterize the H2 gas without CO in a statistically significant sample of interstellar clouds. Methods: We identify individual clouds in the inner Galaxy by fitting the [C ii] and CO isotopologue spectra along each line of sight. We then combine these spectra with those of H i and use them along with excitation models and cloud models of C+ to determine the column densities and fractional mass of CO-dark H2 clouds. Results: We identify1804 narrow velocity [C ii] components corresponding to interstellar clouds in different categories and evolutionary states. About 840 are diffuse molecular clouds with no CO, ~510 are transition clouds containing [C ii] and 12CO, but no 13CO, and the remainder are dense molecular clouds containing 13CO emission. The CO-dark H2 clouds are concentrated between Galactic radii of ~3.5 to 7.5 kpc and the column density of the CO-dark H2 layer varies significantly from cloud to cloud with a global average of 9 × 1020 cm-2. These clouds contain a significant fraction by mass of CO-dark H2, that varies from ~75% for diffuse molecular clouds to ~20% for dense molecular clouds. Conclusions: We find a significant fraction of the warm molecular ISM gas is invisible in H i and CO, but is detected in [C ii]. The fraction of CO-dark H2 is greatest in the diffuse clouds and decreases with increasing total column density, and is lowest in the massive clouds. The column densities and mass fraction of CO-dark H2 are less than predicted by models of diffuse molecular clouds using solar metallicity, which is not surprising as most of our detections are in Galactic regions where the metallicity is larger and shielding more effective. There is an overall trend towards a higher fraction of CO-dark H2 in clouds with increasing Galactic radius, consistent with lower metallicity there. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Diffuse Carbon Dioxide Degassing Monitoring at Santa Ana-Izalco-Coatepeque Volcanic System, El Salvador, Central America

NASA Astrophysics Data System (ADS)

Olmos, R.; Barahona, F.; Cartagena, R.; Soriano, T.; Salazar, J.; Hernandez, P.; Perez, N.; Notsu, K.; Lopez, D.

2001-12-01

Santa Ana volcanic complex (0.22 Ma), located 40 Km west of San Salvador, comprises Santa Ana, Izalco, and Cerro Verde stratovolcanoes, the Coatepeque collapse caldera, as well as several cinder cones and explosion craters. Most recent activity has occurred at Izalco (1966) and Santa Ana which shows a permanent acidic crater lake with an intense fumarolic activity. In addition, Santa Ana exhibits a SO2-rich rising plume though no local seismicity has been reported. Weak fumarolic activity is also present at two locations within the Santa Ana volcanic complex: the summit crater of Izalco and Cerro Pacho at Coatepeque caldera. Other important structural features of this volcanic complex are two fault/fissure systems running NNW-SSE that can be identified by the alignment of the stratovolcanoes and numerous cinder cones and explosion craters. In January 2001, a 7.6 magnitude earthquake occurred about 150 Km SE of Santa Ana volcano. A soil gas and CO2 efflux survey was performed to evaluate the impact of this seismic event upon the diffuse degassing rates in Santa Ana volcanic complex in March 2001. A total of 450 soil gas and diffuse CO2 efflux measurements were carried out covering an area of 209.5 Km2. CO2 efflux ranged from non-detectable values to 293 gm-2d-1, with a median of 8.9 gm-2d-1 and an upper quartile of 5.2 gm-2d-1. The CO2 efflux spatial distribution reveals the existence of areas with CO2 efflux higher than 60 gm-2d-1 associated to the fault/fissure systems of NNW-SSE orientation. One of these areas, Cerro Pacho, was selected for the continuous monitoring of diffuse CO2 efflux in late May 2001. Secular variations of diffuse CO2 efflux ranged from 27.4 to 329 gm-2d-1 with a median of 130 gm-2d-1 and a quartile range of 59.3 gm-2d-1. An increasing trend of 43 gm-2d-1 was observed between May and August 2001 overlapped to high-frequency minor fluctuations related to meteorological variables' changes. However, a larger observation time-span is needed to understand the influence of the rainy-season and meteorological parameters in the observed CO2 efflux time series.

Chemistry in dynamically evolving clouds

NASA Technical Reports Server (NTRS)

Tarafdar, S. P.; Prasad, S. S.; Huntress, W. T., Jr.; Villere, K. R.; Black, D. C.

1985-01-01

A unified model of chemical and dynamical evolution of isolated, initially diffuse and quiescent interstellar clouds is presented. The model uses a semiempirically derived dependence of the observed cloud temperatures on the visual extinction and density. Even low-mass, low-density, diffuse clouds can collapse in this model, because the inward pressure gradient force assists gravitational contraction. In contrast, previous isothermal collapse models required the low-mass diffuse clouds to be unrealistically cold before gravitational contraction could start. Theoretically predicted dependences of the column densities of various atoms and molecules, such as C and CO, on visual extinction in diffuse clouds are in accord with observations. Similarly, the predicted dependences of the fractional abundances of various chemical species (e.g., CO, H2CO, HCN, HCO(+)) on the total hydrogen density in the core of the dense clouds also agree with observations reported to date in the literature. Compared with previous models of interstellar chemistry, the present model has the potential to explain the wide spectrum of chemical and physical properties of both diffuse and dense clouds with a common formalism employing only a few simple initial conditions.

Molecular dynamics simulation of the diffusion of uranium species in clay pores.

PubMed

Liu, Xiao-yu; Wang, Lu-hua; Zheng, Zhong; Kang, Ming-liang; Li, Chun; Liu, Chun-li

2013-01-15

Molecular dynamics simulations were carried out to investigate the diffusive behavior of aqueous uranium species in montmorillonite pores. Three uranium species (UO(2)(2+), UO(2)CO(3), UO(2)(CO(3))(2)(2-)) were confirmed in both the adsorbed and diffuse layers. UO(2)(CO(3))(3)(4-) was neglected in the subsequent analysis due to its scare occurrence. The species-based diffusion coefficients in montmorillonite pores were then calculated, and compared with the water mobility and their diffusivity in aqueous solution/feldspar nanosized fractures. Three factors were considered that affected the diffusive behavior of the uranium species: the mobility of water, the self-diffusion coefficient of the aqueous species, and the electrostatic forces between the negatively charged surface and charged molecules. The mobility of U species in the adsorbed layer decreased in the following sequence: UO(2)(2+)>UO(2)CO(3)>UO(2)(CO(3))(2)(2-). In the diffuse layer, we obtained the highest diffusion coefficient for UO(2)(CO(3))(2)(2-) with the value of 5.48×10(-10) m(2) s(-1), which was faster than UO(2)(2+). For these two charged species, the influence of electrostatic forces on the diffusion of solutes in the diffuse layer is overwhelming, whereas the influence of self-diffusion and water mobility is minor. Our study demonstrated that the negatively charged uranyl carbonate complex must be addressed in the safety assessment of potential radioactive waste disposal systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Diffuse degassing survey at the Higashi Izu monogenetic volcano field, Japan

NASA Astrophysics Data System (ADS)

Notsu, Kenji; Pérez, Nemesio M.; Fujii, Naoyuki; Hernández, Pedro A.; Mori, Toshiya; Padrón, Eleazar; Melián, Gladys

2016-04-01

The Higashi-Izu monogenetic volcanic group, which consists of more than 60 volcanoes, overlies the polygenetic volcanoes in the eastern part of the Izu peninsula, Japan, which are distributed over the area of 350 km2. Some of the monogenetic volcanoes are located on northwest-southeast alignments, suggesting that they developed along fissures. Recent volcanic activity occurred offshore, e.g., at the Izu-Oshima volcano, which erupted in 1986 and a submarine eruption of the small new Teishi knoll off eastern Izu Peninsula in 1989 (Hasebe et al., 2001). This study was carried out to investigate the possible relationship of diffuse CO2 emission and the recent seismic activity recorded NE of Higashi Izu monogenetic volcanic field, to quantify the rate at which CO2 is diffusely degassed from the studied area including Omuroyama volcano and to identify the structures controlling the degassing process. Measurements were carried out over a three day period from 8-10 July 2013. Diffuse CO2 emission surveys were always carried out following the accumulation chamber method and spatial distribution maps were constructed following the sequential Gaussian simulation (sGs) procedure. Soil gas samples were collected at 30-40 cm depth by withdrawal into 60 cc hypodermic syringes to characterize the chemical and isotopic composition of the soil gas. At Omurayama volcano, soil CO2 efflux values ranged from non-detectable to 97.5 g m-2 d-1, while at the seismic swarm zone ranged from 1.5 to 233.2 g m-2 d-1 and at the fault zone ranged from 5.7 to 101.2 g m-2 d-1. Probability-plot technique of all CO2 efflux data showed two different populations, background with a mean of 8.7 g m-2 d-1 and peak with a mean of 92.7 g m-2 d-1. In order to strength the deep seated contribution to the soil gases at the studied are, carbon isotopic analysis were performed in the CO2 gas. Soil gases (He, CO2 and N2) showed a clear mixing trend between air composition and a rich CO2 end member, suggesting the influence of a deep magmatic reservoir on the soil degassing at the studied area. To estimate the total diffuse CO2 output released from Omurayama, the average of 100 simulations was considered, giving an average of 22 ± 2 t d-1 of diffuse CO2 released by Miharayama. Regarding to the geochemical transects along the Amagi Road and perpendicular to the fault, CO2 efflux values >9xBackground were observed close to the location of the fault. These results show possible linear positive anomalies may be caused by the presence of the active fault which has a higher porosity than surrounding soils, allowing an increased flux of CO2 to reach the surface from depth. References: Hasebe et al., 2001. Bull. Volcanol., 63, 377.

Kinetics of CO2 diffusion in human carbonic anhydrase: a study using molecular dynamics simulations and the Markov-state model.

PubMed

Chen, Gong; Kong, Xian; Lu, Diannan; Wu, Jianzhong; Liu, Zheng

2017-05-10

Molecular dynamics (MD) simulations, in combination with the Markov-state model (MSM), were applied to probe CO 2 diffusion from an aqueous solution into the active site of human carbonic anhydrase II (hCA-II), an enzyme useful for enhanced CO 2 capture and utilization. The diffusion process in the hydrophobic pocket of hCA-II was illustrated in terms of a two-dimensional free-energy landscape. We found that CO 2 diffusion in hCA-II is a rate-limiting step in the CO 2 diffusion-binding-reaction process. The equilibrium distribution of CO 2 shows its preferential accumulation within a hydrophobic domain in the protein core region. An analysis of the committors and reactive fluxes indicates that the main pathway for CO 2 diffusion into the active site of hCA-II is through a binding pocket where residue Gln 136 contributes to the maximal flux. The simulation results offer a new perspective on the CO 2 hydration kinetics and useful insights toward the development of novel biochemical processes for more efficient CO 2 sequestration and utilization.

Changes in CO2 diffuse degassing induced by the passing of seismic waves

NASA Astrophysics Data System (ADS)

Gresse, M.; Vandemeulebrouck, J.; Byrdina, S.; Chiodini, G.; Bruno, P. P.

2016-06-01

Solfatara crater, located in the Campi Flegrei caldera, is a volcano with one of the highest degassing rates on Earth, more than 1500 t of CO2 released by diffusion or through vents. Here, we investigated how this gas release can be disrupted by the passage of seismic waves. We performed continuous soil CO2 flux measurements during the propagation of seismic vibrations in the range of 5 Hz to 200 Hz induced by a vibroseis truck. The CO2 flux was continuously recorded using the accumulation chamber method. The data show a temporary and drastic (up to two-fold) increase in CO2 flux exclusively during the vibrations, before returning to the initial flux values. These transient variations are interpreted as fluidization of the surficial granular layer that releases the stored gas. Similar degassing processes might occur at a larger scale during earthquakes, to cause temporary increases in the total gas outflow in volcanic or tectonic areas. Our findings are useful to better assess and monitor the potential hazard from sudden CO2 flux release during earthquakes as several cases of intoxication or death have already been related to volcanic degassing.

Airborne detection of diffuse carbon dioxide emissions at Mammoth Mountain, California

USGS Publications Warehouse

Gerlach, T.M.; Doukas, M.P.; McGee, K.A.; Kessler, R.

1999-01-01

We report the first airborne detection of CO2 degassing from diffuse volcanic sources. Airborne measurement of diffuse CO2 degassing offers a rapid alternative for monitoring CO2 emission rates at Mammoth Mountain. CO2 concentrations, temperatures, and barometric pressures were measured at ~2,500 GPS-referenced locations during a one-hour, eleven-orbit survey of air around Mammoth Mountain at ~3 km from the summit and altitudes of 2,895-3,657 m. A volcanic CO2 anomaly 4-5 km across with CO2 levels ~1 ppm above background was revealed downwind of tree-kill areas. It contained a 1-km core with concentrations exceeding background by >3 ppm. Emission rates of ~250 t d-1 are indicated. Orographic winds may play a key role in transporting the diffusely degassed CO2 upslope to elevations where it is lofted into the regional wind system.We report the first airborne detection of CO2 degassing from diffuse volcanic sources. Airborne measurement of diffuse CO2 degassing offers a rapid alternative for monitoring CO2 emission rates at Mammoth Mountain. CO2 concentrations, temperatures, and barometric pressures were measured at approximately 2,500 GPS-referenced locations during a one-hour, eleven-orbit survey of air around Mammoth Mountain at approximately 3 km from the summit and altitudes of 2,895-3,657 m. A volcanic CO2 anomaly 4-5 km across with CO2 levels approximately 1 ppm above background was revealed downwind of tree-kill areas. It contained a 1-km core with concentrations exceeding background by >3 ppm. Emission rates of approximately 250 t d-1 are indicated. Orographic winds may play a key role in transporting the diffusely degassed CO2 upslope to elevations where it is lofted into the regional wind system.

Limitations to CO2-induced growth enhancement in pot studies.

PubMed

McConnaughay, K D M; Berntson, G M; Bazzaz, F A

1993-07-01

Recently, it has been suggested that small pots may reduce or eliminate plant responses to enriched CO 2 atmospheres due to root restriction. While smaller pot volumes provide less physical space available for root growth, they also provide less nutrients. Reduced nutrient availability alone may reduce growth enhancement under elevated CO 2 . To investigate the relative importance of limited physical rooting space separate from and in conjunction with soil nutrients, we grew plants at ambient and double-ambient CO 2 levels in growth containers of varied volume, shape, nutrient concentration, and total nutrient content. Two species (Abutilon theophrasti, a C 3 dicot with a deep tap root andSetaria faberii, a C 4 monocot with a shallow diffuse root system) were selected for their contrasting physiology and root architecture. Shoot demography was determined weekly and biomass was determined after eight and ten weeks of growth. Increasing total nutrients, either by increasing nutrient concentration or by increasing pot size, increased plant growth. Further, increasing pot size while maintaining equal total nutrients per pot resulted in increased total biomass for both species. CO 2 -induced growth and reproductive yield enhancements were greatest in pots with high nutrient concentrations, regardless of total nutrient content or pot size, and were also mediated by the shape of the pot. CO 2 -induced growth and reproductive yield enhancements were unaffected by pot size (growth) or were greater in small pots (reproductive yield), regardless of total nutrient content, contrary to predictions based on earlier studies. These results suggest that several aspects of growth conditions within pots may influence the CO 2 responses of plants; pot size, pot shape, the concentration and total amount of nutrient additions to pots may lead to over-or underestimates of the CO 2 responses of real-world plants.

Monitoring diffuse degassing in monogentic volcanic field during magmatic reactivation: the case of El Hierro (Canary Islands, Spain)

NASA Astrophysics Data System (ADS)

Morales-Ocaña, C.; Feldman, R. C.; Pointer, Z. R.; Rodríguez, F.; Asensio-Ramos, M.; Melián, G.; Padrón, E.; Hernández, P. A.; Pérez, N. M.

2017-12-01

El Hierro (278 km2), the younger, smallest and westernmost island of the Canarian archipelago, is a 5-km-high edifice constructed by rapid constructive and destructive processes in 1.12 Ma, with a truncated trihedron shape and three convergent ridges of volcanic cones. It experienced a submarine eruption from 12 October, 2011 and 5 March 2012, off its southern coast that was the first one to be monitored from the beginning in the Canary Islands. As no visible emanations occur at the surface environment of El Hierro, diffuse degassing studies have become a useful geochemical tool to monitor the volcanic activity in this volcanic island. Diffuse CO2 emission has been monitored at El Hierro Island since 1998 in a yearly basis, with much higher frequency in the period 2011-2012. At each survey, about 600 sampling sites were selected to obtain a homogeneous distribution. Measurements of soil CO2 efflux were performed in situ following the accumulation chamber method. During pre-eruptive and eruptive periods, the diffuse CO2 emission released by the whole island experienced significant increases before the onset of the submarine eruption and the most energetic seismic events of the volcanic-seismic unrest (Melián et al., 2014. J. Geophys. Res. Solid Earth, 119, 6976-6991). The soil CO2 efflux values of the 2017 survey ranged from non-detectable to 53.1 g m-2 d-1. Statistical-graphical analysis of the data show two different geochemical populations; background (B) and peak (P) represented by 77.6% and 22.4% of the total data, respectively, with geometric means of 1.8 and 9.2 g m-2 d-1, respectively. Most of the area showed B values while the P values were mainly observed at the interception center of the three convergent ridges and the north of the island. To estimate the diffuse CO2 emission for the 2017 survey, we ran about 100 sGs simulations. The estimated 2017 diffuse CO2 output released to atmosphere by El Hierro was at 1,150 ± 42 t d-1, value higher than the background average of CO2 emission estimated on 422 t d-1 and slightly higher than the background range of 181 t d-1 (-1σ) and 930 t d-1 (+1σ) estimated at El Hierro volcano during the quiescence period 1998-2010 (Melián et al., 2014, JGR). Monitoring the diffuse CO2 emission has proven to be a very effective tool to detect early warning signals of volcanic unrest at El Hierro.

Prediction of an Apparent Flame Length in a Co-Axial Jet Diffusion Flame Combustor.

DTIC Science & Technology

1983-04-01

This report is comprised of two parts. In Part I a predictive model for an apparent flame length in a co-axial jet diffusion flame combustor is...Overall mass transfer coefficient, evaluated from an empirically developed correlation, is employed to predict total flame length . Comparison of the...experimental and predicted data on total flame length shows a reasonable agreement within sixteen percent over the investigated air and fuel flow rate

CO2 adsorption using TiO2 composite polymeric membranes: A kinetic study.

PubMed

Hafeez, Sarah; Fan, X; Hussain, Arshad; Martín, C F

2015-09-01

CO2 is the main greenhouse gas which causes global climatic changes on larger scale. Many techniques have been utilised to capture CO2. Membrane gas separation is a fast growing CO2 capture technique, particularly gas separation by composite membranes. The separation of CO2 by a membrane is not just a process to physically sieve out of CO2 through the controlled membrane pore size. It mainly depends upon diffusion and solubility of gases, particularly for composite dense membranes. The blended components in composite membranes have a high capability to adsorb CO2. The adsorption kinetics of the gases may directly affect diffusion and solubility. In this study, we have investigated the adsorption behaviour of CO2 in pure and composite membranes to explore the complete understanding of diffusion and solubility of CO2 through membranes. Pure cellulose acetate (CA) and cellulose acetate-titania nanoparticle (CA-TiO2) composite membranes were fabricated and characterised using SEM and FTIR analysis. The results indicated that the blended CA-TiO2 membrane adsorbed more quantity of CO2 gas as compared to pure CA membrane. The high CO2 adsorption capacity may enhance the diffusion and solubility of CO2 in the CA-TiO2 composite membrane, which results in a better CO2 separation. The experimental data was modelled by Pseudo first-order, pseudo second order and intra particle diffusion models. According to correlation factor R(2), the Pseudo second order model was fitted well with experimental data. The intra particle diffusion model revealed that adsorption in dense membranes was not solely consisting of intra particle diffusion. Copyright © 2015. Published by Elsevier B.V.

Spatial and temporal variations of diffuse CO_{2} degassing at the N-S volcanic rift-zone of Tenerife (Canary Islands, Spain) during 2002-2015 period

NASA Astrophysics Data System (ADS)

Alonso, Mar; Ingman, Dylan; Alexander, Scott; Barrancos, José; Rodríguez, Fátima; Melián, Gladys; Pérez, Nemesio M.

2016-04-01

Tenerife is the largest of the Canary Islands and, together with Gran Canaria Island, is the only one with a central volcanic complex that started to grow at about 3.5 Ma. Nowadays the central complex is formed by Las Cañadas caldera, a volcanic depression measuring 16×9 km that resulted from multiple vertical collapses and was partially filled by post-caldera volcanic products. Up to 297 mafic monogenetic cones have been recognized on Tenerife, and they represent the most common eruptive activity occurring on the island during the last 1 Ma (Dóniz et al., 2008). Most of the monogenetic cones are aligned following a triple junction-shaped rift system, as result of inflation produced by the concentration of emission vents and dykes in bands at 120o to one another as a result of minimum stress fracturing of the crust by a mantle upwelling. The main structural characteristic of the southern volcanic rift (N-S) of the island is an apparent absence of a distinct ridge, and a fan shaped distribution of monogenetic cones. Four main volcanic successions in the southern volcanic rift zone of Tenerife, temporally separated by longer periods (˜70 - 250 ka) without volcanic activity, have been identified (Kröchert and Buchner, 2008). Since there are currently no visible gas emissions at the N-S rift, diffuse degassing surveys have become an important geochemical tool for the surveillance of this volcanic system. We report here the last results of diffuse CO2 efflux survey at the N-S rift of Tenerife, performed using the accumulation chamber method in the summer period of 2015. The objectives of the surveys were: (i) to constrain the total CO2 output from the studied area and (ii) to evaluate occasional CO2 efflux surveys as a volcanic surveillance tool for the N-S rift of Tenerife. Soil CO2 efflux values ranged from non-detectable up to 31.7 g m-2 d-1. A spatial distribution map, constructed following the sequential Gaussian simulation (sGs) procedure, did not show an apparent relation between higher diffuse CO2 emission values and the main N-S axis of the rift. The total CO2 output released to the atmosphere in a diffuse way has been estimated at 707 t d-1, which represents a value three times higher than the average of the three studies conducted previously. This observed increase suggests the occurrence of an episodic enhanced magmatic (endogenous) contribution. This also confirms the need of periodic diffuse emission surveys in the area as a powerful volcanic surveillance tool, mainly in volcanic systems where visible gas emanations are absent. References: Dóniz et al., 2008. J. Volcanol. Geotherm. Res. 173, 185. Kröchert and Buchner, 2008. Geol. Mag. 146, 161.

In General, the Total Voltammetric Current from a Mixture of Redox-Active Substances will Not be the Sum of the Currents that Each Substance would Produce Independently at the Same Concentration as in the Mixture

NASA Technical Reports Server (NTRS)

Leventis, Nicholas; Oh, Woon Su; Gao, Xue-Rong; Rawashdeh, Abdel Monem M.

2003-01-01

At the potential range where both decamethylferrocene (dMeFc) and ferrocene (Fc) are oxidized with rates controlled by linear diffusion, electrogenerated Fc(+) radicals diffusing outwards from the electrode react quantitatively (K23 C=5.8 x 10(exp 8) with dMeFc diffusing towards the electrode and produce Fc and dMeFc. That reaction replaces dMeFc with Fc, whose diffusion coefficient is higher than that of dMeFc(+), and the total mass-transfer limited current from the mixture is increased by approximately 10%. Analogous observations are made when mass-transfer is controlled by convective-diffusion as in RDE voltammetry. Similar results have been obtained with another, and for all practical purposes randomly selected pair of redox-active substances, [Co(bipy)3](2+) and N - methylphenothiazine (MePTZ); reaction of MePTZ(+) with [Co(bipy)3](2+) replaces the latter with MePTZ, which diffuses faster and the current increases by approximately 20%. The experimental voltammograms have been simulated numerically and the role of (a) the rate constant of the homogeneous reaction; (b) the relative concentrations; and, (c) the diffusion coefficients of all species involved have been studied in detail. Importantly, it was also identified that within any given redox system the dependence of the mass-transfer limited current on the bulk concentrations of the redox-active species is expected to be non-linear. These findings are discussed in terms of their electroanalytical implications.

Diffuse CO2 degassing monitoring for the volcanic surveillance of Tenerife North-East Rift Zone (NERZ) volcano, Canary Islands

NASA Astrophysics Data System (ADS)

Rodríguez, F.; Thomas, G. E.; Wong, T.; García, E.; Melián, G.; Padron, E.; Asensio-Ramos, M.; Hernández, P. A.; Perez, N. M.

2017-12-01

The North East Rift zone of Tenerife Island (NERZ, 210 km2) is one of the three major volcanic rift-zones of the island. The most recent eruptive activity along the NERZ took place in the 1704-1705 period with eruptions of Siete Fuentes, Fasnia and Arafo volcanoes. Since fumarolic activity is nowadays absent at the NERZ, soil CO2 degassing monitoring represent a potential geochemical tool for its volcanic surveillance. The aim of this study is to report the results of the last CO2 efflux survey performed in June 2017, with 658 sampling sites. In-situ measurements of CO2 efflux from the surface environment of the NERZ were performed by means of a portable non-dispersive infrared spectrophotometer (NDIR) following the accumulation chamber method. To quantify the total CO2 emission, soil CO2 efflux spatial distribution maps were constructed using Sequential Gaussian Simulation (SGS) as interpolation method. The diffuse CO2 emission values ranged between 0 - 41.1 g m-2 d-1. The probability plot technique applied to the data allowed to distinguish two different geochemical populations; background (B) and peak (P) represented by 81.8% and 18.2% of the total data, respectively, with geometric means of 3.9 and 15.0 g m-2 d-1, respectively. The average map constructed with 100 equiprobable simulations showed an emission rate of 1,361±35 t d-1. This value relatively higher than the background average of CO2 emission estimated on 415 t d-1 and slightly higher than the background range of 148 t d-1 (-1σ) and 1,189 t d-1 (+1σ) observed at the NERZ. This study reinforces the importance of performing soil CO2 efflux surveys as an effective surveillance volcanic tool in the NERZ.

Finite Volume Scheme for Double Convection-Diffusion Exchange of Solutes in Bicarbonate High-Flux Hollow-Fiber Dialyzer Therapy

PubMed Central

Annan, Kodwo

2012-01-01

The efficiency of a high-flux dialyzer in terms of buffering and toxic solute removal largely depends on the ability to use convection-diffusion mechanism inside the membrane. A two-dimensional transient convection-diffusion model coupled with acid-base correction term was developed. A finite volume technique was used to discretize the model and to numerically simulate it using MATLAB software tool. We observed that small solute concentration gradients peaked and were large enough to activate solute diffusion process in the membrane. While CO2 concentration gradients diminished from their maxima and shifted toward the end of the membrane, HCO3 − concentration gradients peaked at the same position. Also, CO2 concentration decreased rapidly within the first 47 minutes while optimal HCO3 − concentration was achieved within 30 minutes of the therapy. Abnormally high diffusion fluxes were observed near the blood-membrane interface that increased diffusion driving force and enhanced the overall diffusive process. While convective flux dominated total flux during the dialysis session, there was a continuous interference between convection and diffusion fluxes that call for the need to seek minimal interference between these two mechanisms. This is critical for the effective design and operation of high-flux dialyzers. PMID:23197994

CO 2 is dominant greenhouse gas emitted from six hydropower reservoirs in southeastern United States during peak summer emissions

DOE PAGES

Bevelhimer, Mark S.; Stewart, Aurthur J.; Fortner, Allison M.; ...

2016-01-06

During August-September 2012, we sampled six hydropower reservoirs in southeastern United States. for CO 2 and CH 4 emissions via three pathways: diffusive emissions from water surface; ebullition in the water column; and losses from dam tailwaters during power generation. Average total emission rates of CO 2 for the six reservoirs ranged from 1,127 to 2,051 mg m -2 d -1, which is low to moderate compared to CO 2 emissions rates reported for tropical hydropower reservoirs and boreal ponds and lakes, and similar to rates reported for other temperate reservoirs. Similar average rates for CH 4 were also relativelymore » low, ranging from 5 to 83 mg m -2 d -1. On a whole-reservoir basis, total emissions of CO 2 ranged nearly 10-fold, from ~51,000 kg per day for Fontana to ~486,000 kg per day for Guntersville, and total emissions of CH 4 ranged nearly 20-fold, from ~5 kg per day for Fontana to ~83 kg per day for Allatoona. Emissions through the tailwater pathway varied among reservoirs, comprising from 20 to 50% of total CO 2 emissions and 0 to 90% of CH 4 emissions, depending on the reservoir. Furthermore, several explanatory factors related to reservoir morphology and water quality were considered for observed differences among reservoirs.« less

Monitoring diffuse degassing in monogentic volcanic field during a quiescent period: the case of Cumbre Vieja (La Palma,Canary Islands, Spain)

NASA Astrophysics Data System (ADS)

Burns, F.; Cole, M.; Vaccaro, W.; Alonso Cótchico, M.; Melián, G.; Asensio-Ramos, M.; Padron, E.; Hernandez Perez, P. A.; Perez, N. M.

2017-12-01

Volcanic activity at La Palma (Canary Islands) in the last 123 ka has taken place exclusively at the southern part of the island, where Cumbre Vieja volcano, which is characterized by a main north-south rift zone 20 km long and up to 1950 m in elevation and covering an area of 220 km2 with vents located also at the northwest and northeast. Cumbre Vieja is the most active basaltic volcano in the Canaries with 7 historical eruptions being San Juan (1949) and Teneguía (1971) the most recent ones. Since no visible degassing (fumaroles, etc.) at Cumbre Vieja occurs, our geochemical program for the volcanic surveillance of Cumbre Vieja is mainly focused on diffuse degassing monitoring. Diffuse CO2 emission surveys are yearly performed in summer to minimize the influence of meteorological variations. About 570 sampling sites were selected for each survey to obtain a homogeneous distribution after taking into consideration the local geology, structure, and accessibility. Measurements of soil CO2 efflux were performed in situ by means of a portable non-dispersive infrared sensor following the accumulation chamber method. The soil CO2 efflux values of the 2017 survey ranged from non-detectable to 47.7 g m-2 d-1. Statistical-graphical analysis of the data show two different geocheleemical populations; background (B) and peak (P) represented by 98.2% and 1.8% of the total data, respectively. The geometric means of the B and P populations are 2.9 and 36.5 g m-2 d-1, respectively. Most of the area showed B values while the P values were mainly observed both flanks of the main N-S volcanic rift. To estimate the diffuse CO2 emission in metric tons per day released from Cumbre Vieja (220 km2) for the 2017 survey, we ran about 100 sGs simulations. The estimated 2017 diffuse CO2 output released to atmosphere by Cumbre Vieja was at 801 ± 27 t d-1, value relatively higher than the background average of CO2 emission estimated on 374 t d-1 and within the background range of 132 t d-1 (-1σ) and 1.254 t d-1 (+1σ) observed at Cumbre Vieja volcano during the period 2001-2013 (Padrón et al., 2015. Bull. Volcanol. 77:28). Monitoring the diffuse CO2 emission contributes to detect early warning signals of volcanic unrest at Cumbre Vieja volcano.

A permanent volcanic hazard hiding in diffuse degassing areas

NASA Astrophysics Data System (ADS)

Viveiros, Fátima; Silva, Catarina; Ferreira, Teresa; Pacheco, Joana; Luís Gaspar, João

2017-04-01

Carbon dioxide (CO2) is one of the most abundant volcanic gases and it is released not only during eruptive events, but also during periods of quiescence through fumaroles, springs and soil diffuse degassing areas. In this last case, CO2 is permanently and silently released from the soils and high CO2 concentrations can be measured if the gas accumulates in depressed and non-ventilated areas (such as caves, pits), or even if it enters in buildings. From a public health perspective CO2 is considered an inert asphyxiant gas and may be lethal when present in concentrations higher than 10 vol.%. In the last 30 years several diffuse degassing areas have been identified in different volcanic systems and lethal incidents due to high CO2 concentrations were reported in volcanic environments of Italy (Alban Hills), New Zealand (Rotorua), Cameroon (Lake Nyos and Lake Cameroon), USA (Mammoth Mountain) and Portugal (Azores archipelago). In the Azores volcanic archipelago several villages are located in diffuse degassing areas, where lethal indoor CO2 concentrations (> 20 vol.%) were measured. Recent studies showed that the rate of CO2 emission may change not only during seismo-volcanic unrest, but also due to changes in the meteorological conditions (e.g. barometric pressure, rainfall, wind speed). Few works are available in the literature with permanent monitoring of indoor CO2 in diffuse degassing environments and the monitoring tests are usually applied during a short period of time. This study shows the results of four years (2012-2016) of permanent CO2 monitoring in 12 buildings placed at Caldeiras da Ribeira Grande, an area located in the north flank of Fogo Volcano (São Miguel Island, Azores archipelago), where thermal anomalies and CO2 emissions were detected. CO2 fluxes as high as 20000 g m-2 d-1 are released from the soils and temperature in some sites reaches 100°C. Spike-like and long term variations are observed in the time series recorded by a total of 52 infrared CO2 detectors installed. Results highlight that CO2 can reach hazardous concentrations (> 15 vol.%) due to meteorological changes and show the occurrence of seasonal variations. Different indoor CO2 patterns are displayed depending on the location of the buildings over thermal anomalous zone. Due to its density at standard temperature and pressure, CO2 tends to accumulate in the underground and/or in the ground floor of the buildings, however in the present study higher CO2 concentrations were also measured in the upper floors of some buildings, fact that is correlated with the presence of thermal anomaly. Results obtained based on this robust and continuous monitoring system show once again that indoor CO2 can reach frequently lethal concentrations even in periods of quiescence and that inhabitants of these buildings are exposed to a permanent and quiet hazard, which is detected only through the use of specific instruments. The existence of thermal anomaly associated with the CO2 emission is also responsible for different patterns when compared with the "cold" CO2 degassing areas.

Proton transport by phosphate diffusion--a mechanism of facilitated CO2 transfer

PubMed Central

1976-01-01

We have measured CO2 fluxes across phosphate solutions at different carbonic anhydrase concentrations, bicarbonate concentration gradients, phosphate concentrations, and mobilities. Temperature was 22-25 degrees C, the pH of the phosphate solutions was 7.0-7.3. We found that under physiological conditions of pH and pCO2 a facilitated diffusion of CO2 occurs in addition to free diffusion when (a) sufficient carbonic anhydrase is present, and (b) a concentration gradient of HCO3- is established along with a pCO2 gradient, and (c) the phosphate buffer has a mobility comparable to that of bicarbonate. When the phosphate was immobilized by attaching 0.25-mm-long cellulose particles, no facilitation of CO2 diffusion was detectable. A mechanism of facilitated CO2 diffusion in phosphate solutions analogous to that in albumin solutions was proposed on the basis of these findings: bicarbonate diffusion together with a facilitated proton transport by phosphate diffusion. A mathematical model of this mechanism was formulated. The CO2 fluxed predicted by the model agree quantitatively with the experimentally determined fluxes. It is concluded that a highly effective proton transport mechanism acts in solutions of mobile phosphate buffers. By this mechanism; CO2 transfer may be increased up to fivefold and proton transfer may be increased to 10,000-fold. PMID:6619

Coordination between leaf CO2 diffusion and Rubisco properties allows maximizing photosynthetic efficiency in Limonium species.

PubMed

Galmés, Jeroni; Molins, Arántzazu; Flexas, Jaume; Conesa, Miquel À

2017-10-01

High photosynthetic efficiency intrinsically demands tight coordination between traits related to CO 2 diffusion capacity and leaf biochemistry. Although this coordination constitutes the basis of existing mathematical models of leaf photosynthesis, it has been barely explored among closely related species, which could reveal rapid adaptation clues in the recent past. With this aim, we characterized the photosynthetic capacity of 12 species of Limonium, possessing contrasting Rubisco catalytic properties, grown under optimal (WW) and extreme drought conditions (WD). The availability of CO 2 at the site of carboxylation (C c ) determined the photosynthetic capacity of Limonium under WD, while both diffusional and biochemical components governed the photosynthetic performance under WW. The variation in the in vivo caboxylation efficiency correlated with both the concentration of active Rubisco sites and the in vitro-based properties of Rubisco, such as the maximum carboxylase turnover rate (k cat c ) and the Michaelis-Menten constant for CO 2 (K c ). Notably, the results confirmed the hypothesis of coordination between the CO 2 offer and demand functions of photosynthesis: those Limonium species with high total leaf conductance to CO 2 have evolved towards increased velocity (i.e. higher k cat c ), at the penalty of lower affinity for CO 2 (i.e. lower specificity factor, S c/o ). © 2017 John Wiley & Sons Ltd.

Diffusivity of nitrous oxide in N-methyldiethanolamine + diethanolamine + water

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

Rinker, E.B.; Russell, J.W.; Tamimi, A.

1995-05-01

The tertiary amine N-methyldiethanolamine and the secondary amine diethanolamine are commonly used in the gas-treating industry as chemical solvents for the removal of acid gases such as CO{sub 2} and H{sub 2}S. The diffusion coefficients for nitrous oxide in aqueous solutions consisting of N-methyldiethanolamine (MDEA) and diethanolamine (DEA) were measured over the temperature range 293--353 K for a total amine concentration of 50 mass % and for the mass ratio of DEA to MDEA varying from 0.0441 to 0.588. The experimental diffusion coefficients were found to be relatively insensitive to the mass ratio of amines.

Volatile emissions and gas geochemistry of Hot Spring Basin, Yellowstone National Park, USA

USGS Publications Warehouse

Werner, C.; Hurwitz, S.; Evans, William C.; Lowenstern, J. B.; Bergfeld, D.; Heasler, H.; Jaworowski, C.; Hunt, A.

2008-01-01

We characterize and quantify volatile emissions at Hot Spring Basin (HSB), a large acid-sulfate region that lies just outside the northeastern edge of the 640??ka Yellowstone Caldera. Relative to other thermal areas in Yellowstone, HSB gases are rich in He and H2, and mildly enriched in CH4 and H2S. Gas compositions are consistent with boiling directly off a deep geothermal liquid at depth as it migrates toward the surface. This fluid, and the gases evolved from it, carries geochemical signatures of magmatic volatiles and water-rock reactions with multiple crustal sources, including limestones or quartz-rich sediments with low K/U (or 40*Ar/4*He). Variations in gas chemistry across the region reflect reservoir heterogeneity and variable degrees of boiling. Gas-geothermometer temperatures approach 300????C and suggest that the reservoir feeding HSB is one of the hottest at Yellowstone. Diffuse CO2 flux in the western basin of HSB, as measured by accumulation-chamber methods, is similar in magnitude to other acid-sulfate areas of Yellowstone and is well correlated to shallow soil temperatures. The extrapolation of diffuse CO2 fluxes across all the thermal/altered area suggests that 410 ?? 140??t d- 1 CO2 are emitted at HSB (vent emissions not included). Diffuse fluxes of H2S were measured in Yellowstone for the first time and likely exceed 2.4??t d- 1 at HSB. Comparing estimates of the total estimated diffuse H2S emission to the amount of sulfur as SO42- in streams indicates ~ 50% of the original H2S in the gas emission is lost into shallow groundwater, precipitated as native sulfur, or vented through fumaroles. We estimate the heat output of HSB as ~ 140-370??MW using CO2 as a tracer for steam condensate, but not including the contribution from fumaroles and hydrothermal vents. Overall, the diffuse heat and volatile fluxes of HSB are as great as some active volcanoes, but they are a small fraction (1-3% for CO2, 2-8% for heat) of that estimated for the entire Yellowstone system.

Major diffusion leaks of clamp-on leaf cuvettes still unaccounted: how erroneous are the estimates of Farquhar et al. model parameters?

PubMed

Rodeghiero, Mirco; Niinemets, Ulo; Cescatti, Alessandro

2007-08-01

Estimates of leaf gas-exchange characteristics using standard clamp-on leaf chambers are prone to errors because of diffusion leaks. While some consideration has been given to CO(2) diffusion leaks, potential water vapour diffusion leaks through chamber gaskets have been neglected. We estimated diffusion leaks of two clamp-on Li-Cor LI-6400 (Li-Cor, Inc., Lincoln, NE, USA) leaf chambers with polymer foam gaskets and enclosing either 2 or 6 cm(2) leaf area, and conducted a sensitivity analysis of the diffusion leak effects on Farquhar et al. photosynthesis model parameters - the maximum carboxylase activity of ribulose 1 x 5-bisphosphate carboxylase/oxygenase (Rubisco) (V(cmax)), capacity for photosynthetic electron transport (J(max)) and non-photorespiratory respiration rate in light (R(d)). In addition, net assimilation rate (A(n)) versus intercellular CO(2) (C(i)) responses were measured in leaves of Mediterranean evergreen species Quercus ilex L. enclosing the whole leaf chamber in a polyvinyl fluoride bag flushed with the exhaust air of leaf chamber, thereby effectively reducing the CO(2) and water vapour gradients between ambient air and leaf chamber. For the empty chambers, average diffusion leak for CO(2), K(CO2), (molar flow rate corresponding to unit CO(2) mole fraction difference) was ca. 0.40 micromol s(-1). K(CO2) increased ca. 50% if a dead leaf was clamped between the leaf chamber. Average diffusion leak for H(2)O was ca. 5- to 10-fold larger than the diffusion leak for CO(2). Sensitivity analyses demonstrated that the consequence of a CO(2) diffusion leak was apparent enhancement of A(n) at high CO(2) mole fraction and reduction at lower CO(2) mole fraction, and overall compression of C(i) range. As the result of these modifications, Farquhar et al. model parameters were overestimated. The degree of overestimation increased in the order of V(cmax) < J(max) < R(d), and was larger for smaller chambers and for leaves with lower photosynthetic capacity, leading to overestimation of all three parameters by 70-290% for 2 cm(2), and by 10-60% for 6 cm(2) chamber. Significant diffusion corrections (5-36%) were even required for leaves with high photosynthetic capacity measured in largest chamber. Water vapour diffusion leaks further enhanced the overestimation of model parameters. For small chambers and low photosynthetic capacities, apparent C(i) was simulated to decrease with increasing A(n) because of simultaneous CO(2) and H(2)O diffusion leaks. Measurements in low photosynthetic capacity Quercus ilex leaves enclosed in 2 cm(2) leaf chamber exhibited negative apparent C(i) values at highest A(n). For the same leaves measured with the entire leaf chamber enclosed in the polyvinyl fluoride bag, C(i) and A(n) increased monotonically. While the measurements without the bag could be corrected for diffusion leaks, the required correction in A(n) and transpiration rates was 100-500%, and there was large uncertainty in Farquhar et al. model parameters derived from 'corrected'A(n)/C(i) response curves because of uncertainties in true diffusion leaks. These data demonstrate that both CO(2) and water vapour diffusion leaks need consideration in measurements with clamp-on leaf cuvettes. As plants in natural environments are often characterized by low photosynthetic capacities, cuvette designs need to be improved for reliable measurements in such species.

TiO2 as diffusion barrier at Co/Alq3 interface studied by x-ray standing wave technique

NASA Astrophysics Data System (ADS)

Phatak Londhe, Vaishali; Gupta, A.; Ponpandian, N.; Kumar, D.; Reddy, V. R.

2018-06-01

Nano-scale diffusion at the interfaces in organic spin valve thin films plays a vital role in controlling the performance of magneto-electronic devices. In the present work, it is shown that a thin layer of titanium dioxide at the interface of Co/Alq3 can act as a good diffusion barrier. The buried interfaces of Co/Alq3/Co organic spin valve thin film has been studied using x-ray standing waves technique. A planar waveguide is formed with Alq3 layer forming the cavity and Co layers as the walls of the waveguide. Precise information about diffusion of Co into Alq3 is obtained through excitation of the waveguide modes. It is found that the top Co layer diffuses deep into the Alq3 resulting in incorporation of 3.1% Co in the Alq3 layer. Insertion of a 1.7 nm thick barrier layer of TiO2 at Co/Alq3 interface results in a drastic reduction in the diffusion of Co into Alq3 to a value of only 0.4%. This suggests a better performance of organic spin valve with diffusion barrier of TiO2.

Nitrous Oxide Production in Co- Versus Counter-Diffusion Nitrifying Biofilms

NASA Astrophysics Data System (ADS)

Peng, Lai; Sun, Jing; Liu, Yiwen; Dai, Xiaohu; Ni, Bing-Jie

2016-06-01

For the application of biofilm processes, a better understanding of nitrous oxide (N2O) formation within the biofilm is essential for design and operation of biofilm reactors with minimized N2O emissions. In this work, a previously established N2O model incorporating both ammonia oxidizing bacteria (AOB) denitrification and hydroxylamine (NH2OH) oxidation pathways is applied in two structurally different biofilm systems to assess the effects of co- and counter-diffusion on N2O production. It is demonstrated that the diffusion of NH2OH and oxygen within both types of biofilms would form an anoxic layer with the presence of NH2OH and nitrite ( ), which would result in a high N2O production via AOB denitrification pathway. As a result, AOB denitrification pathway is dominant over NH2OH oxidation pathway within the co- and counter-diffusion biofilms. In comparison, the co-diffusion biofilm may generate substantially higher N2O than the counter-diffusion biofilm due to the higher accumulation of NH2OH in co-diffusion biofilm, especially under the condition of high-strength ammonium influent (500 mg N/L), thick biofilm depth (300 μm) and moderate oxygen loading (~1-~4 m3/d). The effect of co- and counter-diffusion on N2O production from the AOB biofilm is minimal when treating low-strength nitrogenous wastewater.

Nitrous Oxide Production in Co- Versus Counter-Diffusion Nitrifying Biofilms

PubMed Central

Peng, Lai; Sun, Jing; Liu, Yiwen; Dai, Xiaohu; Ni, Bing-Jie

2016-01-01

For the application of biofilm processes, a better understanding of nitrous oxide (N2O) formation within the biofilm is essential for design and operation of biofilm reactors with minimized N2O emissions. In this work, a previously established N2O model incorporating both ammonia oxidizing bacteria (AOB) denitrification and hydroxylamine (NH2OH) oxidation pathways is applied in two structurally different biofilm systems to assess the effects of co- and counter-diffusion on N2O production. It is demonstrated that the diffusion of NH2OH and oxygen within both types of biofilms would form an anoxic layer with the presence of NH2OH and nitrite ( ), which would result in a high N2O production via AOB denitrification pathway. As a result, AOB denitrification pathway is dominant over NH2OH oxidation pathway within the co- and counter-diffusion biofilms. In comparison, the co-diffusion biofilm may generate substantially higher N2O than the counter-diffusion biofilm due to the higher accumulation of NH2OH in co-diffusion biofilm, especially under the condition of high-strength ammonium influent (500 mg N/L), thick biofilm depth (300 μm) and moderate oxygen loading (~1–~4 m3/d). The effect of co- and counter-diffusion on N2O production from the AOB biofilm is minimal when treating low-strength nitrogenous wastewater. PMID:27353382

Vortex Generators in a Streamline-Traced, External-Compression Supersonic Inlet

NASA Technical Reports Server (NTRS)

Baydar, Ezgihan; Lu, Frank K.; Slater, John W.; Trefny, Charles J.

2017-01-01

Vortex generators within a streamline-traced, external-compression supersonic inlet for Mach 1.66 were investigated to determine their ability to increase total pressure recovery and reduce total pressure distortion. The vortex generators studied were rectangular vanes arranged in counter-rotating and co-rotating arrays. The vane geometric factors of interest included height, length, spacing, angle-of-incidence, and positions upstream and downstream of the inlet terminal shock. The flow through the inlet was simulated numerically through the solution of the steady-state, Reynolds-averaged Navier-Stokes equations on multi-block, structured grids using the Wind-US flow solver. The vanes were simulated using a vortex generator model. The inlet performance was characterized by the inlet total pressure recovery and the radial and circumferential total pressure distortion indices at the engine face. Design of experiments and statistical analysis methods were applied to quantify the effect of the geometric factors of the vanes and search for optimal vane arrays. Co-rotating vane arrays with negative angles-of-incidence positioned on the supersonic diffuser were effective in sweeping low-momentum flow from the top toward the sides of the subsonic diffuser. This distributed the low-momentum flow more evenly about the circumference of the subsonic diffuser and reduced distortion. Co-rotating vane arrays with negative angles-of-incidence or counter-rotating vane arrays positioned downstream of the terminal shock were effective in mixing higher-momentum flow with lower-momentum flow to increase recovery and decrease distortion. A strategy of combining a co-rotating vane array on the supersonic diffuser with a counter-rotating vane array on the subsonic diffuser was effective in increasing recovery and reducing distortion.

Diffusion and Clustering of Carbon Dioxide on Non-porous Amorphous Solid Water

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

He, Jiao; Emtiaz, Shahnewaj M.; Vidali, Gianfranco

2017-03-01

Observations by ISO and Spitzer toward young stellar objects showed that CO{sub 2} segregates in the icy mantles covering dust grains. Thermal processing of the ice mixture was proposed as being responsible for the segregation. Although several laboratories studied thermally induced segregation, a satisfying quantification is still missing. We propose that the diffusion of CO{sub 2} along pores inside water ice is the key to quantify segregation. We combined Temperature Programmed Desorption and Reflection Absorption InfraRed Spectroscopy to study how CO{sub 2} molecules interact on a non-porous amorphous solid water (np-ASW) surface. We found that CO{sub 2} diffuses significantly onmore » an np-ASW surface above 65 K and clusters are formed at well below one monolayer. A simple rate equation simulation finds that the diffusion energy barrier of CO{sub 2} on np-ASW is 2150 ± 50 K, assuming a diffusion pre-exponential factor of 10{sup 12} s{sup −1}. This energy should also apply to the diffusion of CO{sub 2} on the wall of pores. The binding energy of CO{sub 2} from CO{sub 2} clusters and CO{sub 2} from H{sub 2}O ice has been found to be 2415 ± 20 K and 2250 ± 20 K, respectively, assuming the same prefactor for desorption. CO{sub 2}–CO{sub 2} interaction is stronger than CO{sub 2}–H{sub 2}O interaction, in agreement with the experimental finding that CO{sub 2} does not wet the np-ASW surface. For comparison, we carried out similar experiments with CO on np-ASW, and found that the CO–CO interaction is always weaker than CO–H{sub 2}O. As a result, CO wets the np-ASW surface. This study should be of help to uncover the thermal history of CO{sub 2} on the icy mantles of dust grains.« less

Selective Adsorption and Selective Transport Diffusion of CO2-CH4 Binary Mixture in Coal Ultramicropores.

PubMed

Zhao, Yongliang; Feng, Yanhui; Zhang, Xinxin

2016-09-06

The adsorption and diffusion of the CO2-CH4 mixture in coal and the underlying mechanisms significantly affect the design and operation of any CO2-enhanced coal-bed methane recovery (CO2-ECBM) project. In this study, bituminous coal was fabricated based on the Wiser molecular model and its ultramicroporous parameters were evaluated; molecular simulations were established through Grand Canonical Monte Carlo (GCMC) and Molecular Dynamic (MD) methods to study the effects of temperature, pressure, and species bulk mole fraction on the adsorption isotherms, adsorption selectivity, three distinct diffusion coefficients, and diffusivity selectivity of the binary mixture in the coal ultramicropores. It turns out that the absolute adsorption amount of each species in the mixture decreases as temperature increases, but increases as its own bulk mole fraction increases. The self-, corrected, and transport diffusion coefficients of pure CO2 and pure CH4 all increase as temperature or/and their own bulk mole fractions increase. Compared to CH4, the adsorption and diffusion of CO2 are preferential in the coal ultramicropores. Adsorption selectivity and diffusivity selectivity were simultaneously employed to reveal that the optimal injection depth for CO2-ECBM is 800-1000 m at 308-323 K temperature and 8.0-10.0 MPa.

Measurement of CO2 diffusivity for carbon sequestration: a microfluidic approach for reservoir-specific analysis.

PubMed

Sell, Andrew; Fadaei, Hossein; Kim, Myeongsub; Sinton, David

2013-01-02

Predicting carbon dioxide (CO(2)) security and capacity in sequestration requires knowledge of CO(2) diffusion into reservoir fluids. In this paper we demonstrate a microfluidic based approach to measuring the mutual diffusion coefficient of carbon dioxide in water and brine. The approach enables formation of fresh CO(2)-liquid interfaces; the resulting diffusion is quantified by imaging fluorescence quenching of a pH-dependent dye, and subsequent analyses. This method was applied to study the effects of site-specific variables--CO(2) pressure and salinity levels--on the diffusion coefficient. In contrast to established, macro-scale pressure-volume-temperature cell methods that require large sample volumes and testing periods of hours/days, this approach requires only microliters of sample, provides results within minutes, and isolates diffusive mass transport from convective effects. The measured diffusion coefficient of CO(2) in water was constant (1.86 [± 0.26] × 10(-9) m(2)/s) over the range of pressures (5-50 bar) tested at 26 °C, in agreement with existing models. The effects of salinity were measured with solutions of 0-5 M NaCl, where the diffusion coefficient varied up to 3 times. These experimental data support existing theory and demonstrate the applicability of this method for reservoir-specific testing.

Molecular simulations of a CO2/CO mixture in MIL-127

NASA Astrophysics Data System (ADS)

Chokbunpiam, Tatiya; Fritzsche, Siegfried; Parasuk, Vudhichai; Caro, Jürgen; Assabumrungrat, Suttichai

2018-03-01

Adsorption and diffusion of an equimolar feed mixture of CO2 and CO in MIL-127 at three different temperatures and pressures up to 12 bar were investigated by molecular simulations. The adsorption was simulated using Gibbs-Ensemble Monte Carlo (GEMC). The structure of the adsorbed phase and the diffusion in the MIL were investigated using Molecular Dynamics (MD) simulations. The adsorption selectivity of MIL-127 for CO2 over CO at 233 K was about 15. When combining adsorption and diffusion selectivities, a membrane selectivity of about 12 is predicted. For higher temperatures, both adsorption and diffusion selectivity are found to be smaller.

Methane and carbon dioxide emissions from 40 lakes along a north–south latitudinal transect in Alaska

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

Sepulveda-Jauregui, A.; Walter Anthony, K. M.; Martinez-Cruz, K.

Uncertainties in the magnitude and seasonality of various gas emission modes, particularly among different lake types, limit our ability to estimate methane (CH 4) and carbon dioxide (CO 2) emissions from northern lakes. Here we assessed the relationship between CH 4 and CO 2 emission modes in 40 lakes along a latitudinal transect in Alaska to lakes' physicochemical properties and geographic characteristics, including permafrost soil type surrounding lakes. Emission modes included direct ebullition, diffusion, storage flux, and a newly identified ice-bubble storage (IBS) flux. We found that all lakes were net sources of atmospheric CH 4 and CO 2, butmore » the climate warming impact of lake CH 4 emissions was 2 times higher than that of CO 2. Ebullition and diffusion were the dominant modes of CH 4 and CO 2 emissions, respectively. IBS, ~10% of total annual CH 4 emissions, is the release to the atmosphere of seasonally ice-trapped bubbles when lake ice confining bubbles begins to melt in spring. IBS, which has not been explicitly accounted for in regional studies, increased the estimate of springtime emissions from our study lakes by 320%. Geographically, CH 4 emissions from stratified, mixotrophic interior Alaska thermokarst (thaw) lakes formed in icy, organic-rich yedoma permafrost soils were 6-fold higher than from non-yedoma lakes throughout the rest of Alaska. The relationship between CO 2 emissions and geographic parameters was weak, suggesting high variability among sources and sinks that regulate CO 2 emissions (e.g., catchment waters, pH equilibrium). Total CH 4 emission was correlated with concentrations of soluble reactive phosphorus and total nitrogen in lake water, Secchi depth, and lake area, with yedoma lakes having higher nutrient concentrations, shallower Secchi depth, and smaller lake areas. In conclusion, our findings suggest that permafrost type plays important roles in determining CH 4 emissions from lakes by both supplying organic matter to methanogenesis directly from thawing permafrost and by enhancing nutrient availability to primary production, which can also fuel decomposition and methanogenesis.« less

Methane and carbon dioxide emissions from 40 lakes along a north–south latitudinal transect in Alaska

DOE PAGES

Sepulveda-Jauregui, A.; Walter Anthony, K. M.; Martinez-Cruz, K.; ...

2015-06-02

Uncertainties in the magnitude and seasonality of various gas emission modes, particularly among different lake types, limit our ability to estimate methane (CH 4) and carbon dioxide (CO 2) emissions from northern lakes. Here we assessed the relationship between CH 4 and CO 2 emission modes in 40 lakes along a latitudinal transect in Alaska to lakes' physicochemical properties and geographic characteristics, including permafrost soil type surrounding lakes. Emission modes included direct ebullition, diffusion, storage flux, and a newly identified ice-bubble storage (IBS) flux. We found that all lakes were net sources of atmospheric CH 4 and CO 2, butmore » the climate warming impact of lake CH 4 emissions was 2 times higher than that of CO 2. Ebullition and diffusion were the dominant modes of CH 4 and CO 2 emissions, respectively. IBS, ~10% of total annual CH 4 emissions, is the release to the atmosphere of seasonally ice-trapped bubbles when lake ice confining bubbles begins to melt in spring. IBS, which has not been explicitly accounted for in regional studies, increased the estimate of springtime emissions from our study lakes by 320%. Geographically, CH 4 emissions from stratified, mixotrophic interior Alaska thermokarst (thaw) lakes formed in icy, organic-rich yedoma permafrost soils were 6-fold higher than from non-yedoma lakes throughout the rest of Alaska. The relationship between CO 2 emissions and geographic parameters was weak, suggesting high variability among sources and sinks that regulate CO 2 emissions (e.g., catchment waters, pH equilibrium). Total CH 4 emission was correlated with concentrations of soluble reactive phosphorus and total nitrogen in lake water, Secchi depth, and lake area, with yedoma lakes having higher nutrient concentrations, shallower Secchi depth, and smaller lake areas. In conclusion, our findings suggest that permafrost type plays important roles in determining CH 4 emissions from lakes by both supplying organic matter to methanogenesis directly from thawing permafrost and by enhancing nutrient availability to primary production, which can also fuel decomposition and methanogenesis.« less

Red blood cell thickness is evolutionarily constrained by slow, hemoglobin-restricted diffusion in cytoplasm.

PubMed

Richardson, Sarah L; Swietach, Pawel

2016-10-25

During capillary transit, red blood cells (RBCs) must exchange large quantities of CO 2 and O 2 in typically less than one second, but the degree to which this is rate-limited by diffusion through cytoplasm is not known. Gas diffusivity is intuitively assumed to be fast and this would imply that the intracellular path-length, defined by RBC shape, is not a factor that could meaningfully compromise physiology. Here, we evaluated CO 2 diffusivity (D CO2 ) in RBCs and related our results to cell shape. D CO2 inside RBCs was determined by fluorescence imaging of [H + ] dynamics in cells under superfusion. This method is based on the principle that H + diffusion is facilitated by CO 2 /HCO 3 - buffer and thus provides a read-out of D CO2 . By imaging the spread of H + ions from a photochemically-activated source (6-nitroveratraldehyde), D CO2 in human RBCs was calculated to be only 5% of the rate in water. Measurements on RBCs containing different hemoglobin concentrations demonstrated a halving of D CO2 with every 75 g/L increase in mean corpuscular hemoglobin concentration (MCHC). Thus, to compensate for highly-restricted cytoplasmic diffusion, RBC thickness must be reduced as appropriate for its MCHC. This can explain the inverse relationship between MCHC and RBC thickness determined from >250 animal species.

Forest-killing diffuse CO2 emission at Mammoth Mountain as a sign of magmatic unrest

NASA Astrophysics Data System (ADS)

Farrar, C. D.; Sorey, M. L.; Evans, W. C.; Howle, J. F.; Kerr, B. D.; Kennedy, B. M.; King, C.-Y.; Southon, J. R.

1995-08-01

MAMMOTH Mountain, in the western United States, is a large dacitic volcano with a long history of vo lean ism that began 200 kyr ago1 and produced phreatic eruptions as recently as 500 +/- 200 yr BP (ref. 2). Seismicity, ground deformation and changes in fumarole gas composition suggested an episode of shallow dyke intrusion in 1989-90 (refs 3, 4). Areas of dying forest and incidents of near asphyxia in confined spaces, first reported in 1990, prompted us to search for diffuse flank emissions of magmatic CO2, as have been described at Mount Etna5 and Vulcano6. Here we report the results of a soil-gas survey, begun in 1994, that revealed CO2 concentrations of 30-96% in a 30-hectare region of killed trees, from which we estimate a total CO2 flux of >=1,200 tonnes per day. The forest die-off is the most conspicuous surface manifestation of magmatic processes at Mammoth Mountain, which hosts only weak fumarolic vents and no summit activity. Although the onset of tree kill coincided with the episode of shallow dyke intrusion, the magnitude and duration of the CO2 flux indicates that a larger, deeper magma source and/or a large reservoir of high-pressure gas is being tapped.

Forest-killing diffuse CO2 emission at Mammoth Mountain as a sign of magmatic unrest

USGS Publications Warehouse

Farrar, C.D.; Sorey, M.L.; Evans, William C.; Howle, J.F.; Kerr, B.D.; Kennedy, B.M.; King, C.-Y.; Southon, J.R.

1995-01-01

MAMMOTH Mountain, in the western United States, is a large dacitic volcano with a long history of volcamsm that began 200 kyr ago1 and produced phreatic eruptions as recently as 500 ?? 200 yr BP (ref. 2). Seismicity, ground deformation and changes in fumarole gas composition suggested an episode of shallow dyke intrusion in 1989-90 (refs 3, 4). Areas of dying forest and incidents of near asphyxia in confined spaces, first reported in 1990, prompted us to search for diffuse flank emissions of magmatic CO2, as have been described at Mount Etna5 and Vulcano6. Here we report the results of a soil-gas survey, begun in 1994, that revealed CO2 concentrations of 30-96% in a 30-hectare region of killed trees, from which we estimate a total CO2 flux of ???1,200 tonnes per day. The forest die-off is the most conspicuous surface manifestation of magmatic processes at Mammoth Mountam, which hosts only weak fumarolic vents and no summit activity. Although the onset of tree kill coincided with the episode of shallow dyke intrusion, the magnitude and duration of the CO2 flux indicates that a larger, deeper magma source and/or a large reservoir of high-pressure gas is being tapped.

The influence of different diffusion pattern to the sub- and super-critical fluid flow in brown coal

NASA Astrophysics Data System (ADS)

Peng, Peihuo

2018-03-01

Sub- and super-critical CO2 flowing in nanoscale pores are recently becoming of great interest due to that it is closely related to many engineering applications, such as geological burial and sequestration of carbon dioxide, Enhanced Coal Bed Methane recovery ( ECBM), super-critical CO2 fracturing and so on. Gas flow in nanopores cannot be described simply by the Darcy equation. Different diffusion pattern such as Fick diffusion, Knudsen diffusion, transitional diffusion and slip flow at the solid matrix separate the seepage behaviour from Darcy-type flow. According to the principle of different diffusion pattern, the flow of sub- and super-critical CO2 in brown coal was simulated by numerical method, and the results were compared with the experimental results to explore the contribution of different diffusion pattern and swelling effect in sub- and super-critical CO2 flow in nanoscale pores.

A two-dimensional microscale model of gas exchange during photosynthesis in maize (Zea mays L.) leaves.

PubMed

Retta, Moges; Ho, Quang Tri; Yin, Xinyou; Verboven, Pieter; Berghuijs, Herman N C; Struik, Paul C; Nicolaï, Bart M

2016-05-01

CO2 exchange in leaves of maize (Zea mays L.) was examined using a microscale model of combined gas diffusion and C4 photosynthesis kinetics at the leaf tissue level. Based on a generalized scheme of photosynthesis in NADP-malic enzyme type C4 plants, the model accounted for CO2 diffusion in a leaf tissue, CO2 hydration and assimilation in mesophyll cells, CO2 release from decarboxylation of C4 acids, CO2 fixation in bundle sheath cells and CO2 retro-diffusion from bundle sheath cells. The transport equations were solved over a realistic 2-D geometry of the Kranz anatomy obtained from light microscopy images. The predicted responses of photosynthesis rate to changes in ambient CO2 and irradiance compared well with those obtained from gas exchange measurements. A sensitivity analysis showed that the CO2 permeability of the mesophyll-bundle sheath and airspace-mesophyll interfaces strongly affected the rate of photosynthesis and bundle sheath conductance. Carbonic anhydrase influenced the rate of photosynthesis, especially at low intercellular CO2 levels. In addition, the suberin layer at the exposed surface of the bundle sheath cells was found beneficial in reducing the retro-diffusion. The model may serve as a tool to investigate CO2 diffusion further in relation to the Kranz anatomy in C4 plants. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Non-Boussinesq Dissolution-Driven Convection in Porous Media

NASA Astrophysics Data System (ADS)

Amooie, M. A.; Soltanian, M. R.; Moortgat, J.

2017-12-01

Geological carbon dioxide (CO2) sequestration in deep saline aquifers has been increasingly recognized as a feasible technology to stabilize the atmospheric carbon concentrations and subsequently mitigate the global warming. Solubility trapping is one of the most effective storage mechanisms, which is associated initially with diffusion-driven slow dissolution of gaseous CO2 into the aqueous phase, followed by density-driven convective mixing of CO2 throughout the aquifer. The convection includes both diffusion and fast advective transport of the dissolved CO2. We study the fluid dynamics of CO2 convection in the underlying single aqueous-phase region. Two modeling approaches are employed to define the system: (i) a constant-concentration condition for CO2 in aqueous phase at the top boundary, and (ii) a sufficiently low, constant injection-rate for CO2 from top boundary. The latter allows for thermodynamically consistent evolution of the CO2 composition and the aqueous phase density against the rate at which the dissolved CO2 convects. Here we accurately model the full nonlinear phase behavior of brine-CO2 mixture in a confined domain altered by dissolution and compressibility, while relaxing the common Boussinesq approximation. We discover new flow regimes and present quantitative scaling relations for global characters of spreading, mixing, and dissolution flux in two- and three-dimensional media for the both model types. We then revisit the universal Sherwood-Rayleigh scaling that is under debate for porous media convective flows. Our findings confirm the sublinear scaling for the constant-concentration case, while reconciling the classical linear scaling for the constant-injection model problem. The results provide a detailed perspective into how the available modeling strategies affect the prediction ability for the total amount of CO2 dissolved in the long term within saline aquifers of different permeabilities.

Aquaporins and membrane diffusion of CO2 in living organisms.

PubMed

Kaldenhoff, Ralf; Kai, Lei; Uehlein, Norbert

2014-05-01

Determination of CO2 diffusion rates in living cells revealed inconsistencies with existing models about the mechanisms of membrane gas transport. Mainly, these discrepancies exist in the determined CO2 diffusion rates of bio-membranes, which were orders of magnitudes below those for pure lipid bilayers or theoretical considerations as well as in the observation that membrane insertion of specific aquaporins was rescuing high CO2 transport rates. This effect was confirmed by functional aquaporin protein analysis in heterologous expression systems as well as in bacteria, plants and partly in mammals. This review summarizes the arguments in favor of and against aquaporin facilitated membrane diffusion of CO2 and reports about its importance for the physiology of living organisms. Most likely, the aquaporin tetramer forming an additional fifth pore is required for CO2 diffusion facilitation. Aquaporin tetramer formation, membrane integration and disintegration could provide a mechanism for regulation of cellular CO2 exchange. The physiological importance of aquaporin mediated CO2 membrane diffusion could be shown for plants and cyanobacteria and partly for mammals. Taking the mentioned results into account, consequences for our current picture of cell membrane transport emerge. It appears that in some or many instances, membranes might not be as permeable as it was suggested by current bio-membrane models, opening an additional way of controlling the cellular influx or efflux of volatile substances like CO2. This article is part of a Special Issue entitled Aquaporins. © 2013.

The effect of physical back-diffusion of 13CO2 tracer on the coupling between photosynthesis and soil CO2 efflux in grassland.

PubMed

Burri, Susanne; Sturm, Patrick; Baur, Thomas; Barthel, Matti; Knohl, Alexander; Buchmann, Nina

2014-01-01

Pulse labelling experiments provide a common tool to study short-term processes in the plant-soil system and investigate below-ground carbon allocation as well as the coupling of soil CO(2) efflux to photosynthesis. During the first hours after pulse labelling, the measured isotopic signal of soil CO(2) efflux is a combination of both physical tracer diffusion into and out of the soil as well as biological tracer release via root and microbial respiration. Neglecting physical back-diffusion can lead to misinterpretation regarding time lags between photosynthesis and soil CO(2) efflux in grassland or any ecosystem type where the above-ground plant parts cannot be labelled in gas-tight chambers separated from the soil. We studied the effects of physical (13)CO(2) tracer back-diffusion in pulse labelling experiments in grassland, focusing on the isotopic signature of soil CO(2) efflux. Having accounted for back-diffusion, the estimated time lag for first tracer appearance in soil CO(2) efflux changed from 0 to 1.81±0.56 h (mean±SD) and the time lag for maximum tracer appearance from 2.67±0.39 to 9.63±3.32 h (mean±SD). Thus, time lags were considerably longer when physical tracer diffusion was considered. Using these time lags after accounting for physical back-diffusion, high nocturnal soil CO(2) efflux rates could be related to daytime rates of gross primary productivity (R(2)=0.84). Moreover, pronounced diurnal patterns in the δ(13)C of soil CO(2) efflux were found during the decline of the tracer over 3 weeks. Possible mechanisms include diurnal changes in the relative contributions of autotrophic and heterotrophic soil respiration as well as their respective δ(13)C values. Thus, after accounting for physical back-diffusion, we were able to quantify biological time lags in the coupling of photosynthesis and soil CO(2) efflux in grassland at the diurnal time scale.

CO2 diffusion in champagne wines: a molecular dynamics study.

PubMed

Perret, Alexandre; Bonhommeau, David A; Liger-Belair, Gérard; Cours, Thibaud; Alijah, Alexander

2014-02-20

Although diffusion is considered as the main physical process responsible for the nucleation and growth of carbon dioxide bubbles in sparkling beverages, the role of each type of molecule in the diffusion process remains unclear. In the present study, we have used the TIP5P and SPC/E water models to perform force field molecular dynamics simulations of CO2 molecules in water and in a water/ethanol mixture respecting Champagne wine proportions. CO2 diffusion coefficients were computed by applying the generalized Fick's law for the determination of multicomponent diffusion coefficients, a law that simplifies to the standard Fick's law in the case of champagnes. The CO2 diffusion coefficients obtained in pure water and water/ethanol mixtures composed of TIP5P water molecules were always found to exceed the coefficients obtained in mixtures composed of SPC/E water molecules, a trend that was attributed to a larger propensity of SPC/E water molecules to form hydrogen bonds. Despite the fact that the SPC/E model is more accurate than the TIP5P model to compute water self-diffusion and CO2 diffusion in pure water, the diffusion coefficients of CO2 molecules in the water/ethanol mixture are in much better agreement with the experimental values of 1.4 - 1.5 × 10(-9) m(2)/s obtained for Champagne wines when the TIP5P model is employed. This difference was deemed to rely on the larger propensity of SPC/E water molecules to maintain the hydrogen-bonded network between water molecules and form new hydrogen bonds with ethanol, although statistical issues cannot be completely excluded. The remarkable agreement between the theoretical CO2 diffusion coefficients obtained within the TIP5P water/ethanol mixture and the experimental data specific to Champagne wines makes us infer that the diffusion coefficient in these emblematic hydroalcoholic sparkling beverages is expected to remain roughly constant whathever their proportions in sugars, glycerol, or peptides.

Effective diffusion coefficients of gas mixture in heavy oil under constant-pressure conditions

NASA Astrophysics Data System (ADS)

Li, Huazhou Andy; Sun, Huijuan; Yang, Daoyong

2017-05-01

We develop a method to determine the effective diffusion coefficient for each individual component of a gas mixture in a non-volatile liquid (e.g., heavy oil) at high pressures with compositional analysis. Theoretically, a multi-component one-way diffusion model is coupled with the volume-translated Peng-Robinson equation of state to quantify the mass transfer between gas and liquid (e.g., heavy oil). Experimentally, the diffusion tests have been conducted with a PVT setup for one pure CO2-heavy oil system and one C3H8-CO2-heavy oil system under constant temperature and pressure, respectively. Both the gas-phase volume and liquid-phase swelling effect are simultaneously recorded during the measurement. As for the C3H8-CO2-heavy oil system, the gas chromatography method is employed to measure compositions of the gas phase at the beginning and end of the diffusion measurement, respectively. The effective diffusion coefficients are then determined by minimizing the discrepancy between the measured and calculated gas-phase composition at the end of diffusion measurement. The newly developed technique can quantify the contributions of each component of mixture to the bulk mass transfer from gas into liquid. The effective diffusion coefficient of C3H8 in the C3H8-CO2 mixture at 3945 ± 20 kPa and 293.85 K, i.e., 18.19 × 10^{ - 10} {{m}}^{ 2} / {{s}}, is found to be much higher than CO2 at 3950 ± 18 kPa and 293.85 K, i.e., 8.68 × 10^{ - 10} {{m}}^{ 2} / {{s}}. In comparison with pure CO2, the presence of C3H8 in the C3H8-CO2 mixture contributes to a faster diffusion of CO2 from the gas phase into heavy oil and consequently a larger swelling factor of heavy oil.

Swarm intelligence application for optimization of CO2 diffusivity in polystyrene-b-polybutadiene-b-polystyrene (SEBS) foaming

NASA Astrophysics Data System (ADS)

Sharudin, Rahida Wati; Ajib, Norshawalina Muhamad; Yusoff, Marina; Ahmad, Mohd Aizad

2017-12-01

Thermoplastic elastomer SEBS foams were prepared by using carbon dioxide (CO2) as a blowing agent and the process is classified as physical foaming method. During the foaming process, the diffusivity of CO2 need to be controlled since it is one of the parameter that will affect the final cellular structure of the foam. Conventionally, the rate of CO2 diffusion was measured experimentally by using a highly sensitive device called magnetic suspension balance (MSB). Besides, this expensive MSB machine is not easily available and measurement of CO2 diffusivity is quite complicated as well as time consuming process. Thus, to overcome these limitations, a computational method was introduced. Particle Swarm Optimization (PSO) is a part of Swarm Intelligence system which acts as a beneficial optimization tool where it can solve most of nonlinear complications. PSO model was developed for predicting the optimum foaming temperature and CO2 diffusion rate in SEBS foam. Results obtained by PSO model are compared with experimental results for CO2 diffusivity at various foaming temperature. It is shown that predicted optimum foaming temperature at 154.6 °C was not represented the best temperature for foaming as the cellular structure of SEBS foamed at corresponding temperature consisted pores with unstable dimension and the structure was not visibly perceived due to foam shrinkage. The predictions were not agreed well with experimental result when single parameter of CO2 diffusivity is considered in PSO model because it is not the only factor that affected the controllability of foam shrinkage. The modification on the PSO model by considering CO2 solubility and rigidity of SEBS as additional parameters needs to be done for obtaining the optimum temperature for SEBS foaming. Hence stable SEBS foam could be prepared.

Molecular Dynamics Simulations for Loading-Dependent Diffusion of CO2, SO2, CH4, and Their Binary Mixtures in ZIF-10: The Role of Hydrogen Bond.

PubMed

Li, Li; Yang, Deshuai; Fisher, Trevor R; Qiao, Qi; Yang, Zhen; Hu, Na; Chen, Xiangshu; Huang, Liangliang

2017-10-24

The loading-dependent diffusion behavior of CH 4 , CO 2 , SO 2 , and their binary mixtures in ZIF-10 has been investigated in detail by using classical molecular dynamics simulations. Our simulation results demonstrate that the self-diffusion coefficient D i of CH 4 molecules decreases sharply and monotonically with the loading while those of both CO 2 and SO 2 molecules initially display a slight increase at low uptakes and follow a slow decrease at high uptakes. Accordingly, the interaction energies between CH 4 molecules and ZIF-10 remain nearly constant regardless of the loading due to the absence of hydrogen bonds (HBs), while the interaction energies between CO 2 (or SO 2 ) and ZIF-10 decease rapidly with the loading, especially at small amounts of gas molecules. Such different loading-dependent diffusion and interaction mechanisms can be attributed to the relevant HB behavior between gas molecules and ZIF-10. At low loadings, both the number and strength of HBs between CO 2 (or SO 2 ) molecules and ZIF-10 decrease obviously as the loading increases, which is responsible for the slight increase of their diffusion coefficients. However, at high loadings, their HB strength increases with the loading. Similar loading-dependent phenomena of diffusion, interaction, and HB behavior can be observed for CH 4, CO 2 , and SO 2 binary mixtures in ZIF-10, only associated with some HB competition between CO 2 and SO 2 molecules in the case of the CO 2 /SO 2 mixture.

Evaluation of Electroplated Co-P Film as Diffusion Barrier Between In-48Sn Solder and SiC-Dispersed Bi2Te3 Thermoelectric Material

NASA Astrophysics Data System (ADS)

Li, Siyang; Yang, Donghua; Tan, Qing; Li, Liangliang

2015-06-01

The diffusion barrier property of Co-P film as a buffer layer between SiC-dispersed Bi2Te3 bulk material and In-48Sn solder was investigated. A Co-P film with thickness of ~6 µm was electroplated on SiC-dispersed Bi2Te3 substrate, joined with In-48Sn solder by a reflow process, and annealed at 100°C for up to 625 h. The formation and growth kinetics of intermetallic compounds (IMCs) at the interface between the In-48Sn and substrate were studied using transmission electron microscopy and scanning electron microscopy with energy-dispersive x-ray spectroscopy. The results showed that crystalline Co(In,Sn)3 formed as an irregular layer adjacent to the solder side at the solder/Co-P interface due to diffusion of Co towards the solder, and a small amount of amorphous Co45P13In12Sn30 appeared at the Co-P side because of diffusion of In and Sn into Co-P. The growth of Co(In,Sn)3 and Co45P13In12Sn30 during solid-state aging was slow, being controlled by interfacial reaction and diffusion, respectively. For comparison, In-48Sn/Bi2Te3-SiC joints were prepared and the IMCs in the joints analyzed. Without a diffusion barrier, In penetrated rapidly into the substrate, which led to the formation of amorphous In x Bi y phase in crystalline In4Te3 matrix. These IMCs grew quickly with prolongation of the annealing time, and their growth was governed by volume diffusion of elements. The experimental data demonstrate that electroplated Co-P film is an effective diffusion barrier for use in Bi2Te3-based thermoelectric modules.

Diurnal variability of CO2 and CH4 emissions from tropical reservoirs

NASA Astrophysics Data System (ADS)

Linkhorst, Annika; Reinaldo Paranaíba, José; Barros, Nathan; DelSontro, Tonya; Isidorova, Anastasija; Mendonça, Raquel; Sobek, Sebastian

2017-04-01

Reservoirs are important atmospheric sources of carbon dioxide (CO2) and methane (CH4) with CH4 being a greenhouse gas (GHG) at least 28 times more potent than CO2. Reservoir GHG emissions tend to be heterogeneous, however, and thus current emission estimates are likely conservative since they often overlook emission hot spots and hot moments, especially for CH4 ebullition. For CO2, diffusion is the dominant flux pathway, and diurnal patterns in CO2 emissions can largely be linked to photosynthesis. In contrast, ebullition, the release of gases through bubbles that are formed in the sediments and travel through the water column, is a major emission pathway for CH4 in shallow waters. We visually observed a change in quantity and size of bubbles at different times of the day, and therefore conducted a diurnal study in four different Brazilian reservoirs of different size, age, climatic and geographic characteristics. We hypothesized that sub-daily trends in CH4 ebullition occur in Brazilian reservoirs as bubble release depends on physical factors such as turbulence and hydrostatic pressure, which can exhibit sub-daily patterns in large, managed reservoirs. In each reservoir, we performed measurements of CO2 and CH4 fluxes at one location over 24 hours. CH4 ebullition was tracked continuously by an echosounder, and 13 anchored bubble traps per reservoir were sampled every three hours. Further, a custom-built equilibrator monitored dissolved CH4 and CO2 concentrations, and diffusive and total fluxes of CO2 and CH4 were measured using floating chambers in triplicates every 30 minutes during the same period. We observed that CH4 ebullition as well as CH4 and CO2 diffusion peaked during the day, with peak fluxes being up to four times higher than low fluxes. However, the exact timing and magnitude varied for the different sampling events, and could in part be linked to biological and physical properties of the respective reservoir. This study combined different state-of-the-art techniques to show, for the first time, short-scale temporal variability for both diffusion and ebullition of CO2 and CH4 in different tropical reservoirs. It shows substantial and non-negligable diurnal variability in GHG emission from tropical reservoirs. Further studies are needed to find out if the pattern of low flux during night needs to be accounted for in estimations of GHG emission from reservoirs.

Methane and carbon dioxide emissions from 40 lakes along a north–south latitudinal transect in Alaska

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

Sepulveda-Jauregui, A.; Walter Anthony, K. M.; Martinez-Cruz, K.

Uncertainties in the magnitude and seasonality of various gas emission modes, particularly among different lake types, limit our ability to estimate methane (CH 4) and carbon dioxide (CO 2) emissions from northern lakes. Here we assessed the relationship between CH 4 and CO 2 emission modes in 40 lakes along a latitudinal transect in Alaska to physicochemical limnology and geographic characteristics, including permafrost soil type surrounding lakes. Emission modes included Direct Ebullition, Diffusion, Storage flux, and a newly identified Ice-Bubble Storage (IBS) flux. We found that all lakes were net sources of atmospheric CH 4 and CO 2, but themore » climate warming impact of lake CH 4 emissions was two times higher than that of CO 2. Ebullition and Diffusion were the dominant modes of CH 4 and CO 2 emissions respectively. IBS, ~ 10% of total annual CH 4 emissions, is the release to the atmosphere of seasonally ice-trapped bubbles when lake ice confining bubbles begins to melt in spring. IBS, which has not been explicitly accounted for in regional studies, increased the estimate of springtime emissions from our study lakes by 320%. Geographically, CH 4 emissions from stratified, dystrophic interior Alaska thermokarst (thaw) lakes formed in icy, organic-rich yedoma permafrost soils were 6-fold higher than from non-yedoma lakes throughout the rest of Alaska. Total CH 4 emission was correlated with concentrations of phosphate and total nitrogen in lake water, Secchi depth and lake area, with yedoma lakes having higher nutrient concentrations, shallower Secchi depth, and smaller lake areas. Our findings suggest that permafrost type plays important roles in determining CH 4 emissions from lakes by both supplying organic matter to methanogenesis directly from thawing permafrost and by enhancing nutrient availability to primary production, which can also fuel decomposition and methanogenesis.« less

Methane and carbon dioxide emissions from 40 lakes along a north–south latitudinal transect in Alaska

DOE PAGES

Sepulveda-Jauregui, A.; Walter Anthony, K. M.; Martinez-Cruz, K.; ...

2014-09-12

Uncertainties in the magnitude and seasonality of various gas emission modes, particularly among different lake types, limit our ability to estimate methane (CH 4) and carbon dioxide (CO 2) emissions from northern lakes. Here we assessed the relationship between CH 4 and CO 2 emission modes in 40 lakes along a latitudinal transect in Alaska to physicochemical limnology and geographic characteristics, including permafrost soil type surrounding lakes. Emission modes included Direct Ebullition, Diffusion, Storage flux, and a newly identified Ice-Bubble Storage (IBS) flux. We found that all lakes were net sources of atmospheric CH 4 and CO 2, but themore » climate warming impact of lake CH 4 emissions was two times higher than that of CO 2. Ebullition and Diffusion were the dominant modes of CH 4 and CO 2 emissions respectively. IBS, ~ 10% of total annual CH 4 emissions, is the release to the atmosphere of seasonally ice-trapped bubbles when lake ice confining bubbles begins to melt in spring. IBS, which has not been explicitly accounted for in regional studies, increased the estimate of springtime emissions from our study lakes by 320%. Geographically, CH 4 emissions from stratified, dystrophic interior Alaska thermokarst (thaw) lakes formed in icy, organic-rich yedoma permafrost soils were 6-fold higher than from non-yedoma lakes throughout the rest of Alaska. Total CH 4 emission was correlated with concentrations of phosphate and total nitrogen in lake water, Secchi depth and lake area, with yedoma lakes having higher nutrient concentrations, shallower Secchi depth, and smaller lake areas. Our findings suggest that permafrost type plays important roles in determining CH 4 emissions from lakes by both supplying organic matter to methanogenesis directly from thawing permafrost and by enhancing nutrient availability to primary production, which can also fuel decomposition and methanogenesis.« less

Diffuse volcanic emissions of carbon dioxide from Vulcano Island, Italy.

PubMed

Baubron, J C; Allard, P; Toutain, J P

1990-03-01

RECENT investigations on Mount Etna (Sicily)(1-3) have revealed that volcanoes may release abundant carbon dioxide not only from their active craters, but also from their flanks, as diffuse soil emanations. Here we present analyses of soil gases and air in water wells on Vulcano Island which provide further evidence of such lateral degassing. Nearly pure carbon dioxide, enriched in helium and radon, escapes from the slopes of the Fossa active cone, adding a total output of 30 tonnes per day to the fumarolic crater discharge ( 180 tonnes CO(2) per day). This emanation has similar He/CO(2) and (13)C/(12)C ratios to those of the crater fumaroles (300%ndash;500 degrees C) and therefore a similar volcanic origin. Gases rich in carbon dioxide also escape at sea level along the isthmus between the Fossa and Vulcanello volcanic cones, but their depletion in both He and (13)C suggests a distinct source. Diffuse volcanic gas emanations, once their genetic link with central fumarole degassing has been demonstrated, can be used for continuous volcano monitoring, at safe distances from active craters. Such monitoring has been initiated at Vulcano, where soil and well emanations of nearly pure CO(2) themselves represent a threat to the local population.

Short-term variations of diffuse CO2 emission from the summit crater of Teide volcano, Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Melián, Gladys V.; Ocampo, Stephany; Nisbet, Andrew; McKnight, Samara; Monzón, Tania; Asensio-Ramos, María; Alonso, Mar; Rodríguez, Fátima; García-Merino, Marta; Amonte, Cecilia; Pérez, Nemesio M.

2017-04-01

Teide volcano in Tenerife, Canary Islands, is characterized by the presence of a weak fumarolic system, steamy ground, and high rates of diffuse CO2 degassing all around this area. The temperature of the fumaroles (83˚ C) corresponds to the boiling point of water at discharge conditions. Previous diffuse CO2 surveys have shown to be an important tool to detect early warnings of possible impending volcanic unrests at Tenerife Island (Melián et al., 2012; Pérez et al., 2013). During June, July and August 2016, twelve soil gas surveys were performed at the summit crater of Teide volcano in order to evaluate short-term variations of diffuse CO2 degassing pattern. Soil CO2 efflux and soil temperature were always measured at the same 38 observation sites homogeneously distributed within an area of about 6,972 m2 inside the summit crater. Soil CO2 diffuse effluxes were estimated according to the accumulation chamber method and using a non-dispersive infrared (NDIR) LICOR-820 CO2analyzer. Soil CO2 efflux values presented a range from non-detectable (˜0.5 gṡm-2ṡd-1) to 10.8 kgṡm-2ṡd-1, with an average value of 2.7 kgṡm-2ṡd-1, while soil temperature ranged from 13.1 to 83.6˚ C with a mean value of 55.6˚ C. Sequential Gaussian simulations (sGs) were used for mapping and estimate the volcanic diffuse CO2 emission at each survey. The highest values of diffuse CO2 efflux were measured along the east (>8 kgṡm-2ṡd-1) and west (>5 kgṡm-2ṡd-1) sectors of the crater. Areas with highest diffuse CO2 effluxes were also characterized by a relatively high soil temperature (>60˚ C) and by an intense hydrothermal alteration. Weekly diffuse CO2 emission variations from the summit crater during the study period showed a range between 13.5 and 24.7 tṡd-1 with an average value of 18.9 tṡd-1. During these 3 months, the seismic activity rate was about 10 seismic events per month registered by the Instituto Geográfico Nacional (IGN; http://www.ign.es). We compared these observed weekly variations with monthly variations of a longer period with similar seismic rate such as 2014 (about 8 seismic events per month, and values ranged from 15.6 to 22.4 tṡd-1, and an average value of 19.0 tṡd-1. These values are in the same order than the observed during our study. However, for a longer period of observation, from 1999 to 2010, diffuse CO2 emission rates varied from 2.2 to 36.3 tṡd-1, with a mean value of 15.7 tṡd-1 (Melián et al., 2012). The long-term variations observed in the diffuse CO2 emission rates during this period of 10 years were significantly higher than short-term variations observed in the period of study. It is also important to note that the volcanic-seismic crisis of 2004 occurred with an increase on the CO2 emission from Teide summit crater (Melián et al., 2012). This study shows that during periods of seismic tranquility, diffuse CO2 emission rates will not suffer significant variations, whether performed on a weekly or monthly basis. References: Melián et al., 2012. Bull. Volcanol. DOI 10.1007/s00445-012-0613-1 Pérez et al., 2013. J. Geol. Soc. DOI 10.1144/jgs2012-125 .

First principles studies of structure stability and lithium intercalation of ZnCo2 O4

NASA Astrophysics Data System (ADS)

Zhang, Yanning; Liu, Weiwei; Beijing Computational Science Research Center Team

Among the metal oxides, which are the most widely investigated alternative anodes for use in lithium ion batteries (LIBs), binary and ternary transition metal oxides have received special attention due to their high capacity values. ZnCo2O4 is a promising candidate as anode for LIB, and one can expect a total capacity corresponding to 7.0 - 8.33 mol of recyclable Li per mole of ZnCo2O4. Here we studied the structural stability, electronic properties, lithium intercalation and diffusion barrier of ZnCo2O4 through density functional calculations. The calculated structural and energetic parameters are comparable with experiments. Our theoretical studies provide insights in understanding the mechanism of lithium ion displacement reactions in this ternary metal oxide.

First principles calculations of stability and lithium intercalation potentials of ZnCo2O4

NASA Astrophysics Data System (ADS)

Yu, L. C.; Wu, J.; Liu, H.; Zhang, Y. N.

2015-03-01

Among the metal oxides, which are the most widely investigated alternative anodes for use in lithium ion batteries (LIBs), binary and ternary tin oxides have received special attention due to their high capacity values. ZnCo2O4 is a promising candidate as the anode material for LIB, and one can expect a total capacity corresponding to 7.0 - 8.33 mol of recyclable Li per mole of ZnCo2O4. Here we studied the structural stability, electronic properties, diffusion barrier and lithium intercalation potentials of ZnCo2O4 through density functional calculations. The calculated structural and energetic parameters are comparable with experiments. Our DFT studies provide insights in understanding the mechanism of lithium ion displacement reactions in this ternary metal oxide.

Selectivity and self-diffusion of CO2 and H2 in a mixture on a graphite surface

PubMed Central

Trinh, Thuat T.; Vlugt, Thijs J. H.; Hägg, May-Britt; Bedeaux, Dick; Kjelstrup, Signe

2013-01-01

We performed classical molecular dynamics (MD) simulations to understand the mechanism of adsorption from a gas mixture of CO2 and H2 (mole fraction of CO2 = 0.30) and diffusion along a graphite surface, with the aim to help enrich industrial off-gases in CO2, separating out H2. The temperature of the system in the simulation covered typical industrial conditions for off-gas treatment (250–550 K). The interaction energy of single molecules CO2 or H2 on graphite surface was calculated with classical force fields (FFs) and with Density Functional Theory (DFT). The results were in good agreement. The binding energy of CO2 on graphite surface is three times larger than that of H2. At lower temperatures, the selectivity of CO2 over H2 is five times larger than at higher temperatures. The position of the dividing surface was used to explain how the adsorption varies with pore size. In the temperature range studied, the self-diffusion coefficient of CO2 is always smaller than of H2. The temperature variation of the selectivities and the self-diffusion coefficient imply that the carbon molecular sieve membrane can be used for gas enrichment of CO2. PMID:24790965

Biomass hydrolysis inhibition at high hydrogen partial pressure in solid-state anaerobic digestion.

PubMed

Cazier, E A; Trably, E; Steyer, J P; Escudie, R

2015-08-01

In solid-state anaerobic digestion, so-called ss-AD, biogas production is inhibited at high total solids contents. Such inhibition is likely caused by a slow diffusion of dissolved reaction intermediates that locally accumulate. In this study, we investigated the effect of H2 and CO2 partial pressure on ss-AD. Partial pressure of H2 and/or CO2 was artificially fixed, from 0 to 1 557mbars for H2 and from 0 to 427mbars for CO2. High partial pressure of H2 showed a significant effect on methanogenesis, while CO2 had no impact. At high [Formula: see text] , the overall substrate degradation decreased with no accumulation of metabolites from acidogenic bacteria, indicating that the hydrolytic activity was specifically impacted. Interestingly, such inhibition did not occur when CO2 was added with H2. This result suggests that CO2 gas transfer is probably a key factor in ss-AD from biomass. Copyright © 2015 Elsevier Ltd. All rights reserved.

Impact of mesophyll diffusion on estimated global land CO 2 fertilization

DOE PAGES

Sun, Ying; Gu, Lianhong; Dickinson, Robert E.; ...

2014-10-13

In C 3 plants, CO 2 concentrations drop considerably along mesophyll diffusion pathways from substomatal cavities to chloroplasts where CO 2 assimilation occurs. Global carbon cycle models have not explicitly represented this internal drawdown and so overestimate CO 2 available for carboxylation and underestimate photosynthetic responsiveness to atmospheric CO 2. An explicit consideration of mesophyll diffusion increases the modeled cumulative CO 2 fertilization effect (CFE) for global gross primary production (GPP) from 915 PgC to 1057 PgC for the period of 1901 to 2010. This increase represents a 16% correction, large enough to explain the persistent overestimation of growth ratesmore » of historical atmospheric CO 2 by Earth System Models. Without this correction, the CFE for global GPP is underestimated by 0.05 PgC yr -1ppm -1. This finding implies that the contemporary terrestrial biosphere is more CO 2-limited than previously thought.« less

Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

2015-10-01

Fuel flexibility is a significant advantage of solid oxide fuel cell (SOFC). A comprehensive macroscopic framework is proposed for synthesis gas (syngas) fueled electrochemistry and transport in SOFC anode with two main novelties, i.e. analytical H2/CO electrochemical co-oxidation, and correction of gas species concentration at triple phase boundary considering competitive absorption and surface diffusion. Staring from analytical approximation of the decoupled charge and mass transfer, we present analytical solutions of two defined variables, i.e. hydrogen current fraction and enhancement factor. Giving explicit answer (rather than case-by-case numerical calculation) on how many percent of the current output contributed by H2 or CO and on how great the water gas shift reaction plays role on, this approach establishes at the first time an adaptive superposition mechanism of H2-fuel and CO-fuel electrochemistry for syngas fuel. Based on the diffusion equivalent circuit model, assuming series-connected resistances of surface diffusion and bulk diffusion, the model predicts well at high fuel utilization by keeping fixed porosity/tortuosity ratio. The model has been validated by experimental polarization behaviors in a wide range of operation on a button cell for H2-H2O-CO-CO2-N2 fuel systems. The framework could be helpful to narrow the gap between macro-scale and meso-scale SOFC modeling.

Atmospheric inversion of the surface CO2 flux with 13CO2 constraint

NASA Astrophysics Data System (ADS)

Chen, J. M.; Mo, G.; Deng, F.

2013-10-01

Observations of 13CO2 at 73 sites compiled in the GLOBALVIEW database are used for an additional constraint in a global atmospheric inversion of the surface CO2 flux using CO2 observations at 210 sites for the 2002-2004 period for 39 land regions and 11 ocean regions. This constraint is implemented using the 13CO2/CO2 flux ratio modeled with a terrestrial ecosystem model and an ocean model. These models simulate 13CO2 discrimination rates of terrestrial photosynthesis and respiration and ocean-atmosphere diffusion processes. In both models, the 13CO2 disequilibrium between fluxes to and from the atmosphere is considered due to the historical change in atmospheric 13CO2 concentration. For the 2002-2004 period, the 13CO2 constraint on the inversion increases the total land carbon sink from 3.40 to 3.70 Pg C yr-1 and decreases the total oceanic carbon sink from 1.48 to 1.12 Pg C yr-1. The largest changes occur in tropical areas: a considerable decrease in the carbon source in the Amazon forest, and this decrease is mostly compensated by increases in the ocean region immediately west of the Amazon and the southeast Asian land region. Our further investigation through different treatments of the 13CO2/CO2 flux ratio used in the inversion suggests that variable spatial distributions of the 13CO2 isotopic discrimination rate simulated by the models over land and ocean have considerable impacts on the spatial distribution of the inverted CO2 flux over land and the inversion results are not sensitive to errors in the estimated disequilibria over land and ocean.

Effect of sorbed methanol, current, and temperature on multicomponent transport in nafion-based direct methanol fuel cells.

PubMed

Rivera, Harry; Lawton, Jamie S; Budil, David E; Smotkin, Eugene S

2008-07-24

The CO2 in the cathode exhaust of a liquid feed direct methanol fuel cell (DMFC) has two sources: methanol diffuses through the membrane electrode assembly (MEA) to the cathode where it is catalytically oxidized to CO2; additionally, a portion of the CO2 produced at the anode diffuses through the MEA to the cathode. The potential-dependent CO2 exhaust from the cathode was monitored by online electrochemical mass spectrometry (ECMS) with air and with H2 at the cathode. The precise determination of the crossover rates of methanol and CO2, enabled by the subtractive normalization of the methanol/air to the methanol/H2 ECMS data, shows that methanol decreases the membrane viscosity and thus increases the diffusion coefficients of sorbed membrane components. The crossover of CO2 initially increases linearly with the Faradaic oxidation of methanol, reaches a temperature-dependent maximum, and then decreases. The membrane viscosity progressively increases as methanol is electrochemically depleted from the anode/electrolyte interface. The crossover maximum occurs when the current dependence of the diffusion coefficients and membrane CO2 solubility dominate over the Faradaic production of CO2. The plasticizing effect of methanol is corroborated by measurements of the rotational diffusion of TEMPONE (2,2,6,6-tetramethyl-4-piperidone N-oxide) spin probe by electron spin resonance spectroscopy. A linear inverse relationship between the methanol crossover rate and current density confirms the absence of methanol electro-osmotic drag at concentrations relevant to operating DMFCs. The purely diffusive transport of methanol is explained in terms of current proton solvation and methanol-water incomplete mixing theories.

Markov-state model for CO2 binding with carbonic anhydrase under confinement

NASA Astrophysics Data System (ADS)

Chen, Gong; Xu, Weina; Lu, Diannan; Wu, Jianzhong; Liu, Zheng

2018-01-01

Enzyme immobilization with a nanostructure material can enhance its stability and facilitate reusability. However, the apparent activity is often compromised due to additional diffusion barriers and complex interactions with the substrates and solvent molecules. The present study elucidates the effects of the surface hydrophobicity of nano-confinement on CO2 diffusion to the active site of human carbonic anhydrase II (CA), an enzyme that is able to catalyze CO2 hydration at extremely high turnover rates. Using the Markov-state model in combination with coarse-grained molecular dynamics simulations, we demonstrate that a hydrophobic cage increases CO2 local density but hinders its diffusion towards the active site of CA under confinement. By contrast, a hydrophilic cage hinders CO2 adsorption but promotes its binding with CA. An optimal surface hydrophobicity can be identified to maximize both the CO2 occupation probability and the diffusion rate. The simulation results offer insight into understanding enzyme performance under nano-confinement and help us to advance broader applications of CA for CO2 absorption and recovery.

High CO2 emissions through porous media: Transport mechanisms and implications for flux measurement and fractionation

USGS Publications Warehouse

Evans, William C.; Sorey, M.L.; Kennedy, B.M.; Stonestrom, David A.; Rogie, J.D.; Shuster, D.L.

2001-01-01

Diffuse emissions of CO2 are known to be large around some volcanoes and hydrothermal areas. Accumulation-chamber measurements of CO2 flux are increasingly used to estimate the total magmatic or metamorphic CO2 released from such areas. To assess the performance of accumulation chamber systems at fluxes one to three orders of magnitude higher than normally encountered in soil respiration studies, a test system was constructed in the laboratory where known fluxes could be maintained through dry sand. Steady-state gas concentration profiles and fractionation effects observed in the 30-cm sand column nearly match those predicted by the Stefan-Maxwell equations, indicating that the test system was functioning successfully as a uniform porous medium. Eight groups of investigators tested their accumulation chamber equipment, all configured with continuous infrared gas analyzers (IRGA), in this system. Over a flux range of ~ 200-12,000 g m-2 day-1, 90% of their 203 flux measurements were 0-25% lower than the imposed flux with a mean difference of - 12.5%. Although this difference would seem to be within the range of acceptability for many geologic investigations, some potential sources for larger errors were discovered. A steady-state pressure gradient of -20 Pa/m was measured in the sand column at a flux of 11,200 g m-2 day-1. The derived permeability (50 darcies) was used in the dusty-gas model (DGM) of transport to quantify various diffusive and viscous flux components. These calculations were used to demonstrate that accumulation chambers, in addition to reducing the underlying diffusive gradient, severely disrupt the steady-state pressure gradient. The resultant diversion of the net gas flow is probably responsible for the systematically low flux measurements. It was also shown that the fractionating effects of a viscous CO2 efflux against a diffusive influx of air will have a major impact on some important geochemical indicators, such as N2/Ar, ??15N-N2, and 4He/22Ne. Published by Elsevier Science B.V.

Measurement of diffusion coefficients important in modeling the absorption rate of carbon dioxide into aqueous N-methyldiethanolamine

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

Rowley, R.L.; Adams, M.E.; Marshall, T.L.

1997-03-01

Natural gas processors use amine treating processes to remove the acid gases H{sub 2}S and CO{sub 2} from gas streams. Absorption rates of gaseous CO{sub 2} into aqueous N-methyldiethanolamine (MDEA) solutions were measured in a quiescent, inverted-tube diffusiometer by monitoring the rate of pressure drop. The absorption rate was found to be insensitive to the diffusion coefficient of CO{sub 2} in solution but very sensitive to the diffusion rate of bicarbonate and protonated MDEA ions. Evidence also suggested that chemical reaction equilibrium is rapid relative to diffusion. A numerical model was developed on the basis of these observations. The modelmore » was used to regress diffusion coefficients of bicarbonate and protonated amine, which must be equivalent by electroneutrality arguments, from measured absorption rates. Complete modeling of the absorption process also required data for the diffusion coefficient of MDEA in water. These were measured using a Taylor dispersion apparatus. CO{sub 2} absorption rates and diffusion coefficients of bicarbonate and protonated MDEA were obtained at 298.2 K and 318.2 K in solutions containing 20, 35, and 50 mass % MDEA in water.« less

Adsorption, dissociation and diffusion of hydrogen on the ZrCo surface and subsurface: A comprehensive study using first principles approach

NASA Astrophysics Data System (ADS)

Chattaraj, D.; Kumar, Nandha; Ghosh, Prasenjit; Majumder, C.; Dash, Smruti

2017-11-01

With increasing demand for hydrogen economy driven world, the fundamental research of hydrogen-metal interactions has gained momentum. In this work we report a systematic theoretical study of the stability of different surfaces of intermetallic ZrCo that is a possible candidate as a getter bed for tritium. Our first principles ab initio thermodynamic calculations predict that amongst the (100), (110) and (111) surfaces, the stoichiometric (110) surface is the most stable one over a wide range of Co chemical potential. We have also studied adsorption, dissociation and diffusion of hydrogen on the (110) surface. On the basis of total energy, it is seen that adsorption of molecular hydrogen (H2) on the surface is much weaker than atomic hydrogen. The H2 decomposition on ZrCo surface can easily take place and the dissociation barrier is calculated to be 0.70 eV. The strength of binding of H atom on the surface is more or less independent of surface coverage till 1.0 ML of H. The thermodynamic stability of atomic H adsorbed on the surface, in subsurface and bulk decreases from surface to bulk to subsurface. Though the H atoms are mobile on the surface, their diffusion to the subsurface involves a barrier of about 0.79 eV.

Explaining CO2 fluctuations observed in snowpacks

NASA Astrophysics Data System (ADS)

Graham, Laura; Risk, David

2018-02-01

Winter soil carbon dioxide (CO2) respiration is a significant and understudied component of the global carbon (C) cycle. Winter soil CO2 fluxes can be surprisingly variable, owing to physical factors such as snowpack properties and wind. This study aimed to quantify the effects of advective transport of CO2 in soil-snow systems on the subdiurnal to diurnal (hours to days) timescale, use an enhanced diffusion model to replicate the effects of CO2 concentration depletions from persistent winds, and use a model-measure pairing to effectively explore what is happening in the field. We took continuous measurements of CO2 concentration gradients and meteorological data at a site in the Cape Breton Highlands of Nova Scotia, Canada, to determine the relationship between wind speeds and CO2 levels in snowpacks. We adapted a soil CO2 diffusion model for the soil-snow system and simulated stepwise changes in transport rate over a broad range of plausible synthetic cases. The goal was to mimic the changes we observed in CO2 snowpack concentration to help elucidate the mechanisms (diffusion, advection) responsible for observed variations. On subdiurnal to diurnal timescales with varying winds and constant snow levels, a strong negative relationship between wind speed and CO2 concentration within the snowpack was often identified. Modelling clearly demonstrated that diffusion alone was unable to replicate the high-frequency CO2 fluctuations, but simulations using above-atmospheric snowpack diffusivities (simulating advective transport within the snowpack) reproduced snow CO2 changes of the observed magnitude and speed. This confirmed that wind-induced ventilation contributed to episodic pulsed emissions from the snow surface and to suppressed snowpack concentrations. This study improves our understanding of winter CO2 dynamics to aid in continued quantification of the annual global C cycle and demonstrates a preference for continuous wintertime CO2 flux measurement systems.

Interannual variability in the atmospheric CO2 rectification over a boreal forest region

NASA Astrophysics Data System (ADS)

Chen, Baozhang; Chen, Jing M.; Worthy, Douglas E. J.

2005-08-01

Ecosystem CO2 exchange with the atmosphere and the planetary boundary layer (PBL) dynamics are correlated diurnally and seasonally. The strength of this kind of covariation is quantified as the rectifier effect, and it affects the vertical gradient of CO2 and thus the global CO2 distribution pattern. An 11-year (1990-1996, 1999-2002), continuous CO2 record from Fraserdale, Ontario (49°52'29.9″N, 81°34'12.3″W), along with a coupled vertical diffusion scheme (VDS) and ecosystem model named Boreal Ecosystem Productivity Simulator (BEPS), are used to investigate the interannual variability of the rectifier effect over a boreal forest region. The coupled model performed well (r2 = 0.70 and 0.87, at 40 m at hourly and daily time steps, respectively) in simulating CO2 vertical diffusion processes. The simulated annual atmospheric rectifier effect varies from 3.99 to 5.52 ppm, while the diurnal rectifying effect accounted for about a quarter of the annual total (22.8˜28.9%).The atmospheric rectification of CO2 is not simply influenced by terrestrial source and sink strengths, but by seasonal and diurnal variations in the land CO2 flux and their interaction with PBL dynamics. Air temperature and moisture are found to be the dominant climatic factors controlling the rectifier effect. The annual rectifier effect is highly correlated with annual mean temperature (r2 = 0.84), while annual mean air relative humidity can explain 51% of the interannual variation in rectification. Seasonal rectifier effect is also found to be more sensitive to climate variability than diurnal rectifier effect.

Monitoring fugitive CH4 and CO2 emissions from a closed landfill at Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Asensio-Ramos, María; Tompkins, Mitchell R. K.; Turtle, Lara A. K.; García-Merino, Marta; Amonte, Cecilia; Rodrígez, Fátima; Padrón, Eleazar; Melián, Gladys V.; Padilla, Germán; Barrancos, José; Pérez, Nemesio M.

2017-04-01

Solid waste must be managed systematically to ensure environmental best practices. One of the ways to manage this huge problem is to systematic dispose waste materials in locations such as landfills. However, landfills could face possible threats to the environment such as groundwater pollution and the release of landfill gases (CH4, volatile organic compounds, etc.) to the atmosphere. These structures should be carefully filled, monitored and maintained while they are active and for up to 30 years after they are closed. Even after years of being closed, a systematically amount of landfill gas could be released to the atmosphere through its surface in a diffuse and fugitive form. During the period 1999-2016, we have studied the spatial-temporal distribution of the surface fugitive emission of CO2 and CH4 into the atmosphere in a cell in the Arico's municipal landfill (0.3 km2) at Tenerife, Canary Islands, Spain. This cell was operative until 2004, when it was filled and closed. Monitoring these diffuse landfill emissions provides information of how the closed landfill is degassing. To do so, we have performed 9 gas emission surveys during the period 1999-2016. Surface landfill CO2 efflux measurements were carried out at around 450 sampling site by means of a portable non-dispersive infrared spectrophotometer (NDIR) model LICOR Li800 following the accumulation chamber method. Landfill gases taken in the chamber were analyzed using a double channel VARIAN 4900 micro-GC. CH4 efflux measurements were computed combining CO2 efflux measurements and CH4/CO2 ratio in the landfill's surface gas. To quantify the total CH4 emission, CH4 efflux contour map was constructed using sequential Gaussian simulation (sGs) as interpolation method. In general, a decrease in the CO2 emission is observed since the cell was closed (2004) to the present. The total CO2 and CH4 diffuse emissions estimated in the 2016 survey were 4.54 ± 0.14 t d-1 and 268.65 ± 17.99 t d-1, respectively. These types of studies provide knowledge of how a landfill degasses and serves to public and private entities to establish effective systems for extraction of biogas. This aims not only to achieve higher levels of controlled gas release from landfills resulting in a higher level of energy production but also will contribute to minimize air pollution caused by them.

Diffusivity of Carbon Dioxide in Aqueous Solutions under Geologic Carbon Sequestration Conditions.

PubMed

Perera, Pradeep N; Deng, Hang; Schuck, P James; Gilbert, Benjamin

2018-04-26

Accurate assessment of the long-term security of geologic carbon sequestration requires knowledge of the mobility of carbon dioxide in brines under pressure and temperature conditions that prevail in subsurface aquifers. Here, we report Raman spectroscopic measurements of the rate of CO 2 diffusion in water and brines as a function of pressure, salinity, and concentration of CO 2 . In pure water at 50 ± 2 °C and 90 ± 2 bar, we find the diffusion coefficient, D, to be (3.08 ± 0.03) × 10 -9 m 2 /s, a value that is consistent with a recent microfluidic study but lower than earlier PVT measurements. Under reservoir conditions, salinity affects the mobility of CO 2 significantly and D decreased by 45% for a 4 M solution of NaCl. We find significant differences of diffusivity of CO 2 in brines (0-4 M NaCl), in both the absolute values and the trend compared to the Stokes-Einstein prediction under our experimental conditions. We observe that D decreases significantly at the high CO 2 concentrations expected in subsurface aquifers (∼15% reduction at 0.55 mol/kg of CO 2 ) and provides an empirical correction to the commonly reported D values that assume a tracer concentration dependence on diffusivity.

Atomistic simulations of CO2 and N2 within cage-type silica zeolites.

PubMed

Madison, Lindsey; Heitzer, Henry; Russell, Colin; Kohen, Daniela

2011-03-01

The behavior of CO(2) and N(2), both as single components and as binary mixtures, in two cage-type silica zeolites was studied using atomistic simulations. The zeolites considered, ITQ-3 and paradigm cage-type zeolite ZK4 (the all-silica analog of LTA), were chosen so that the principles illustrated can be generalized to other adsorbent/adsorbate systems with similar topology and types of interactions. N(2) was chosen both because of the potential uses of N(2)/CO(2) separations and because it differs from CO(2) most significantly in the magnitude of its Coulombic interactions with zeolites. Despite similarities between N(2) and CO(2) diffusion in other materials, we show here that the diffusion of CO(2) within cage-type zeolites is dominated by an energy barrier to diffusion located at the entrance to the narrow channels connecting larger cages. This barrier originates in Coulombic interactions between zeolites and CO(2)'s quadrupole and results in well-defined orientations for the diffusing molecules. Furthermore, CO(2)'s favorable electrostatic interactions with the zeolite framework result in preferential binding in the windows between cages. N(2)'s behavior, in contrast, is more consistent with that of molecules previously studied. Our analysis suggests that CO(2)'s behavior might be common for adsorbates with quadrupoles that interact strongly with a material that has narrow windows between cages.

Molecular clouds without detectable CO

NASA Technical Reports Server (NTRS)

Blitz, Leo; Bazell, David; Desert, F. Xavier

1990-01-01

The clouds identified by Desert, Bazell, and Boulanger (DBB clouds) in their search for high-latitude molecular clouds were observed in the CO (J = 1-0) line, but only 13 percent of the sample was detected. The remaining 87 percent are diffuse molecular clouds with CO abundances of about 10 to the -6th, a typical value for diffuse clouds. This hypothesis is shown to be consistent with Copernicus data. The DBB clouds are shown to ben an essentially complete catalog of diffuse molecular clouds in the solar vicinity. The total molecular surface density in the vicinity of the sun is then only about 20 percent greater than the 1.3 solar masses/sq pc determined by Dame et al. (1987). Analysis of the CO detections indicates that there is a sharp threshold in extinction of 0.25 mag before CO is detectable and is derived from the IRAS I(100) micron threshold of 4 MJy/sr. This threshold is presumably where the CO abundance exhibits a sharp increase

Molecular clouds without detectable CO

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

Blitz, L.; Bazell, D.; Desert, F.X.

1990-03-01

The clouds identified by Desert, Bazell, and Boulanger (DBB clouds) in their search for high-latitude molecular clouds were observed in the CO (J = 1-0) line, but only 13 percent of the sample was detected. The remaining 87 percent are diffuse molecular clouds with CO abundances of about 10 to the -6th, a typical value for diffuse clouds. This hypothesis is shown to be consistent with Copernicus data. The DBB clouds are shown to be an essentially complete catalog of diffuse molecular clouds in the solar vicinity. The total molecular surface density in the vicinity of the sun is thenmore » only about 20 percent greater than the 1.3 solar masses/sq pc determined by Dame et al. (1987). Analysis of the CO detections indicates that there is a sharp threshold in extinction of 0.25 mag before CO is detectable and is derived from the IRAS I(100) micron threshold of 4 MJy/sr. This threshold is presumably where the CO abundance exhibits a sharp increase 18 refs.« less

Thermal analysis of a diffusion bonded Er3+,Yb3+:glass/Co2+: MgAl2O4 microchip lasers

NASA Astrophysics Data System (ADS)

Belghachem, Nabil; Mlynczak, Jaroslaw; Kopczynski, krzysztof; Mierczyk, Zygmunt; Gawron, Michal

2016-10-01

The analysis of thermal effects in a diffusion bonded Er3+,Yb3+:glass/Co2+:MgAl2O4 microchip laser is presented. The analysis is performed for both wavelengths at 940 nm and at 975 nm as well as for two different sides of pumping, glass side and saturable absorber side. The heat sink effect of Co2+:MgAl2O4, as well as the impact of the thermal expansion and induced stress on the diffusion bonding are emphasised. The best configurations for reducing the temperature peaks, the Von Mises stresses on the diffusion bonding, and the thermal lensing are determined.

Horizon Partitioning of Soil CO2 Sources and their Isotopic Composition (13C) in a Pinus Sylvestris Stand

NASA Astrophysics Data System (ADS)

Goffin, S.; Parent, F.; Plain, C.; Maier, M.; Schack-Kirchner, H.; Aubinet, M.; Longdoz, B.

2012-12-01

The overall aim of this study is to contribute to a better understanding of mechanisms behind soil CO2 efflux using carbon stable isotopes. The approach combines a soil multilayer analysis and the isotopic tool in an in situ study. The specific goal of this work is to quantify the origin and the determinism of 13CO2 and 12CO2 production processes in the different soil layers using the gradient-efflux approach. To meet this, the work includes an experimental setup and a modeling approach. The experimental set up (see also communication of Parent et al., session B008) comprised a combination of different systems, which were installed in a Scot Pine temperate forest at the Hartheim site (Southwestern Germany). Measurements include (i) half hourly vertical profiles of soil CO2 concentration (using soil CO2 probes), soil water content and temperature; (ii) half hourly soil surface CO2 effluxes (automatic chambers); (iii) half hourly isotopic composition of surface CO2 efflux and soil CO2 concentration profile and (iv) estimation of soil diffusivity through laboratory measurements conducted on soil samples taken at several depths. Using the data collected in the experimental part, we developed and used a diffusive transport model to simulate CO2 (13CO2 and 12CO2) flows inside and out of the soil based on Fick's first law. Given the horizontal homogeneity of soil physical parameters in Hartheim, we treated the soil as a structure consisting of distinctive layers of 5 cm thick and expressed the Fick's first law in a discrete formalism. The diffusion coefficient used in each layer was derived from (i) horizon specific relationships, obtained from laboratory measurements, between soil relative diffusivity and its water content and (ii) the soil water content values measured in situ. The concentration profile was obtained from in situ measurements. So, the main model inputs are the profiles of (i) CO2 (13CO2 and 12CO2) concentration, (ii) soil diffusion coefficient and (iii) soil water content. Once the diffusive fluxes deduced at each layer interface, the CO2 (13CO2 and 12CO2) production profile was calculated using the (discretized) mass balance equation in each layer. The results of the Hartheim measurement campaign will be presented. The CO2 source vertical profile and its link with the root and the Carbon organic content distribution will be showed. The dynamic of CO2 sources and their isotopic signature will be linked to climatic variables such soil temperature and soil water content. For example, we will show that the dynamics of CO2 sources was mainly related to temperature while changing of isotopic signature was more correlated to soil moisture.

Three-Man Solid Electrolyte Carbon Dioxide Electrolysis Breadboard

NASA Technical Reports Server (NTRS)

Isenberg, Arnold O.

1989-01-01

The development of the Three-Man (2.2 lb CO2/man-day) Solid Electrolyte CO2 Electrolysis Breadboard consisted of a Phase 1 and 2 effort. The Phase 1 effort constituted fabrication of three electrolysis cell types and performing parametric testing, off-design testing, and cell life testing. The Phase 2 consisted of the preliminary design, incorporation of palladium (Pd) tubes for hydrogen separation from the electrolyzer cathode feed gases, design support testing, final design, fabrication, and performance testing of the breadboard system. The results of performance tests demonstrated that CO2 electrolysis in an oxygen reclamation system for long duration space-based habitats is feasible. Closure of the oxygen system loop, therefore, can be achieved by CO2 electrolysis. In a two step process the metabolic CO2 and H2O vapor are electrolyzed into O2, H2, and CO. The CO can subsequently be disproportionated into carbon and CO2 in a carbon deposition reactor and the CO2 in turn be recycled and electrolyzed for total O2 recovery. The development effort demonstrated electrolyzer system can be designed and built to operate safely and reliably and the incorporation of Pd tubes for hydrogen diffusion can be integrated safely with predictable performance.

Diffusion mechanism in the sodium-ion battery material sodium cobaltate.

PubMed

Willis, T J; Porter, D G; Voneshen, D J; Uthayakumar, S; Demmel, F; Gutmann, M J; Roger, M; Refson, K; Goff, J P

2018-02-16

High performance batteries based on the movement of Li ions in Li x CoO 2 have made possible a revolution in mobile electronic technology, from laptops to mobile phones. However, the scarcity of Li and the demand for energy storage for renewables has led to intense interest in Na-ion batteries, including structurally-related Na x CoO 2 . Here we have determined the diffusion mechanism for Na 0.8 CoO 2 using diffuse x-ray scattering, quasi-elastic neutron scattering and ab-initio molecular dynamics simulations, and we find that the sodium ordering provides diffusion pathways and governs the diffusion rate. Above T ~ 290 K the so-called partially disordered stripe superstructure provides channels for quasi-1D diffusion, and melting of the sodium ordering leads to 2D superionic diffusion above T ~ 370 K. We obtain quantitative agreement between our microscopic study of the hopping mechanism and bulk self-diffusion measurements. Our approach can be applied widely to other Na- or Li-ion battery materials.

Monitoring diffuse volcanic degassing during volcanic unrests: the case of Campi Flegrei (Italy).

PubMed

Cardellini, C; Chiodini, G; Frondini, F; Avino, R; Bagnato, E; Caliro, S; Lelli, M; Rosiello, A

2017-07-28

In volcanoes with active hydrothermal systems, diffuse CO 2 degassing may constitute the primary mode of volcanic degassing. The monitoring of CO 2 emissions can provide important clues in understanding the evolution of volcanic activity especially at calderas where the interpretation of unrest signals is often complex. Here, we report eighteen years of CO 2 fluxes from the soil at Solfatara of Pozzuoli, located in the restless Campi Flegrei caldera. The entire dataset, one of the largest of diffuse CO 2 degassing ever produced, is made available for the scientific community. We show that, from 2003 to 2016, the area releasing deep-sourced CO 2 tripled its extent. This expansion was accompanied by an increase of the background CO 2 flux, over most of the surveyed area (1.4 km 2 ), with increased contributions from non-biogenic source. Concurrently, the amount of diffusively released CO 2 increased up to values typical of persistently degassing active volcanoes (up to 3000 t d -1 ). These variations are consistent with the increase in the flux of magmatic fluids injected into the hydrothermal system, which cause pressure increase and, in turn, condensation within the vapor plume feeding the Solfatara emission.

Re-evaluating alkenone based CO2 estimates

NASA Astrophysics Data System (ADS)

Pagani, M.

2013-05-01

Multi-million year patterns of ocean temperatures and ice accumulation are relatively consistent with reconstructed CO2 records. Existing records allow for broad statements regarding climate sensitivity, but uncertainties in reconstructions can lead to considerable error. For example, alkenone-based CO2 reconstructions assume that diffusion of CO2aq is the dominant source of inorganic carbon for photosynthesis. However, the concentration of CO2aq is the lowest of all dissolved carbon species, constituting <1% of the total inorganic aqueous pool. This poses a problem for sustaining reasonable algal growth rates because the half saturation constant for the enzyme Rubisco, the primary carboxylase involved in algal photosythesis, is commonly higher than the average concentration of seawater CO2aq. That is, the concentration of CO2aq in the modern ocean is too low to maintain adequate reactions rates for Rubisco, and thus, algal growth. In order to maintain algal growth rates, most modern algae have strategies to increase intercellular CO2 concentrations. But, if such strategies were prevalent for alkenone-producing algae in the past, CO2 reconstructions could be compromised. This presentation will assess time periods when carbon-concentration strategies were potentially in play and consequences for existing CO2 records.

Combining cross flow ultrafiltration and diffusion gradients in thin-films approaches to determine trace metal speciation in freshwaters

NASA Astrophysics Data System (ADS)

Liu, Ruixia; Lead, Jamie R.; Zhang, Hao

2013-05-01

Cross flow ultrafiltration (CFUF) and diffusive gradients in thin films (DGT) with open pore gel (OP) and restricted pore gel (RP) were used to measure trace metal speciation in selected UK freshwaters. The proportions of metals present in particulate forms (>1 μm) varied widely between 40-85% Pb, 60-80% Al, 7-56% Mn, 10-49% Cu, 0-55% Zn, 20-38% Cr, 20-30% Fe, 6-25% Co, 5-22% Cd and <7% Ni. In the colloidal fraction (2 kDa-1 μm) values varied between 53-91% Pb, 33-55% Al, 21-55% Cu, 20-44% Fe, 34-36% Cr, 20-40% Cd, 7-28% Co and Ni, 2-32% Zn and <8% Mn. Wide variations were also observed in the ultrafiltered fraction (<2 kDa). These results indicated that colloids indeed influenced the occurrence and transport of Al, Fe, Cr, Co, Ni, Cu, Zn, Cr and Pb metals in rivers, while inorganic or organic colloids did not exert an important control on Mn transport in the selected freshwaters. Of total species, total labile metal measured by DGT-OP accounted for 1.4-50% for Al, Fe, Co, Ni, Cu, Cd and Pb in all selected waters. Of these metals total labile Pb concentration was the lowest with value less than 1.4% although this value slightly increased after deducting particulate fractions. In some waters, a majority of total Mn, Zn and Cr is DGT labile, in which the DGT labile Mn fraction accounted for 98-118% of the total dissolved phase. In most cases, the inorganic labile concentration measured by DGT-RP was lower than the total labile metal concentration. By the combination of CFUF and DGT techniques, the concentrations of total labile and inorganic labile metal species in CFUF-derived truly dissolved phase were measured in four water samples. 100% of ultrafiltered Mn species was found to be total DGT labile. The proportions of total labile metal species were lower than those of ultrafiltered fraction for Al, Fe, Co, Ni, Cu, Cd and Pb in all selected waters, and Cr and Zn in some cases, indicating a large amount of natural complexing ligands with smaller size for the metals to form kinetically inert species or thermodynamically stable complexes. Observed discrepancies in metal speciation between metals and within sampling sites were related to the differences in the characteristics of the metals and the nature of water sources.

CO2 fluxes from diffuse degassing in Italy

NASA Astrophysics Data System (ADS)

Cardellini, C.; Chiodini, G.; Frondini, F.; Caliro, S.

2016-12-01

Central and southern Italy are affected by an intense process of CO2 Earth degassing from both active volcanoes, and tectonically active areas. Regional scale studies, based on C mass balance of groundwater of regional aquifers in not volcanically active areas, highlighted the presence of two large CO2 degassing structures that, for magnitude and the geochemical-isotopic features, were related to a regional process of mantle degassing. Quantitative estimates provided a CO2 flux of 9 Mt/y for the region (62000 km2). Besides the magnitude of the process, a strong link between the deep CO2 degassing and the seismicity of the region and a strict correlation between migration of deep CO2-rich fluids and the heat flux have been highlighted. In addition, the region is also characterised by the presence of many cold gas emissions where deeply derived CO2 is released by vents and soil diffuse degassing areas. Both direct CO2 expulsion at the surface and C-rich groundwater are different manifestations of the same process, in fact, the deeply produced gas can be dissolved by groundwater or emitted directly to the atmosphere depending on the gas flux rate, and the geological-structural and hydrogeological settings. Quantitative estimations of the CO2 fluxes are available only for a limited number ( 30) of the about 270 catalogued gas manifestations allowing an estimations of a CO2 flux of 1.4 Mt/y. Summing the two estimates the non-volcanic CO2 flux from the region results globally relevant, being from 2 to 10% of the estimated present-day global CO2 discharge from subaerial volcanoes. Large amounts of CO2 is also discharged by soil diffuse degassing in volcanic-hydrothermal systems. Specific surveys at Solfatara of Pozzuoli (Campi Flegrei Caldera) pointed out the relevance of this process. CO2 diffuse degassing at Solfatara, measured since 1998 shows a persistent CO2 flux of 1300 t/d (± 390 t/d), a flux comparable to an erupting volcano. The quantification of diffuse CO2 degassing in Italy points out the relevance of non-volcanic CO2 degassing and of soil degassing from volcanoes, suggesting that the actual underestimation of the global CO2 degassing, may arise also from the lack of specific and systematic studies of the numerous "degassing areas" of the world, that would contribute to better constrain the global CO2 budget.

Evaluation of advanced bladder technology

NASA Technical Reports Server (NTRS)

Christensen, M. V.; Pasternak, R. A.

1972-01-01

Research conducted during this period is reported. Studies presented include: (1) diffusion and permeation of CO2, O2, N2, and NO2 through polytetra fluoroethylene; (2) diffusion, permeation and solubility of simple gases (CO2, O2, N2, CH4, C2H6, C3H8, and C2H4) through a copolymer of hexafluoro propylene and tetrafluoro ethylene (FEP); (3) viscous flow and diffusion of gases throug small apertures; (4) diffusion and permeation of O2, N2, CO2, CH4, C2H6, and C3H8 through nitroso rubber; and (5) results of gas transport studies with carborane siloxane, nitroso rubber, silicone membrane, krytox coating on teflon, and FEP coated glass cloth. Publications generated under this program are listed.

Spatial and temporal variations of diffuse CO2 degassing at El Hierro volcanic system: Relation to the 2011-2012 submarine eruption

NASA Astrophysics Data System (ADS)

Melián, Gladys; Hernández, Pedro A.; Padrón, Eleazar; Pérez, Nemesio M.; Barrancos, José; Padilla, Germán.; Dionis, Samara; Rodríguez, Fátima; Calvo, David; Nolasco, Dacil

2014-09-01

We report herein the results of extensive diffuse CO2 emission surveys performed on El Hierro Island in the period 1998-2012. More than 17,000 measurements of the diffuse CO2 efflux were carried out, most of them during the volcanic unrest period that started in July 2011. Two significant precursory signals based on geochemical and geodetical studies suggest that a magma intrusion processes might have started before 2011 in El Hierro Island. During the preeruptive and eruptive periods, the time series of the diffuse CO2 emission released by the whole island experienced two significant increases. The first started almost 2 weeks before the onset of the submarine eruption, reflecting a clear geochemical anomaly in CO2 emission, most likely due to increasing release of deep-seated magmatic gases to the surface. The second one, between 24 October and 27 November 2011, started before the most energetic seismic events of the volcanic-seismic unrest. The data presented here demonstrate that combined continuous monitoring studies and discrete surveys of diffuse CO2 emission provide important information to optimize the early warning system in volcano monitoring programs and to monitor the evolution of an ongoing volcanic eruption, even though it is a submarine eruption.

Is the wall of a cellulose fiber saturated with liquid whether or not permeable with CO2 dissolved molecules? Application to bubble nucleation in champagne wines.

PubMed

Liger-Belair, Gérard; Topgaard, Daniel; Voisin, Cédric; Jeandet, Philippe

2004-05-11

In this paper, the transversal diffusion coefficient D perpendicular of CO2 dissolved molecules through the wall of a hydrated cellulose fiber was approached, from the liquid bulk diffusion coefficient of CO2 dissolved molecules modified by an obstruction factor. The porous network between the cellulose microfibrils of the fiber wall was assumed being saturated with liquid. We retrieved information from previous NMR experiments on the self-diffusion of water in cellulose fibers to reach an order of magnitude for the transversal diffusion coefficient of CO2 molecules through the fiber wall. A value of about D perpendicular approximately 0.2D0 was proposed, D0 being the diffusion coefficient of CO2 molecules in the liquid bulk. Because most of bubble nucleation sites in a glass poured with carbonated beverage are cellulose fibers cast off from paper or cloth which floated from the surrounding air, or remaining from the wiping process, this result directly applies to the kinetics of carbon dioxide bubble formation from champagne and sparkling wines. If the cellulose fiber wall was impermeable with regard to CO2 dissolved molecules, it was suggested that the kinetics of bubbling would be about three times less than it is.

Greenhouse gas (CO2 and CH4) emissions from a high altitude hydroelectric reservoir in the tropics (Riogrande II, Colombia)

NASA Astrophysics Data System (ADS)

Guérin, Frédéric; Leon, Juan

2015-04-01

Tropical hydroelectric reservoirs are considered as very significant source of methane (CH4) and carbon dioxide (CO2), especially when flooding dense forest. We report emissions from the Rio Grande II Reservoir located at 2000 m.a.s.l. in the Colombian Andes. The dam was built at the confluence of the Rio Grande and Rio Chico in 1990. The reservoir has a surface of 12 km2, a maximum depth of 40m and a residence time of 2.5 month. Water quality (temperature, oxygen, pH, conductivity), nitrate, ammonium, dissolved and particulate organic carbon (DOC and POC), CO2 and CH4 were monitored bi-monthly during 1.5 year at 9 stations in the reservoir. Diffusive fluxes of CO2 and CH4 and CH4 ebullition were measured at 5 stations. The Rio grande II Reservoir is weakly stratified thermally with surface temperature ranging from 20 to 24°C and a constant bottom temperature of 18°C. The reservoir water column is well oxygenated at the surface and usually anoxic below 10m depth. At the stations close to the tributaries water inputs, the water column is well mixed and oxygenated from the surface to the bottom. As reported for other reservoirs located in "clear water" watersheds, the concentrations of nutrients are low (NO3-<0.1ppm, NH4+<0.2ppm), the concentrations of DOC are high (2-8 mg L-1) and POC concentrations are low (< 3 mg L-1). Surface CH4 concentrations at the central stations of the reservoirs are 0.5 μmol L-1 (0.07-2.14 μmol L-1) and 3 times higher at the stations close to the tributaries inputs (up to 7 μmol L-1). In the hypolimnion, CH4 concentration is <100 μmol L-1 in the wet season and can reach up to 400 μmol L-1 in the dry season. The spatial and temporal variability are lower for CO2. Surface CO2 concentration was on average 72 μmol L-1 (up to 300) and hypolimnic concentration ranged between 250 and 1000 μmol L-1. The CO2 diffusive flux is 517±331 mmol m-2 d-1 with little seasonal and spatial variations. At the center of the reservoir, the median diffusive flux of CH4 is 1.75 mmol m-2 d-1 and sporadic high fluxes (>10 mmol m-2 d-1) were observed during the dry season. Close to the tributaries water inputs where the water column is well mixed, the average diffusive flux is 8 mmol m-2 d-1. CH4 ebullition was 3.5 mmol m-2 d-1 and no ebullition was observed for a water depth higher than 5m. The zone under the influence of the water inputs from tributaries represents 25% of the surface of the reservoir but contributed half of total CH4 emissions from the reservoir (29MgC month-1). Ebullition contributed only to 12% of total CH4 emissions over a year but it contributed up to 60% during the dry season. CH4 emissions from the Rio Grande Reservoir contributed 30% of the total GHG emissions (38GgCO2eq y-1). Overall, this study show that the majority of CH4 emissions from this reservoir occur through hotspot and hot moments and that mountainous reservoir located in the tropics could have emission factors as high as Amazonian reservoirs.

Redox-stratification controlled biofilm (ReSCoBi) for completely autotrophic nitrogen removal: the effect of co- versus counter-diffusion on reactor performance.

PubMed

Terada, Akihiko; Lackner, Susanne; Tsuneda, Satoshi; Smets, Barth F

2007-05-01

A multi-population biofilm model for completely autotrophic nitrogen removal was developed and implemented in the simulation program AQUASIM to corroborate the concept of a redox-stratification controlled biofilm (ReSCoBi). The model considers both counter- and co-diffusion biofilm geometries. In the counter-diffusion biofilm, oxygen is supplied through a gas-permeable membrane that supports the biofilm while ammonia (NH(4)(+)) is supplied from the bulk liquid. On the contrary, in the co-diffusion biofilm, both oxygen and NH(4)(+) are supplied from the bulk liquid. Results of the model revealed a clear stratification of microbial activities in both of the biofilms, the resulting chemical profiles, and the obvious effect of the relative surface loadings of oxygen and NH(4)(+) (J(O(2))/J(NH(4)(+))) on the reactor performances. Steady-state biofilm thickness had a significant but different effect on T-N removal for co- and counter-diffusion biofilms: the removal efficiency in the counter-diffusion biofilm geometry was superior to that in the co-diffusion counterpart, within the range of 450-1,400 microm; however, the efficiency deteriorated with a further increase in biofilm thickness, probably because of diffusion limitation of NH(4)(+). Under conditions of oxygen excess (J(O(2))/J(NH(4)(+)) > 3.98), almost all NH(4)(+) was consumed by aerobic ammonia oxidation in the co-diffusion biofilm, leading to poor performance, while in the counter-diffusion biofilm, T-N removal efficiency was maintained because of the physical location of anaerobic ammonium oxidizers near the bulk liquid. These results clearly reveal that counter-diffusion biofilms have a wider application range for autotrophic T-N removal than co-diffusion biofilms. (c) 2006 Wiley Periodicals, Inc.

In situ TEM study of electron-beam radiation induced boron diffusion and effects on phase and microstructure evolution in nanostructured CoFeB/SiO2 thin film

NASA Astrophysics Data System (ADS)

Liu, B. H.; Teo, H. W.; Mo, Z. H.; Mai, Z. H.; Lam, J.; Xue, J. M.; Zhao, Y. Z.; Tan, P. K.

2017-01-01

Using in situ transmission electron microscopy (TEM), we studied boron diffusion and segregation in CoFeB/SiO2 nanostructured thin film stacks. We also investigated how these phenomena affected the phase and microstructure of CoFeB thin films under electron beam irradiation at 300 kV. A unique phase transformation was observed in CoFeB thin films under high-dose electron irradiation, from a polycrystalline Co3Fe to a unilateral amorphous phase of Co3Fe and nanocrystalline FexCo23-xB6. The unilateral amorphization of the Co3Fe film showed an electron-dose-rate sensitivity with a threshold dose rate. Detailed in situ TEM studies revealed that the unilateral amorphization of the Co3Fe film arose from boron segregation at the bottom of the Co3Fe thin film induced by radiation-enhanced diffusion of boron atoms that were displaced by electron knock-on effects. The radiation-induced nanocrystallization of FexCo23-xB6 was also found to be dose-rate sensitive with a higher electron beam current leading to earlier nucleation and more rapid grain growth. The nanocrystallization of FexCo23-xB6 occurred preferentially at the CoFeB/SiO2 interface. Kinetic studies by in situ TEM revealed the surface crystallization and diffusion-controlled nucleation and grain growth mechanisms. The radiation-enhanced atomic diffusivity and high-concentration of radiation-induced point defects at the Co3Fe/SiO2 interface enhanced the local short-range ordering of Fe, Co, and B atoms, favoring nucleation and grain growth of FexCo23-xB6 at the interface.

Mars - The regolith-atmosphere-cap system and climate change

NASA Technical Reports Server (NTRS)

Fanale, F. P.; Salvail, J. R.; Banerdt, W. B.; Saunders, R. S.

1982-01-01

A model is derived for the prediction of the Martian regolith-atmosphere-cap CO2 regime's behavior, as well as for the description of the roly of the regime in climate change, through descriptions of the time-temperature histories of 90 regolith 'chunks' on a latitude-depth grid. The influence of differences in regolith adsorption laws for basalt and clay, and the influence of variations in regolith depth with (1) latitude, (2) regolith thermal diffusivity, and (3) total exchangeable CO2 inventory on predicted variations in atmospheric pressure and cap mass, are examined. It is found that the atmosphere acts as a low capacity conduit between two reservoirs through which 10-100 times the current atmospheric mass of CO2 flows. The exchange between the reservoirs is driven by obliquity variations, with the polar cap the dominant CO2 sink at low obliquity and the regolith dominating at high obliquity.

Influence of Liquid Structure on Fickian Diffusion in Binary Mixtures of n-Hexane and Carbon Dioxide Probed by Dynamic Light Scattering, Raman Spectroscopy, and Molecular Dynamics Simulations.

PubMed

Klein, Tobias; Wu, Wenchang; Rausch, Michael Heinrich; Giraudet, Cédric; Koller, Thomas M; Fröba, Andreas Paul

2018-06-11

This study contributes to a fundamental understanding how the liquid structure in a model system consisting of weakly associative n-hexane ( n-C 6 H 14 ) and carbon dioxide (CO 2 ) influences the Fickian diffusion process. For this, the benefits of light scattering experiments and molecular dynamics (MD) simulations at macroscopic thermodynamic equilibrium were combined synergistically. Our reference Fickian diffusivities measured by dynamic light scattering (DLS) revealed an unusual trend with increasing CO 2 mole fractions up to a CO 2 concentration of about 70 mol%, which agrees with our simulation results. The molecular impacts on the Fickian diffusion were analyzed by MD simulations, where kinetic contributions related to the Maxwell-Stefan (MS) diffusivity and structural contributions quantified by the thermodynamic factor were studied separately. Both the MS diffusivity and the thermodynamic factor indicate the deceleration of Fickian diffusion compared to an ideal mixture behavior. Computed radial distribution functions as well as a significant blue-shift of the CH-stretching modes of n-C 6 H 14 identified by Raman spectroscopy show that the slowing-down of the diffusion is caused by a structural organization in the binary mixtures over a broad concentration range in the form of self-associated n-C 6 H 14 and CO 2 domains. These networks start to form close to the infinite dilution limits and seem to have their largest extent at a solute-solvent transition point at about 70 mol% of CO 2 . The current results not only improve the general understanding of mass diffusion in liquids, but also serve to develop sound prediction models for Fick diffusivities.

Electron-stimulated reactions in layered CO/H2O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

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

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Low-energy (100 eV) electron-stimulated reactions in layered H2O/CO/H2O ices are investigated. For CO trapped within approximately 50 ML of the vacuum interface in the amorphous solid water (ASW) films, both oxidation and reduction reactions are observed. However for CO buried more deeply in the film, only the reduction of CO to methanol is observed. Experiments with layered films of H2O and D2O show that the hydrogen atoms participating in the reduction of the buried CO originate in region from ~10 – 40 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried COmore » layers, the CO reduction reactions quickly increase with temperature above ~60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol that accounts for the observations.« less

Elementary reaction modeling of reversible CO/CO2 electrochemical conversion on patterned nickel electrodes

NASA Astrophysics Data System (ADS)

Luo, Yu; Shi, Yixiang; Li, Wenying; Cai, Ningsheng

2018-03-01

CO/CO2 are the major gas reactant/product in the fuel electrode of reversible solid oxide cells (RSOC). This study proposes a two-charge-transfer-step mechanism to describe the reaction and transfer processes of CO-CO2 electrochemical conversion on a patterned Ni electrode of RSOC. An elementary reaction model is developed to couple two charge transfer reactions, C(Ni)+O2-(YSZ) ↔ CO(Ni)+(YSZ) +2e- and CO(Ni)+O2-(YSZ) ↔ CO2(Ni)+(YSZ)+2e-, with adsorption/desorption, surface chemical reactions and surface diffusion. This model well validates in both solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes by the experimental data from a patterned Ni electrode with 10 μm stripe width at different pCO (0-0.25 atm), pCO2 (0-0.35 atm) and operating temperature (600-700 °C). This model indicates SOEC mode is dominated by charge transfer step C(Ni)+O2-(YSZ)↔CO(Ni)+(YSZ) +2e-, while SOFC mode by CO(Ni)+ O2-(YSZ)↔CO2(Ni)+(YSZ)+2e- on the patterned Ni electrode. The sensitivity analysis shows charge transfer step is the major rate-determining step for RSOC, besides, surface diffusion of CO and CO2 as well as CO2 adsorption also plays a significant role in the electrochemical reaction of SOEC while surface diffusion of CO and CO2 desorption could be co-limiting in SOFC.

Quantification of carbon dioxide emissions of Ciomadul, the youngest volcano of the Carpathian-Pannonian Region (Eastern-Central Europe, Romania)

NASA Astrophysics Data System (ADS)

Kis, Boglárka-Mercédesz; Ionescu, Artur; Cardellini, Carlo; Harangi, Szabolcs; Baciu, Călin; Caracausi, Antonio; Viveiros, Fátima

2017-07-01

We provide the first high-resolution CO2 flux data for the Neogene to Quaternary volcanic regions of the entire Carpathian-Pannonian Region, Eastern-Central Europe, and estimate the CO2 emission of the seemingly inactive Ciomadul volcanic complex, the youngest volcano of this area. Our estimate includes data from focused and diffuse CO2 emissions from soil. The CO2 fluxes of focused emissions range between 277 and 8172 g d- 1, corresponding to a CO2 output into the atmosphere between 0.1 and 2.98 t per year. The investigated areas for diffuse soil gas emissions were characterized by wide range of CO2 flux values, at Apor Baths, ranging from 1.7 × 101 to 8.2 × 104 g m- 2 d- 1, while at Lăzărești ranging between 1.43 and 3.8 × 104 g m- 2 d- 1. The highest CO2 focused gas fluxes at Ciomadul were found at the periphery of the youngest volcanic complex, which could be explained either by tectonic control across the brittle older volcanic edifices or by degassing from a deeper crustal zone resulting in CO2 flux at the periphery of the supposed melt-bearing magma body beneath Ciomadul. The estimate of the total CO2 output in the area is 8.70 × 103 t y- 1, and it is consistent with other long (> 10 kyr) dormant volcanoes with similar age worldwide, such as in Italy and USA. Taking into account the isotopic composition of the gases that indicate deep origin of the CO2 emissions, this yields further support that Ciomadul may be considered indeed a dormant, or PAMS volcano (volcano with potentially active magma storage) rather than an inactive one. Furthermore, hazard of CO2 outpourings has to be taken into account and it has to be communicated to the visitors. Finally, we suggest that CO2 output of dormant volcanic systems has to be also accounted in the estimation of the global volcanic CO2 budget.

The mechanistic basis of internal conductance: a theoretical analysis of mesophyll cell photosynthesis and CO2 diffusion.

PubMed

Tholen, Danny; Zhu, Xin-Guang

2011-05-01

Photosynthesis is limited by the conductance of carbon dioxide (CO(2)) from intercellular spaces to the sites of carboxylation. Although the concept of internal conductance (g(i)) has been known for over 50 years, shortcomings in the theoretical description of this process may have resulted in a limited understanding of the underlying mechanisms. To tackle this issue, we developed a three-dimensional reaction-diffusion model of photosynthesis in a typical C(3) mesophyll cell that includes all major components of the CO(2) diffusion pathway and associated reactions. Using this novel systems model, we systematically and quantitatively examined the mechanisms underlying g(i). Our results identify the resistances of the cell wall and chloroplast envelope as the most significant limitations to photosynthesis. In addition, the concentration of carbonic anhydrase in the stroma may also be limiting for the photosynthetic rate. Our analysis demonstrated that higher levels of photorespiration increase the apparent resistance to CO(2) diffusion, an effect that has thus far been ignored when determining g(i). Finally, we show that outward bicarbonate leakage through the chloroplast envelope could contribute to the observed decrease in g(i) under elevated CO(2). Our analysis suggests that physiological and anatomical features associated with g(i) have been evolutionarily fine-tuned to benefit CO(2) diffusion and photosynthesis. The model presented here provides a novel theoretical framework to further analyze the mechanisms underlying diffusion processes in the mesophyll.

The Mechanistic Basis of Internal Conductance: A Theoretical Analysis of Mesophyll Cell Photosynthesis and CO2 Diffusion1[W][OA

PubMed Central

Tholen, Danny; Zhu, Xin-Guang

2011-01-01

Photosynthesis is limited by the conductance of carbon dioxide (CO2) from intercellular spaces to the sites of carboxylation. Although the concept of internal conductance (gi) has been known for over 50 years, shortcomings in the theoretical description of this process may have resulted in a limited understanding of the underlying mechanisms. To tackle this issue, we developed a three-dimensional reaction-diffusion model of photosynthesis in a typical C3 mesophyll cell that includes all major components of the CO2 diffusion pathway and associated reactions. Using this novel systems model, we systematically and quantitatively examined the mechanisms underlying gi. Our results identify the resistances of the cell wall and chloroplast envelope as the most significant limitations to photosynthesis. In addition, the concentration of carbonic anhydrase in the stroma may also be limiting for the photosynthetic rate. Our analysis demonstrated that higher levels of photorespiration increase the apparent resistance to CO2 diffusion, an effect that has thus far been ignored when determining gi. Finally, we show that outward bicarbonate leakage through the chloroplast envelope could contribute to the observed decrease in gi under elevated CO2. Our analysis suggests that physiological and anatomical features associated with gi have been evolutionarily fine-tuned to benefit CO2 diffusion and photosynthesis. The model presented here provides a novel theoretical framework to further analyze the mechanisms underlying diffusion processes in the mesophyll. PMID:21441385

Oxide ion diffusion mechanism related to Co and Fe ions in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ using in-situ X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Itoh, Takanori; Imai, Hideto

2018-03-01

The time changes of the white line and pre-edge intensities of Co and Fe K-edge in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ (BSCF) were observed to estimate the oxide ion diffusion related to Co and Fe ions by using in - situ X-ray absorption spectroscopy (XAS) during oxidation. The 20 μm self-standing BSCF film was prepared for in - situ XAS measurements. The time changes of absorption were fitted to the exponential decay function with two terms. The longer relaxation time (τ), related to the oxide ion diffusion during the oxidation of BSCF, is dependent on temperature. The oxide ion diffusion coefficients (D) were calculated from the τ s estimated by in - situ XAS. The values of the activation energy (Ea) for D related to Co K-edge white line, Co pre-edge, and Fe pre-edge were 1.8-2.0 eV. The value of Ea for D related to Fe K-edge white line, however, was higher than other absorption values at approximately 2.3 eV. We discussed the oxide ion diffusion mechanism related to Co and Fe ions in BSCF using in - situ XAS.

Subsurface Growth of CoSi2 by Deposition of Co on Si-Capped CoSi2 Seed Regions

NASA Technical Reports Server (NTRS)

Fathauer, R. W.; George, T.; Pike, W. T.

1991-01-01

At a growth temperature of 800 C, Co deposited on Si(111) diffuses through a Si cap and exhibits oriented growth on buried CoSi2 grains, a process referred to as endotaxy. This occurs preferentially to surface nucleation of CoSi2 provided the thickness of the Si cap is less than a critical value between 100 and 200 nm for a deposition rate of 0.01 nm/s. Steady-state endotaxy is modeled under the assumption that the process is controlled by Co diffusion.

CO2 diffuse emission from maar lake: An example in Changbai volcanic field, NE China

NASA Astrophysics Data System (ADS)

Sun, Yutao; Guo, Zhengfu; Liu, Jiaqi; Du, Jianguo

2018-01-01

Numerous maars and monogenetic volcanic cones are distributed in northeast China, which are related to westward deep subduction of the Pacific Ocean lithosphere, comprising a significant part of the "Pacific Ring of Fire". It is well known that diffuse CO2 emissions from monogenetic volcanoes, including wet (e.g., maar lake) and dry degassing systems (e.g., soil diffuse emission, fault degassing, etc.), may contribute to budget of globally nature-derived greenhouse gases. However, their relationship between wet (e.g., maar lake) and concomitant dry degassing systems (e.g., soil diffuse emission, fault degassing, etc.) related to monogenetic volcanic field is poorly understood. Yuanchi maar, one of the typical monogenetic volcanic systems, is located on the eastern flank of Tianchi caldera in Changbai volcanic field of northeast China, which displays all of three forms of CO2 degassing including the maar lake, soil micro-seepage and fault degassing. Measurements of efflux of CO2 diffusion from the Yuanchi maar system (YMS) indicate that the average values of CO2 emissions from soil micro-seepage, fault degassing and water-air interface diffusion are 24.3 ± 23.3 g m- 2 d- 1, 39.2 ± 22.4 g m- 2 d- 1 and 2.4 ± 1.1 g m- 2 d- 1, respectively. The minimum output of CO2 diffuse emission from the YMS to the atmosphere is about 176.1 ± 88.3 ton/yr, of which 80.4% results from the dry degassing system. Degassing from the fault contributes to the most of CO2 emissions in all of the three forms of degassing in the YMS. Contributions of mantle, crust, air and organic CO2 to the soil gas are 0.01-0.10%, 10-20%, 32-36% and 48-54%, respectively, which are quantitatively constrained by a He-C isotope coupling calculation model. We propose that CO2 exsolves from the upper mantle melting beneath the Tianchi caldera, which migrates to the crustal magma chamber and further transports to the surface of YMS along the deep fault system. During the transportation processes, the emission of gas experiences crustal contamination, influence of magma chamber beneath the YMS, sub-surface processes and air dilution.

Application of gas diffusion biocathode in microbial electrosynthesis from carbon dioxide.

PubMed

Bajracharya, Suman; Vanbroekhoven, Karolien; Buisman, Cees J N; Pant, Deepak; Strik, David P B T B

2016-11-01

Microbial catalysis of carbon dioxide (CO 2 ) reduction to multi-carbon compounds at the cathode is a highly attractive application of microbial electrosynthesis (MES). The microbes reduce CO 2 by either taking the electrons or reducing the equivalents produced at the cathode. While using gaseous CO 2 as the carbon source, the biological reduction process depends on the dissolution and mass transfer of CO 2 in the electrolyte. In order to deal with this issue, a gas diffusion electrode (GDE) was investigated by feeding CO 2 through the GDE into the MES reactor for its reduction at the biocathode. A combination of the catalyst layer (porous activated carbon and Teflon binder) and the hydrophobic gas diffusion layer (GDL) creates a three-phase interface at the electrode. So, CO 2 and reducing equivalents will be available to the biocatalyst on the cathode surface. An enriched inoculum consisting of acetogenic bacteria, prepared from an anaerobic sludge, was used as a biocatalyst. The cathode potential was maintained at -1.1 V vs Ag/AgCl to facilitate direct and/or hydrogen-mediated CO 2 reduction. Bioelectrochemical CO 2 reduction mainly produced acetate but also extended the products to ethanol and butyrate. Average acetate production rates of 32 and 61 mg/L/day, respectively, with 20 and 80 % CO 2 gas mixture feed were achieved with 10 cm 2 of GDE. The maximum acetate production rate remained 238 mg/L/day for 20 % CO 2 gas mixture. In conclusion, a gas diffusion biocathode supported bioelectrochemical CO 2 reduction with enhanced mass transfer rate at continuous supply of gaseous CO 2 . Graphical abstract ᅟ.

The Relative Importance of Methanogenesis in the Decomposition of Organic Matter in Northern Peatlands

NASA Technical Reports Server (NTRS)

Corbett, J. Elizabeth; Tfaily, Malak M.; Burdige, David J.; Glaser, Paul H.; Chanton, Jeffrey P.

2015-01-01

Using an isotope-mass balance approach and assuming the equimolar production of CO2 and CH4 from methanogenesis (e.g., anaerobic decomposition of cellulose), we calculate that the proportion of total CO2 production from methanogenesis varies from 37 to 83% across a variety of northern peatlands. In a relative sense, methanogenesis was a more important pathway for decomposition in bogs (80 +/- 13% of CO2 production) than in fens (64 +/- 5.7% of CO2 production), but because fens contain more labile substrates they may support higher CH4 production overall. The concentration of CO2 produced from methanogenesis (CO2-meth) can be considered equivalent to CH4 concentration before loss due to ebullition, plant-mediated transport, or diffusion. Bogs produced slightly less CO2-meth than fens (2.9 +/- 1.3 and 3.7 +/- 1.4 mmol/L, respectively). Comparing the quantity of CH4 present to CO2-meth, fens lost slightly more CH4 than bogs (89 +/- 2.8% and 82 +/- 5.3%, respectively) likely due to the presence of vascular plant roots. In collapsed permafrost wetlands, bog moats produced half the amount of CO2-meth (0.8 +/- 0.2mmol/L) relative to midbogs (1.6 +/- 0.6 mmol/L) and methanogenesis was less important (42 +/- 6.6% of total CO2 production relative to 55 +/- 8.1%).We hypothesize that the lower methane production potential in collapsed permafrost wetlands occurs because recently thawed organic substrates are being first exposed to the initial phases of anaerobic decomposition following collapse and flooding. Bog moats lost a comparable amount of CH4 as midbogs (63 +/- 7.0% and 64 +/- 9.3%).

The relative importance of methanogenesis in the decomposition of organic matter in northern peatlands

NASA Astrophysics Data System (ADS)

Corbett, J. Elizabeth; Tfaily, Malak M.; Burdige, David J.; Glaser, Paul H.; Chanton, Jeffrey P.

2015-02-01

Using an isotope-mass balance approach and assuming the equimolar production of CO2 and CH4 from methanogenesis (e.g., anaerobic decomposition of cellulose), we calculate that the proportion of total CO2 production from methanogenesis varies from 37 to 83% across a variety of northern peatlands. In a relative sense, methanogenesis was a more important pathway for decomposition in bogs (80 ± 13% of CO2 production) than in fens (64 ± 5.7% of CO2 production), but because fens contain more labile substrates they may support higher CH4 production overall. The concentration of CO2 produced from methanogenesis (CO2-meth) can be considered equivalent to CH4 concentration before loss due to ebullition, plant-mediated transport, or diffusion. Bogs produced slightly less CO2-meth than fens (2.9 ± 1.3 and 3.7 ± 1.4 mmol/L, respectively). Comparing the quantity of CH4 present to CO2-meth, fens lost slightly more CH4 than bogs (89 ± 2.8% and 82 ± 5.3%, respectively) likely due to the presence of vascular plant roots. In collapsed permafrost wetlands, bog moats produced half the amount of CO2-meth (0.8 ± 0.2 mmol/L) relative to midbogs (1.6 ± 0.6 mmol/L) and methanogenesis was less important (42 ± 6.6% of total CO2 production relative to 55 ± 8.1%). We hypothesize that the lower methane production potential in collapsed permafrost wetlands occurs because recently thawed organic substrates are being first exposed to the initial phases of anaerobic decomposition following collapse and flooding. Bog moats lost a comparable amount of CH4 as midbogs (63 ± 7.0% and 64 ± 9.3%).

Diffuse CO2 fluxes from Santiago and Congro volcanic lakes (São Miguel, Azores archipelago)

NASA Astrophysics Data System (ADS)

Andrade, César; Cruz, José; Viveiros, Fátima; Branco, Rafael

2017-04-01

Diffuse CO2 degassing occurring in Santiago and Congro lakes, both located in depressions associated to maars from São Miguel Island (Azores, Portugal), was studied through detailed flux measurements. Four sampling campaigns were developed between 2013 and 2016 in each water body, split by the cold and wet seasons. São Miguel has an area of 744.6 km2, being the largest island of the archipelago. The geology of the island is dominated by three quiescent central volcanoes (Sete Cidades, Fogo and Furnas), linked by volcanic fissural zones (Picos and Congro Fissural Volcanic systems). The oldest volcanic systems of the island are located in its eastern part (Povoação-Nordeste). Santiago lake, with a surface area of 0.26 km2 and a depth of 30.5 m, is located inside a maar crater in the Sete Cidades volcano at an altitude of 355 m. The watershed of the lake has an area of 0.97 km2 and a surface flow estimated as 1.54x10 m3/a. A total of 1612 CO2 flux measurements using the accumulation chamber method were made at Santiago lake, 253 in the first campaign (November 2013), and 462, 475 and 422 in the three other campaigns, respectively, in April 2014, September 2016 and December 2016. The total CO2 flux estimated for this lake varies between 0.4 t d-1 and 0.59 t d-1, for the surveys performed, respectively, in November 2013 and September 2016; higher CO2 outputs of 1.57 and 5.87 t d-1 were calculated for the surveys carried out in April 2014 and December 2016. These higher CO2 emissions were associated with a period without water column stratification. Similarly to Santiago lake, Congro lake is located inside a maar, in the Congro Fissural Volcanic system, and has a surface area of 0.04 km2 with 18.5 m depth and a storage of about 2.4x105 m3/a. The lake, located at an altitude of 420 m, is fed by a watershed with an area of 0.33 km2 and a runoff estimated as about 8x104 m3/a. In Congro lake a total of 713 CO2 flux measurements were performed during four surveys from November 2013 to February 2016. The CO2 flux output was estimated as ranging between 0.06 t d-1 and 0.31 t d-1; the lower CO2 emission occurred in July 2015 and should reflect the stratification of the water column that prevents the CO2 flux release at the lake surface. Considering both volcanic lakes, the mean CO2 emissions, standardized per area, in the cold season were ˜14.9 t km-2 d-1 and ˜7.1 t km-2 d-1, respectively, for Santiago and Congro lakes. During summer period, CO2 emissions were lower in both lakes (˜1.9 t km-2 d-1 and ˜4.1 t km-2 d-1 for Santiago and Congro, correspondingly), what is explained by the lake stratification. Due to the organic processes that occur in the lakes, the CO2 emission is mostly associated to a biogenic origin, but a volcanic influence cannot be excluded and further research using carbon isotopic data is crucial to discriminate the CO2 sources. Key words: volcanic lakes, CO2 flux, maars, São Miguel Island

A Herschel [C ii] Galactic plane survey. I. The global distribution of ISM gas components

NASA Astrophysics Data System (ADS)

Pineda, J. L.; Langer, W. D.; Velusamy, T.; Goldsmith, P. F.

2013-06-01

Context. The [C ii] 158 μm line is an important tool for understanding the life cycle of interstellar matter. Ionized carbon is present in a variety of phases of the interstellar medium (ISM), including the diffuse ionized medium, warm and cold atomic clouds, clouds in transition from atomic to molecular, and dense and warm photon dominated regions. Aims: Velocity-resolved observations of [C ii] are the most powerful technique available to disentangle the emission produced by these components. These observations can also be used to trace CO-dark H2 gas and determine the total mass of the ISM. Methods: The Galactic Observations of Terahertz C+ (GOT C+) project surveys the [C ii] 158 μm line over the entire Galactic disk with velocity-resolved observations using the Herschel/HIFI instrument. We present the first longitude-velocity maps of the [C ii] emission for Galactic latitudes b = 0°, ±0.5°, and ±1.0°. We combine these maps with those of H i, 12CO, and 13CO to separate the different phases of the ISM and study their properties and distribution in the Galactic plane. Results: [C ii] emission is mostly associated with spiral arms, mainly emerging from Galactocentric distances between 4 and 10 kpc. It traces the envelopes of evolved clouds as well as clouds that are in the transition between atomic and molecular. We estimate that most of the observed [C ii] emission is produced by dense photon dominated regions (~47%), with smaller contributions from CO-dark H2 gas (~28%), cold atomic gas (~21%), and ionized gas (~4%). Atomic gas inside the Solar radius is mostly in the form of cold neutral medium (CNM), while the warm neutral medium gas dominates the outer galaxy. The average fraction of CNM relative to total atomic gas is ~43%. We find that the warm and diffuse CO-dark H2 is distributed over a larger range of Galactocentric distances (4-11 kpc) than the cold and dense H2 gas traced by 12CO and 13CO (4-8 kpc). The fraction of CO-dark H2 to total H2 increases with Galactocentric distance, ranging from ~20% at 4 kpc to ~80% at 10 kpc. On average, CO-dark H2 accounts for ~30% of the molecular mass of the Milky Way. When the CO-dark H2 component is included, the radial distribution of the CO-to-H2 conversion factor is steeper than that when only molecular gas traced by CO is considered. Most of the observed [C ii] emission emerging from dense photon dominated regions is associated with modest far-ultraviolet fields in the range χ0 ≃ 1 - 30. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.Appendices are available in electronic form at http://www.aanda.org

Diffuse CO_{2} degassing monitoring of the oceanic active volcanic island of El Hierro, Canary Islands, Spain

NASA Astrophysics Data System (ADS)

Hernández, Pedro A.; Norrie, Janice; Withoos, Yannick; García-Merino, Marta; Melián, Gladys; Padrón, Eleazar; Barrancos, José; Padilla, Germán; Rodríguez, Fátima; Pérez, Nemesio M.

2017-04-01

Even during repose periods, volcanoes release large amounts of gases from both visible (fumaroles, solfataras, plumes) and non-visible emanations (diffuse degassing). In the last 20 years, there has been considerable interest in the study of diffuse degassing as a powerful tool in volcano monitoring programs, particularly in those volcanic areas where there are no visible volcanic-hydrothermal gas emissions. Historically, soil gas and diffuse degassing surveys in volcanic environments have focused mainly on CO2 because it is, after water vapor, the most abundant gas dissolved in magma. As CO2 travels upward by advective-diffusive transport mechanisms and manifests itself at the surface, changes in its flux pattern over time provide important information for monitoring volcanic and seismic activity. Since 1998, diffuse CO2 emission has been monitored at El Hierro Island, the smallest and south westernmost island of the Canarian archipelago with an area of 278 km2. As no visible emanations occur at the surface environment of El Hierro, diffuse degassing studies have become the most useful geochemical tool to monitor the volcanic activity in this volcanic island. The island experienced a volcano-seismic unrest that began in July 2011, characterized by the location of a large number of relatively small earthquakes (M<2.5) beneath El Hierro at depths between 8 and 15 km. On October 12, 2011, a submarine eruption was confirmed during the afternoon of October 12, 2011 by visual observations off the coast of El Hierro, about 2 km south of the small village of La Restinga in the southernmost part of the island. During the pre-eruptive and eruptive periods, the time series of the diffuse CO2 emission released by the whole island experienced two significant increases. The first started almost 2 weeks before the onset of the submarine eruption, reflecting a clear geochemical anomaly in CO2 emission, most likely due to increasing release of deep seated magmatic gases to the surface. The second one, between October 24 and November 27, 2011, before the most energetic seismic events of the volcanic-seismic unrest (Melián et al., 2014. J. Geophys. Res. Solid Earth, 119, 6976-6991). The highest CO2 degassing rate measured in the last three years (1684 t/d) was observed during a seismo-volcanic unrest. This value decreased until close to background value (˜422 t/d, Melián et al., 2014) contemporaneously with the decline of the seismic activity during the first half of 2013. The last diffuse CO2 degassing survey was carried out in the summer of 2016, showing a emission rate of 854 t/d. Discrete surveys of diffuse CO2 emission have provided important information to optimize the early warning system in the volcano monitoring programs of El Hierro and to monitor the evolution of an ongoing volcanic eruption, even though is a submarine eruption.

Unveiling the Interplay Between Diffusing CO2 and Ethanol Molecules in Champagne Wines by Classical Molecular Dynamics and (13)C NMR Spectroscopy.

PubMed

Bonhommeau, David A; Perret, Alexandre; Nuzillard, Jean-Marc; Cilindre, Clara; Cours, Thibaud; Alijah, Alexander; Liger-Belair, Gérard

2014-12-18

The diffusion coefficients of carbon dioxide (CO2) and ethanol (EtOH) in carbonated hydroalcoholic solutions and Champagne wines are evaluated as a function of temperature by classical molecular dynamics (MD) simulations and (13)C NMR spectroscopy measurements. The excellent agreement between theoretical and experimental diffusion coefficients suggest that ethanol is the main molecule, apart from water, responsible for the value of the CO2 diffusion coefficients in typical Champagne wines, a result that could likely be extended to most sparkling wines with alike ethanol concentrations. CO2 and EtOH hydrodynamical radii deduced from viscometry measurements by applying the Stokes-Einstein relationship are found to be mostly constant and in close agreement with MD predictions. The reliability of our approach should be of interest to physical chemists aiming to model transport phenomena in supersaturated aqueous solutions or water/alcohol mixtures.

Photosynthetic limitations in two Antarctic vascular plants: importance of leaf anatomical traits and Rubisco kinetic parameters.

PubMed

Sáez, Patricia L; Bravo, León A; Cavieres, Lohengrin A; Vallejos, Valentina; Sanhueza, Carolina; Font-Carrascosa, Marcel; Gil-Pelegrín, Eustaquio; Javier Peguero-Pina, José; Galmés, Jeroni

2017-05-17

Particular physiological traits allow the vascular plants Deschampsia antarctica Desv. and Colobanthus quitensis (Kunth) Bartl. to inhabit Antarctica. The photosynthetic performance of these species was evaluated in situ, focusing on diffusive and biochemical constraints to CO2 assimilation. Leaf gas exchange, Chl a fluorescence, leaf ultrastructure, and Rubisco catalytic properties were examined in plants growing on King George and Lagotellerie islands. In spite of the species- and population-specific effects of the measurement temperature on the main photosynthetic parameters, CO2 assimilation was highly limited by CO2 diffusion. In particular, the mesophyll conductance (gm)-estimated from both gas exchange and leaf chlorophyll fluorescence and modeled from leaf anatomy-was remarkably low, restricting CO2 diffusion and imposing the strongest constraint to CO2 acquisition. Rubisco presented a high specificity for CO2 as determined in vitro, suggesting a tight co-ordination between CO2 diffusion and leaf biochemistry that may be critical ultimately to optimize carbon balance in these species. Interestingly, both anatomical and biochemical traits resembled those described in plants from arid environments, providing a new insight into plant functional acclimation to extreme conditions. Understanding what actually limits photosynthesis in these species is important to anticipate their responses to the ongoing and predicted rapid warming in the Antarctic Peninsula. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Measuring volcanic gases at Taal Volcano Main Crater for monitoring volcanic activity and possible gas hazard

NASA Astrophysics Data System (ADS)

Arpa, M.; Hernandez Perez, P. A.; Reniva, P.; Bariso, E.; Padilla, G.; Melian Rodriguez, G.; Barrancos, J.; Calvo, D.; Nolasco, D.; Padron, E.; Garduque, R.; Villacorte, E.; Fajiculay, E.; Perez, N.; Solidum, R.

2012-12-01

Taal is an active volcano located in southwest Luzon, Philippines. It consists of mainly tuff cones which have formed an island at the center of a 30 km wide Taal Caldera. Most historical eruptions, since 1572 on Taal Volcano Island, have been characterized as hydromagmatic eruptions. Taal Main Crater, produced during the 1911 eruption, is the largest crater in the island currently filled by a 1.2 km wide, 85 m deep acidic lake. The latest historical eruption occurred in 1965-1977. Monitoring of CO2 emissions from the Main Crater Lake (MCL) and fumarolic areas within the Main Crater started in 2008 with a collaborative project between ITER and PHIVOLCS. Measurements were done by accumulation chamber method using a Westsystem portable diffuse fluxmeter. Baseline total diffuse CO2 emissions of less than 1000 t/d were established for the MCL from 3 campaign-type surveys between April, 2008 to March, 2010 when seismicity was within background levels. In May, 2010, anomalous seismic activity from the volcano started and the total CO2 emission from the MCL increased to 2716±54 t/d as measured in August, 2010. The CO2 emission from the lake was highest last March, 2011 at 4670±159 t/d when the volcano was still showing signs of unrest. Because CO2 emissions increased significantly (more than 3 times the baseline value) at this time, this activity may be interpreted as magmatic and not purely hydrothermal. Most likely deep magma intrusions occurred but did not progress further to shallower depths and no eruption occurred. No large increase in lake water temperature near the surface (average for the whole lake area) during the period when CO2 was above background, it remained at 30-34°C and a few degrees lower than average ambient temperature. Total CO2 emissions from the MCL have decreased to within baseline values since October, 2011. Concentrations of CO2, SO2 and H2S in air in the fumarolic area within the Main Crater also increased in March, 2011. The measurements were made using a multigas sensor. In terms of volcanic gas hazard, CO2 in air near a fumarole vent can be as high as 25,000 ppm, while the highest H2S recorded was at 14 ppm (March, 2011). Without a multigas sensor, we measured the concentrations of only CO2 and H2S in air near the fumaroles using the Westsystem fluxmeter. During the latest survey last July 2012, the highest measured CO2 in air was 13,000 ppm and for H2S it was 28 ppm to above detection limit. The campaign-type CO2 efflux surveys in the MCL and measurements of the fumaroles are done at least once or twice a year with increased frequency of surveys when signs of unrest are detected. These measurements are important because Taal Volcano Island, although designated as a permanent danger zone, is permanently inhabited.

Decadal-scale variability of diffuse CO2 emissions and seismicity revealed from long-term monitoring (1995–2013) at Mammoth Mountain, California, USA

USGS Publications Warehouse

Werner, Cynthia A.; Bergfeld, Deborah; Farrar, Chris; Doukas, Michael P.; Kelly, Peter; Kern, Christoph

2014-01-01

Mammoth Mountain, California, is a dacitic volcano that has experienced several periods of unrest since 1989. The onset of diffuse soil CO2 emissions at numerous locations on the flanks of the volcano began in 1989–1990 following an 11-month period of heightened seismicity. CO2 emission rates were measured yearly from 1995 to 2013 at Horseshoe Lake (HSL), the largest tree kill area on Mammoth Mountain, and measured intermittently at four smaller degassing areas around Mammoth from 2006 to 2013. The long-term record at HSL shows decadal-scale variations in CO2 emissions with two peaks in 2000–2001 and 2011–2012, both of which follow peaks in seismicity by 2–3 years. Between 2000 and 2004 emissions gradually declined during a seismically quiet period, and from 2004 to 2009 were steady at ~ 100 metric tonnes per day (t d− 1). CO2emissions at the four smaller tree-kill areas also increased by factors of 2–3 between 2006 and 2011–2012, demonstrating a mountain-wide increase in degassing. Delays between the peaks in seismicity and degassing have been observed at other volcanic and hydrothermal areas worldwide, and are thought to result from an injection of deep CO2-rich fluid into shallow subsurface reservoirs causing a pressurization event with a delayed transport to the surface. Such processes are consistent with previous studies at Mammoth, and here we highlight (1) the mountain-wide response, (2) the characteristic delay of 2–3 years, and (3) the roughly decadal reoccurrence interval for such behavior. Our best estimate of total CO2 degassing from Mammoth Mountain was 416 t d− 1 in 2011 during the peak of emissions, over half of which was emitted from HSL. The cumulative release of CO2 between 1995 and 2013 from diffuse emissions is estimated to be ~ 2–3 Mt, and extrapolation back to 1989 gives ~ 4.8 Mt. This amount of CO2 release is similar to that produced by the mid-sized (VEI 3) 2009 eruption of Redoubt Volcano in Alaska (~ 2.3 Mt over 11 months), and significantly lower than long-term emissions from hydrothermal areas such as Solfatara in Campi Flegrei, Italy (16 Mt over 28 years).

Carbon dioxide emissions from vegetation-kill zones around the resurgent dome of Long Valley caldera, eastern California, USA

NASA Astrophysics Data System (ADS)

Bergfeld, Deborah; Evans, William C.; Howle, James F.; Farrar, Christopher D.

2006-04-01

A survey of diffuse CO 2 efflux, soil temperature and soil-gas chemistry over areas of localized vegetation-kill on and around the resurgent dome of Long Valley caldera California was performed to evaluate the premise that gaseous and thermal anomalies are related to renewed intrusion of magma. Some kill sites are long-lived features and others have developed in the past few years. Total anomalous CO 2 emissions from the thirteen areas average around 8.7 t per day; but the majority of the emissions come from four sites west of the Casa Diablo geothermal power plant. Geochemical analyses of the soil-gases from locations west and east of the plant revealed the presence of isobutane related to plant operations. The δ13C values of diffuse CO 2 range from - 5.7‰ to - 3.4‰, similar to values previously reported for CO 2 from hot springs and thermal wells around Long Valley. At many of the vegetation-kill sites soil temperatures reach boiling at depths ≤ 20 cm. Soil temperature/depth profiles at two of the high-emissions areas indicate that the conductive thermal gradient in the center of the areas is around 320 °C m - 1 . We estimate total heat loss from the two areas to be about 6.1 and 2.3 MW. Given current thinking on the rate of hydrothermal fluid flow across the caldera and using the CO 2 concentration in the thermal fluids, the heat and CO 2 loss from the kill areas is easily provided by the shallow hydrothermal system, which is sourced to the west of the resurgent dome. We find no evidence that the development of new areas of vegetation kill across the resurgent dome are related to new input of magma or magmatic fluids from beneath the resurgent dome. Our findings indicate that the areas have developed as a response to changes in the shallow hydrologic system. Some of the changes are likely related to fluid production at the power plant, but at distal sites the changes are more likely related to seismicity and uplift of the dome.

Surface geothermal exploration in the Canary Islands by means of soil CO_{2} degassing surveys

NASA Astrophysics Data System (ADS)

García-Merino, Marta; Rodríguez, Fátima; Padrón, Eleazar; Melián, Gladys; Asensio-Ramos, María; Barrancos, José; Hernández, Pedro A.; Pérez, Nemesio M.

2017-04-01

With the exception of the Teide fumaroles, there is not any evidence of hydrothermal fluid discharges in the surficial environment of the Canary Islands, the only Spanish territory with potential high enthalpy geothermal resources. Here we show the results of several diffuse CO2 degassing surveys carried out at five mining licenses in Tenerife and Gran Canaria with the aim of sorting the possible geothermal potential of these five mining licenses. The primary objective of the study was to reduce the uncertainty inherent to the selection of the areas with highest geothermal potential for future exploration works. The yardstick used to classify the different areas was the contribution of volcano-hydrothermal CO2 in the diffuse CO2 degassing at each study area. Several hundreds of measurements of diffuse CO2 emission, soil CO2 concentration and isotopic composition were performed at each mining license. Based in three different endmembers (biogenic, atmospheric and deep-seated CO2) with different CO2 concentrations (100, 0.04 and 100%, respectively) and isotopic compositions (-24, -8 and -3 per mil vs. VPDB respectively) a mass balance to distinguish the different contribution of each endmember in the soil CO2 at each sampling site was made. The percentage of the volcano-hydrothermal contribution in the current diffuse CO2 degassing was in the range 0-19%. The Abeque mining license, that comprises part of the north-west volcanic rift of Tenerife, seemed to show the highest geothermal potential, with an average of 19% of CO2 being released from deep sources, followed by Atidama (south east of Gran Canaria) and Garehagua (southern volcanic rift of Tenerife), with 17% and 12% respectively.

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

J. L. Lewicki; G. E. Hilley; L. Dobeck

A set of CO2 flux, geochemical, and hydrologic measurement techniques was used to characterize the source of and quantify gaseous and dissolved CO2 discharges from the area of Soda Springs, southeastern Idaho. An eddy covariance system was deployed for approximately one month near a bubbling spring and measured net CO2 fluxes from - 74 to 1147 g m- 2 d- 1. An inversion of measured eddy covariance CO2 fluxes and corresponding modeled source weight functions mapped the surface CO2 flux distribution within and quantified CO2 emission rate (24.9 t d- 1) from a 0.05 km2 area surrounding the spring. Soilmore » CO2 fluxes (< 1 to 52,178 g m- 2 d- 1) were measured within a 0.05 km2 area of diffuse degassing using the accumulation chamber method. The estimated CO2 emission rate from this area was 49 t d- 1. A carbon mass balance approach was used to estimate dissolved CO2 discharges from contributing sources at nine springs and the Soda Springs geyser. Total dissolved inorganic carbon (as CO2) discharge for all sampled groundwater features was 57.1 t d- 1. Of this quantity, approximately 3% was derived from biogenic carbon dissolved in infiltrating groundwater, 35% was derived from carbonate mineral dissolution within the aquifer(s), and 62% was derived from deep source(s). Isotopic compositions of helium (1.74–2.37 Ra) and deeply derived carbon (d13C approximately 3‰) suggested contribution of volatiles from mantle and carbonate sources. Assuming that the deeply derived CO2 discharge estimated for sampled groundwater features (approximately 35 t d- 1) is representative of springs throughout the study area, the total rate of deeply derived CO2 input into the groundwater system within this area could be ~ 350 t d- 1, similar to CO2 emission rates from a number of quiescent volcanoes.« less

Modeling experimental stable isotope results from CO2 adsorption and diffusion experiments

NASA Astrophysics Data System (ADS)

Larson, T. E.

2012-12-01

Transport of carbon dioxide through porous media can be affected by diffusion, advection and adsorption processes. Developing new tools to understand which of these processes dominates migration of CO2 or other gases in the subsurface is important to a wide range of applications including CO2 storage. Whereas advection rates are not affected by isotope substitution in CO2, adsorption and diffusion constants are. For example, differences in the binary diffusion constant calculated between C12O2-He and C13O2-He results in a carbon isotope fractionation whereby the front of the chromatographic peak is enriched in carbon-12 and the tail of the peak is enriched in carbon-13. Interestingly, adsorption is shown to have an opposite, apparent inverse affect whereby the lighter isotopologues of CO2 are preferentially retained by the chromatographic column and the heavier isotopologues are eluted first. This apparent inverse chromatographic effect has been ascribed to Van der Waals dispersion forces. Smaller molar volumes of the heavier isotopologues resulting from increased bond strength (shorter bond length) effectively decreases Van der Waals forces in heavier isotopologues compared to lighter isotopologues. Here we discuss the possible application of stable isotope values measured across chromatographic peaks to differentiate diffusion-dominated from adsorption-dominated transport processes for CO2. Separate 1-dimensional flow-through columns were packed with quartz and illite, and one remained empty. Dry helium was used as a carrier gas. Constant flow rate, temperature and column pressure were maintained. After background CO2 concentrations were minimized and constant, a sustained pulse of CO2 was injected at the head of the column and the effluent was sampled at 4 minute intervals for CO2 concentration, and carbon and oxygen isotope ratios. The quartz-sand packed and empty columns resulted in similar trends in concentration and isotope ratios whereby CO2 concentrations steadily increased and became constant after two pore volumes of CO2 flushed through the column. Carbon and oxygen isotope values of the front of the peak (first pore volume) are 2‰ and 5‰ lower than the injected CO2 values, respectively. These results are fit very well using a mass transfer model that only includes binary diffusion between CO2 and helium that account for isotope substitution in the reduced mass coefficient. In contrast to these diffusion-dominated systems, CO2 break through curves from the illite packed column show strong adsorption effects that include a +180‰ increase in the carbon isotope ratio at the front of the peak followed by a 20‰ decrease. Up to 20 pore volumes of CO2 were flushed through the column before the carbon and oxygen isotope values stabilized to their starting values. These adsorption effects cannot be modeled using mass isotope effects alone, and instead must include additional parameters such as volume effects. These results demonstrate the importance of understanding the isotopic effects of CO2 in different substrates, and potentially offers a tracer tool that can be used to quantify surface area, transport distance, and surface reactivity of CO2. Additional applications may include more affectively determining transfer rates of CO2 across low permeability zones.

Temperature Response of Mesophyll Conductance. Implications for the Determination of Rubisco Enzyme Kinetics and for Limitations to Photosynthesis in Vivo

PubMed Central

Bernacchi, Carl J.; Portis, Archie R.; Nakano, Hiromi; von Caemmerer, Susanne; Long, Stephen P.

2002-01-01

CO2 transfer conductance from the intercellular airspaces of the leaf into the chloroplast, defined as mesophyll conductance (gm), is finite. Therefore, it will limit photosynthesis when CO2 is not saturating, as in C3 leaves in the present atmosphere. Little is known about the processes that determine the magnitude of gm. The process dominating gm is uncertain, though carbonic anhydrase, aquaporins, and the diffusivity of CO2 in water have all been suggested. The response of gm to temperature (10°C–40°C) in mature leaves of tobacco (Nicotiana tabacum L. cv W38) was determined using measurements of leaf carbon dioxide and water vapor exchange, coupled with modulated chlorophyll fluorescence. These measurements revealed a temperature coefficient (Q10) of approximately 2.2 for gm, suggesting control by a protein-facilitated process because the Q10 for diffusion of CO2 in water is about 1.25. Further, gm values are maximal at 35°C to 37.5°C, again suggesting a protein-facilitated process, but with a lower energy of deactivation than Rubisco. Using the temperature response of gm to calculate CO2 at Rubisco, the kinetic parameters of Rubisco were calculated in vivo from 10°C to 40°C. Using these parameters, we determined the limitation imposed on photosynthesis by gm. Despite an exponential rise with temperature, gm does not keep pace with increased capacity for CO2 uptake at the site of Rubisco. The fraction of the total limitations to CO2 uptake within the leaf attributable to gm rose from 0.10 at 10°C to 0.22 at 40°C. This shows that transfer of CO2 from the intercellular air space to Rubisco is a very substantial limitation on photosynthesis, especially at high temperature. PMID:12481082

Temperature-Dependent Lithium-Ion Diffusion and Activation Energy of Li1.2Co0.13Ni0.13Mn0.54O2 Thin-Film Cathode at Nanoscale by Using Electrochemical Strain Microscopy.

PubMed

Yang, Shan; Yan, Binggong; Wu, Jiaxiong; Lu, Li; Zeng, Kaiyang

2017-04-26

This paper presents the in situ mapping of temperature-dependent lithium-ion diffusion at the nanometer level in thin film Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 cathode using electrochemical strain microscopy. The thin-film Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 cathode exhibits higher lithium-ion diffusivities with increasing temperature, which explains the higher capacity observed in the lithium-ion batteries with a Li-rich cathode at elevated temperature. In addition, the activation energy for lithium-ion diffusion can be extracted in an Arrhenius-type plot at the level of grain structure with the assumption that the ionic movement is diffusion controlled. Compared with the grain interiors, the grain boundaries show relatively lower activation energy; hence, it is the preferred diffusion path for lithium ions. This study has bridged the gap between atomistic calculations and traditional macroscopic experiments, showing direct evidence as well as mechanisms for ionic diffusion for Li-rich cathode material.

Development and validation of a portable gas phase standard generation and calibration system for volatile organic compounds

Treesearch

P. Veres; J. B. Gilman; J. M. Roberts; W. C. Kuster; C. Warneke; I. R. Burling; J. de Gouw

2010-01-01

We report on the development of an accurate, portable, dynamic calibration system for volatile organic compounds (VOCs). The Mobile Organic Carbon Calibration System (MOCCS) combines the production of gas-phase VOC standards using permeation or diffusion sources with quantitative total organic carbon (TOC) conversion on a palladium surface to CO2 in the presence of...

Design of an efficient space constrained diffuser for supercritical CO2 turbines

NASA Astrophysics Data System (ADS)

Keep, Joshua A.; Head, Adam J.; Jahn, Ingo H.

2017-03-01

Radial inflow turbines are an arguably relevant architecture for energy extraction from ORC and supercritical CO 2 power cycles. At small scale, design constraints can prescribe high exit velocities for such turbines, which lead to high kinetic energy in the turbine exhaust stream. The inclusion of a suitable diffuser in a radial turbine system allows some exhaust kinetic energy to be recovered as static pressure, thereby ensuring efficient operation of the overall turbine system. In supercritical CO 2 Brayton cycles, the high turbine inlet pressure can lead to a sealing challenge if the rotor is supported from the rotor rear side, due to the seal operating at rotor inlet pressure. An alternative to this is a cantilevered layout with the rotor exit facing the bearing system. While such a layout is attractive for the sealing system, it limits the axial space claim of any diffuser. Previous studies into conical diffuser geometries for supercritical CO 2 have shown that in order to achieve optimal static pressure recovery, longer geometries of a shallower cone angle are necessitated when compared to air. A diffuser with a combined annular-radial arrangement is investigated as a means to package the aforementioned geometric characteristics into a limited space claim for a 100kW radial inflow turbine. Simulation results show that a diffuser of this design can attain static pressure rise coefficients greater than 0.88. This confirms that annular-radial diffusers are a viable design solution for supercritical CO2 radial inflow turbines, thus enabling an alternative cantilevered rotor layout.

Diffuse Carbon Dioxide (CO2) degassing from the summit crater of Pico do Fogo during the 2014-15 eruption, Cape Verde

NASA Astrophysics Data System (ADS)

Rodríguez, Fatima; Dionis, Samara; Padrón, Eleazar; Fernandes, Paulo; Melián, Gladys V.; Pérez, Nemesio M.; Hernández, Pedro A.; Silva, Sónia; Pereira, José Manuel; Cardoso, Nadir; Asensio-Ramos, María; Barrancos, José; Padilla, Germán; Calvo, David; Semedo, Helio

2015-04-01

On January 3, 2015, a new diffuse CO2 degassing survey at the summit crater of Pico do Fogo volcano (2,829 m above sea level) was carried out by ITER/INVOLCAN/UNICV/OVCV research team to investigate the effect of the 2014-15 Fogo eruption on the diffuse degassing through the summit crater. Before the eruption onset on November 23, 2014, these type of surveys were periodically performed by ITER/INVOLCAN/UNICV/OVCV research team since May 2007. The first published data on diffuse CO2 degassing rate from the summit crater of Pico do Fogo volcano (219 ± 36 t d-1) is related to a survey performed on February 2010 (Dionis et al., 2015). Each survey implies about 65 CO2 efflux measurements to obtain a good spatial distribution and cover homogeneously the summit crater area (0.14 km2). Because of the sudden falls of rocks of different sizes inside the summit crater during the January 3 survey, the research team aborted continues working in the summit crater without completing the survey only 32 of the 65 CO2 efflux measurements were performed covering a smaller area (0.065 km2). Observed CO2 efflux values ranged from non detectable (< 1.5 g m-2 d-1) up to 12188 g m-2 d-1 and showed a mean value of 1090.2 g m-2 d-1. The observed CO2 efflux median values from the same sampling sites in previous surveys (83.1 g m-2 d-1 for March 2014; 15.5 g m-2 d-1 for October 2013; 2.3 g m-2 d-1 for April 2013; 14.6 g m-2 d-1 for February 2012; 64.7 g m-2 d-1 for March 2011; 64.5 for Febraury 2010 ) were lower than the median of the January 2015 survey (249.4 g m-2 d-1) suggesting a higher degassing rate for this new survey. The diffuse CO2 emission from the study area of 0.065 km2, within the summit crater, was 74 t d-1 on January 3, 2015, which is a similar degassing rate to those estimated for the same study area on the July 2014 (90 t d-1) and August 2014 (66 t d-1) surveys, and relatively higher than the estimated for October 2012 survey (27 t d-1). Since the diffuse CO2 emission rate on July and August 2014 were 323 and 337 t d-1, respectively, it can be expected a relatively high diffuse CO2 degassing rate from the summit crater of Pico do Fogo for the January 3, 2015 survey (> 300 t d-1). This most recent survey did not cover the hydrothermal alteration zone within the crater, where the highest CO2 efflux measurements are usually recorded. Dionis et al. (2015), Bull. Volcanol., in press;

Spatial and Temporal Correlates of Greenhouse Gas Diffusion from a Hydropower Reservoir in the Southern United States

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

Mosher, Jennifer; Fortner, Allison M.; Phillips, Jana Randolph

Emissions of CO 2 and CH 4 from freshwater reservoirs constitute a globally significant source of atmospheric greenhouse gases (GHGs), but knowledge gaps remain with regard to spatiotemporal drivers of emissions. We document the spatial and seasonal variation in surface diffusion of CO 2 and CH 4 from Douglas Lake, a hydropower reservoir in Tennessee, USA. Monthly estimates across 13 reservoir sites from January to November 2010 indicated that surface diffusions ranged from 236 to 18,806 mg m -2 day -1 for CO 2 and 0 to 0.95 mg m -2 day -1 for CH 4. Next, we developed statisticalmore » models using spatial and physicochemical variables to predict surface diffusions of CO 2 and CH 4. Models explained 22.7 and 20.9% of the variation in CO 2 and CH4 diffusions, respectively, and identified pH, temperature, dissolved oxygen, and Julian day as the most informative important predictors. These findings provide baseline estimates of GHG emissions from a reservoir in eastern temperate North America a region for which estimates of reservoir GHGs emissions are limited. Our statistical models effectively characterized non-linear and threshold relationships between physicochemical predictors and GHG emissions. Further refinement of such models will aid in predicting current GHG emissions in unsampled reservoirs and forecasting future GHG emissions.« less

Spatial and Temporal Correlates of Greenhouse Gas Diffusion from a Hydropower Reservoir in the Southern United States

DOE PAGES

Mosher, Jennifer; Fortner, Allison M.; Phillips, Jana Randolph; ...

2015-10-29

Emissions of CO 2 and CH 4 from freshwater reservoirs constitute a globally significant source of atmospheric greenhouse gases (GHGs), but knowledge gaps remain with regard to spatiotemporal drivers of emissions. We document the spatial and seasonal variation in surface diffusion of CO 2 and CH 4 from Douglas Lake, a hydropower reservoir in Tennessee, USA. Monthly estimates across 13 reservoir sites from January to November 2010 indicated that surface diffusions ranged from 236 to 18,806 mg m -2 day -1 for CO 2 and 0 to 0.95 mg m -2 day -1 for CH 4. Next, we developed statisticalmore » models using spatial and physicochemical variables to predict surface diffusions of CO 2 and CH 4. Models explained 22.7 and 20.9% of the variation in CO 2 and CH4 diffusions, respectively, and identified pH, temperature, dissolved oxygen, and Julian day as the most informative important predictors. These findings provide baseline estimates of GHG emissions from a reservoir in eastern temperate North America a region for which estimates of reservoir GHGs emissions are limited. Our statistical models effectively characterized non-linear and threshold relationships between physicochemical predictors and GHG emissions. Further refinement of such models will aid in predicting current GHG emissions in unsampled reservoirs and forecasting future GHG emissions.« less

Atmospheric dispersion of natural carbon dioxide emissions on Vulcano Island, Italy

NASA Astrophysics Data System (ADS)

Granieri, D.; Carapezza, M. L.; Barberi, F.; Ranaldi, M.; Ricci, T.; Tarchini, L.

2014-07-01

La Fossa quiescent volcano and its surrounding area on the Island of Vulcano (Italy) are characterized by intensive, persistent degassing through both fumaroles and diffuse soil emissions. Periodic degassing crises occur, with marked increase in temperature and steam and gas output (mostly CO2) from crater fumaroles and in CO2 soil diffuse emission from the crater area as well as from the volcano flanks and base. The gas hazard of the most inhabited part of the island, Vulcano Porto, was investigated by simulating the CO2 dispersion in the atmosphere under different wind conditions. The DISGAS (DISpersion of GAS) code, an Eulerian model based on advection-diffusion equations, was used together with the mass-consistent Diagnostic Wind Model. Numerical simulations were validated by measurements of air CO2 concentration inside the village and along the crater's rim by means of a Soil CO2 Automatic Station and a Tunable Diode Laser device. The results show that in the village of Vulcano Porto, the CO2 air concentration is mostly due to local soil degassing, while the contribution from the crater gas emission is negligible at the breathing height for humans and always remains well below the lowest indoor CO2 concentration threshold recommended by the health authorities (1000 ppm). Outdoor excess CO2 maxima up to 200 ppm above local background CO2 air concentration are estimated in the center of the village and up to 100 ppm in other zones. However, in some ground excavations or in basements the health code threshold can be exceeded. In the crater area, because of the combined effect of fumaroles and diffuse soil emissions, CO2 air concentrations can reach 5000-7000 ppm in low-wind conditions and pose a health hazard for visitors.

The influence of the ocean circulation state on ocean carbon storage and CO2 drawdown potential in an Earth system model

NASA Astrophysics Data System (ADS)

Ödalen, Malin; Nycander, Jonas; Oliver, Kevin I. C.; Brodeau, Laurent; Ridgwell, Andy

2018-03-01

During the four most recent glacial cycles, atmospheric CO2 during glacial maxima has been lowered by about 90-100 ppm with respect to interglacials. There is widespread consensus that most of this carbon was partitioned in the ocean. It is, however, still debated which processes were dominant in achieving this increased carbon storage. In this paper, we use an Earth system model of intermediate complexity to explore the sensitivity of ocean carbon storage to ocean circulation state. We carry out a set of simulations in which we run the model to pre-industrial equilibrium, but in which we achieve different states of ocean circulation by changing forcing parameters such as wind stress, ocean diffusivity and atmospheric heat diffusivity. As a consequence, the ensemble members also have different ocean carbon reservoirs, global ocean average temperatures, biological pump efficiencies and conditions for air-sea CO2 disequilibrium. We analyse changes in total ocean carbon storage and separate it into contributions by the solubility pump, the biological pump and the CO2 disequilibrium component. We also relate these contributions to differences in the strength of the ocean overturning circulation. Depending on which ocean forcing parameter is tuned, the origin of the change in carbon storage is different. When wind stress or ocean diapycnal diffusivity is changed, the response of the biological pump gives the most important effect on ocean carbon storage, whereas when atmospheric heat diffusivity or ocean isopycnal diffusivity is changed, the solubility pump and the disequilibrium component are also important and sometimes dominant. Despite this complexity, we obtain a negative linear relationship between total ocean carbon and the combined strength of the northern and southern overturning cells. This relationship is robust to different reservoirs dominating the response to different forcing mechanisms. Finally, we conduct a drawdown experiment in which we investigate the capacity for increased carbon storage by artificially maximising the efficiency of the biological pump in our ensemble members. We conclude that different initial states for an ocean model result in different capacities for ocean carbon storage due to differences in the ocean circulation state and the origin of the carbon in the initial ocean carbon reservoir. This could explain why it is difficult to achieve comparable responses of the ocean carbon pumps in model inter-comparison studies in which the initial states vary between models. We show that this effect of the initial state is quantifiable. The drawdown experiment highlights the importance of the strength of the biological pump in the control state for model studies of increased biological efficiency.

Anomalous Diffuse CO2 Emission Changes at San Vicente Volcano Related to Earthquakes in El Salvador, Central America

NASA Astrophysics Data System (ADS)

Salazar, J.; Hernandez, P.; Perez, N.; Barahona, F.; Olmos, R.; Cartagena, R.; Soriano, T.; Notsu, K.; Lopez, D.

2001-12-01

San Vicente or Chichontepeque (2,180 m a.s.l.) is a composite andesitic volcano located 50 Km east of San Salvador. Its paired edifice rises from the so-called Central Graben, an extensional structure parallel to the Pacific coast, and has been inactive for the last 3000 yrs. Fumaroles (98.2°C ) and hot spring waters are present along radial faults at two localities on the northern slope of the volcano (Aguas Agrias and El Infiernillo). CO2 is the most abundant component in the dry gas (>90%) and its mean isotopic composition (δ 13C(CO2)=-2.11 ‰ and 3He/4He of 6.9 Ra) suggests a magmatic origin for the CO2. These manifestations are supposed to be linked to a 1,200 m depth 250°C reservoir with a CO2 partial pressure of 14 bar extended beneath the volcano (Aiuppa et al., 1997). In February 13, 2001, a 6.6 magnitude earthquake with epicenter about 20 Km W of San Vicente damaged and destroyed many towns and villages in the north area of the volcano causing some deceases. In addition, two seismic swarms were recorded beneath the northeastern flank of the volcano in April and May 2001. Searching for any link between the actual seismic activity and changes in the diffuse CO2 degassing at San Vicente, an NDIR instrument for continuos monitoring of the diffuse CO2 degassing was set up at Aguas Agrias in March 2001. Soil CO2 efflux and several meteorological and soil physical variables were measured in an hourly basis. Very significative pre-seismic and post-seismic relationships have been found in the observed diffuse CO2 efflux temporal variations related to the May 2001 seismic swarms. A sustained 50% increase on the average diffuse CO2 efflux was observed 8 days before the May 8, 5.1 magnitude earthquake. This pre-seismic behaviour may be considered a precursor of the May 2001 seismic swarm at San Vicente volcano. However, about a three-fold increase in the diffuse CO2 efflux was also observed after the intense seismicity recorded on May 8-9. These preliminary results suggest that changes in the fluid pore-pressure within faults/fractures associated to the volcanic roots may be triggering, enhancing and responding (aperture and closure of fractures) to the local seismicity in the area of San Vicente volcano.

OT1_tvelusam_2: HIFI studies of the small-scale structures in the Galactic diffuse clouds with [CII] and [CI

NASA Astrophysics Data System (ADS)

Velusamy, T.

2010-07-01

The 1.9 THz [CII] observations provide a powerful probe of warm diffuse clouds, because they can observe them in emission and are useful as a tracer of their molecular H2 not directly traced by CO or other means. HIFI observations of [CII] provide a high resolution of 12 arcsec, better than that for single dish CO (> 30 arcsec) maps, and much better than HI (>30 arcsec). Thus with HIFI we have an opportunity probe the small scale structures in diffuse clouds in the inner Galaxy at distances > 3 kpc. To study the structure of diffuse ISM gas at small scales we propose HIFI maps of 1.9 THz (158 micron) [CII] line emission in a selection of 16 lines of sight (LOSs) towards the inner Galaxy, which are also being observed as part of the GOT C+ survey of [CII] in the Galactic plane. GOT C+ provides mainly single point spectra without any spatial data. Maps of [CII] will constrain better the cloud properties and models when combining [CII] and HI data. The proposed OTF X map will be along the longitude and latitude centered on 18 selected GOT C+ LOS over a length of 3 arcmin in each direction, which is adequate enough to provide sufficient spatial information on the small scale structures at larger distances (>3 kpc) and to characterize the CII filling factor in the larger beams of the ancillary (HI, CO, and CI data). The [CI] 609 & 370micron and the 12CO(7-6) (which lies within the CI band) are excellent diagnostics of the physical conditions of transition clouds and PDRs. We will use the ratio of the [CI] lines to constrain the kinetic temperature and volume density of the CII/CI/CO transition zones in molecular clouds using radiative transfer codes. We also propose OTF X maps in both the [CI] lines for all CII target LOSs. We anticipate fully resolved structural data in [CII] on at least 300 velocity resolved clouds along with their [CI] emissions. We request a total of 33.2 hrs of HIFI observing time.

CO2 diffusion into pore spaces limits weathering rate of an experimental basalt landscape

USGS Publications Warehouse

van Haren, Joost; Dontsova, Katerina; Barron-Gafford, Greg A.; Troch, Peter A.; Chorover, Jon; DeLong, Stephen B.; Breshears, David D.; Huxman, Travis E.; Pelletier, Jon D.; Saleska, Scott; Zeng, Xubin; Ruiz, Joaquin

2017-01-01

Basalt weathering is a key control over the global carbon cycle, though in situ measurements of carbon cycling are lacking. In an experimental, vegetation-free hillslope containing 330 m3 of ground basalt scoria, we measured real-time inorganic carbon dynamics within the porous media and seepage flow. The hillslope carbon flux (0.6–5.1 mg C m–2 h–1) matched weathering rates of natural basalt landscapes (0.4–8.8 mg C m–2 h–1) despite lacking the expected field-based impediments to weathering. After rainfall, a decrease in CO2 concentration ([CO2]) in pore spaces into solution suggested rapid carbon sequestration but slow reactant supply. Persistent low soil [CO2] implied that diffusion limited CO2 supply, while when sufficiently dry, reaction product concentrations limited further weathering. Strong influence of diffusion could cause spatial heterogeneity of weathering even in natural settings, implying that modeling studies need to include variable soil [CO2] to improve carbon cycling estimates associated with potential carbon sequestration methods.

Sampling Soil CO2 for Isotopic Flux Partitioning: Non Steady State Effects and Methodological Biases

NASA Astrophysics Data System (ADS)

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

2014-12-01

Measurements of δ13C of soil CO2 are used to partition the surface flux into autotrophic and heterotrophic components. Models predict that the δ13CO2 of the soil efflux is perturbed by non-steady state (NSS) diffusive conditions. These could be large enough to render δ13CO2 unsuitable for accurate flux partitioning. Field studies sometimes find correlations between efflux δ13CO2 and flux or temperature, or that efflux δ13CO2 is not correlated as expected with biological drivers. We tested whether NSS effects in semi-natural soil were comparable with those predicted. We compared chamber designs and their sensitivity to changes in efflux δ13CO2. In a natural soil mesocosm, we controlled temperature to generate NSS conditions of CO2 production. We measured the δ13C of soil CO2 using in situ probes to sample the subsurface, and dynamic and forced-diffusion chambers to sample the surface efflux. Over eight hours we raised soil temperature by 4.5 OC to increase microbial respiration. Subsurface CO2 concentration doubled, surface efflux became 13C-depleted by 1 ‰ and subsurface CO2 became 13C-enriched by around 2 ‰. Opposite changes occurred when temperature was lowered and CO2 production was decreasing. Different chamber designs had inherent biases but all detected similar changes in efflux δ13CO2, which were comparable to those predicted. Measurements using dynamic chambers were more 13C-enriched than expected, probably due to advection of CO2 into the chamber. In the mesocosm soil, δ13CO2 of both efflux and subsurface was determined by physical processes of CO2 production and diffusion. Steady state conditions are unlikely to prevail in the field, so spot measurements of δ13CO2 and assumptions based on the theoretical 4.4 ‰ diffusive fractionation will not be accurate for estimating source δ13CO2. Continuous measurements could be integrated over a period suitable to reduce the influence of transient NSS conditions. It will be difficult to disentangle biologically driven changes in soil δ13CO2 from physical controls, particularly as they occur on similar timescales and are driven by the same environmental variables, such as temperature, moisture and daylight.

Net energy payback and CO2 emissions from three midwestern wind farms: An update

USGS Publications Warehouse

White, S.W.

2006-01-01

This paper updates a life-cycle net energy analysis and carbon dioxide emissions analysis of three Midwestern utility-scale wind systems. Both the Energy Payback Ratio (EPR) and CO2 analysis results provide useful data for policy discussions regarding an efficient and low-carbon energy mix. The EPR is the amount of electrical energy produced for the lifetime of the power plant divided by the total amount of energy required to procure and transport the materials, build, operate, and decommission the power plants. The CO2 analysis for each power plant was calculated from the life-cycle energy input data. A previous study also analyzed coal and nuclear fission power plants. At the time of that study, two of the three wind systems had less than a full year of generation data to project the life-cycle energy production. This study updates the analysis of three wind systems with an additional four to eight years of operating data. The EPR for the utility-scale wind systems ranges from a low of 11 for a two-turbine system in Wisconsin to 28 for a 143-turbine system in southwestern Minnesota. The EPR is 11 for coal, 25 for fission with gas centrifuge enriched uranium and 7 for gaseous diffusion enriched uranium. The normalized CO2 emissions, in tonnes of CO2 per GW eh, ranges from 14 to 33 for the wind systems, 974 for coal, and 10 and 34 for nuclear fission using gas centrifuge and gaseous diffusion enriched uranium, respectively. ?? Springer Science+Business Media, LLC 2007.

Device for determining carbon activity through pressure

DOEpatents

Roche, Michael F.

1976-01-01

A hollow iron capsule of annular shape having an interior layer of Fe.sub.0.947 0 and a near absolute internal vacuum is submersed within a molten metal with the inner chamber of the capsule connected to a pressure sensor. Carbon present in the molten metal diffuses through the capsule wall and reacts with the Fe.sub.0.947 0 layer to generate a CO.sub.2 --CO gas mixture within the internal chamber. The total absolute pressure of the gas measured by the pressure sensor is directly proportional to the carbon activity of the molten metal.

Characterization of double oxide system Cu-Cr-O supported on γ-Al2O3

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z.; Kolev, H.; Krstić, J.; Dimitrov, D.; Ivanov, K.; Loncarević, D.; Jovanović, D.; Mitov, I.

2009-09-01

Series of alumina supported chromium-copper catalysts were prepared by co-impregnation method. The samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and UV-visible diffuse reflectance spectroscopy. Dispersion and porosity was also obtained. The experimental and catalytic test results have drawn a conclusion that an interaction between copper and chromium ions takes place. This interaction is responsible for the enhanced catalytic activity of studied catalysts in reaction of total oxidation of industrial formaldehyde production exhaust gas, which contains CO, dimethyl ether and methanol as main components.

Direct-to-diffuse UV Solar Irradiance Ratio for a UV rotating Shadowband Spectroradiometer and a UV Multi-filter Rotating Shadowband Radiometer

NASA Astrophysics Data System (ADS)

Lantz, K.; Kiedron, P.; Petropavlovskikh, I.; Michalsky, J.; Slusser, J.

2008-12-01

. Two spectroradiometers reside that measure direct and diffuse UV solar irradiance are located at the Table Mountain Test Facility, 8 km north of Boulder, CO. The UV- Rotating Shadowband Spectrograph (UV-RSS) measures diffuse and direct solar irradiance from 290 - 400 nm. The UV Multi-Filter Rotating Shadowband Radiometer (UV-MFRSR) measures diffuse and direct solar irradiance in seven 2-nm wide bands, i.e. 300, 305, 311, 317, 325, and 368 nm. The purpose of the work is to compare radiative transfer model calculations (TUV) with the results from the UV-Rotating Shadowband Spectroradiometer (UV-RSS) and the UV-MFRSR to estimate direct-to-diffuse solar irradiance ratios (DDR) that are used to evaluate the possibility of retrieving aerosol single scattering albedo (SSA) under a variety of atmospheric conditions: large and small aerosol loading, large and small surface albedo. For the radiative transfer calculations, total ozone measurements are obtained from a collocated Brewer spectrophotometer.

Anomalous changes of diffuse CO_{2} emission and seismic activity at Teide volcano, Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

García-Hernández, Rubén; Melián, Gladys; D'Auria, Luca; Asensio-Ramos, María; Alonso, Mar; Padilla, Germán D.; Rodríguez, Fátima; Padrón, Eleazar; Barrancos, José; García-Merino, Marta; Amonte, Cecilia; Pérez, Aarón; Calvo, David; Hernández, Pedro A.; Pérez, Nemesio M.

2017-04-01

Tenerife (2034 km2) is the largest of the Canary Islands and hosts four main active volcanic edifices: three volcanic rifts and a central volcanic complex, Las Cañadas, which is characterized by the eruption of differentiated magmas. Laying inside Las Cañadas a twin stratovolcanoes system, Pico Viejo and Teide, has been developed. Although there are no visible gas emanations along the volcanic rifts of Tenerife, the existence of a volcanic-hydrothermal system beneath Teide volcano is suggested by the occurrence of a weak fumarolic system, steamy ground and high rates of diffuse CO2 degassing all around the summit cone of Teide. Soil CO2 efflux surveys have been performed at the summit crater of Teide volcano since 1999, to determine the diffuse CO2 emission from the summit crater and to evaluate the temporal variations of CO2 efflux and their relationships with seismic-volcanic activity. Soil CO2 efflux and soil temperature have been always measured at the same 38 observation sites homogeneously distributed within an area of about 6,972 m2 inside the summit crater. Soil CO2 diffuse effluxes were estimated according to the accumulation chamber method by means of a non-dispersive infrared (NDIR) LICOR-820 CO2 analyzer. Historical seismic activity in Tenerife has been characterized by low- to moderate-magnitude events (M <2.5), and most of the earthquake's epicenters have been clustered in an offshore area SE of Tenerife. However, very few earthquakes have occurred in other areas, including Teide volcano. At 12:18 of January 6, 2017, the Canary Seismic Network belonged to the Instituto Volcanológico de Canarias (INVOLCAN) registered an earthquake of M 2.5 located in the vertical of Teide volcano with a depth of 6.6 km. It was the strongest earthquake located inside Cañadas caldera since 2004. Between October 11 and December 13, 2016, a continuous increase on the diffuse CO2 emission was registered, from 21.3 ± 2.0 to 101.7 ± 20.7 t d-1, suggesting the occurrence of future increase in the seismic-volcanic activity. In fact, this precursory signal preceded the occurrence of the 2.5 seismic event and no significant horizontal and vertical displacements were registered by the Canary GPS network belonged to INVOLCAN. This seismic event was probably due to the increase of fluid pressure in the hydrothermal-magmatic system of Tenerife. With the aim of investigate the relationship of the observed temporal variation on diffuse CO2 emission and the seismic event occurred beneath Teide volcano in January 6, 2016, the anomalous peak of diffuse CO2 emission was tested following the Material Failure Forecast Method (FFM). To do so, a Geochemical Window Precursory Signal (GWPS) was selected between October 11 and December 13, 2016. Plotting the inverse of diffuse CO2 emission rate versus time, the interception of the linear fit of the data with the time axis indicates the theoretical moment when seismicity is most likely to occur. Surprisingly, interception of the linear fit occurred for a time window between January 6 and 9, 2017, showing an excellent correlation with the occurrence of the M 2.5 earthquake registered at Teide in January 6, 2017.

Microfluidic diffusivity meter: a tool to optimize CO2 driven enhanced oil recovery

NASA Astrophysics Data System (ADS)

Puneeth, S. B.; Kim, Young Ho; Goel, Sanket

2017-02-01

As the energy demands continue to swell with growing population and there persists a lack of unexploited oilfields, the prime focus of any nation would be to maximize the oil recovery factor from existing oil fields. CO2-Enhanced oil recovery is a process to improve the recovery of crude oil from an oil field and works at high pressure and in very deep conditions. CO2 and oil are miscible at high pressure, resulting in low viscosity and oil swells. This swelling can be measured based on mathematical calculations in real time and correlated with the CO2 concentration. This process has myriad advantages over its counterparts which include being able to harness oil trapped in reservoirs besides being cheaper and more efficient. A Diffusivity meter is inevitable in the measurement of the diffusion co-efficient of two samples. Diffusivity meters currently available in the market are weighed down by disadvantages like the requirement of large samples for testing, high cost and complexity. This elicits the need for a Microfluidic based diffusivity meter capable of analyzing Nano-liter sample volumes besides being more precise and affordable. The scope of this work involves the design and development of a Microfluidic robust and inexpensive prototype diffusivity meter using a capillary tube and endorsing its performance by comparison of results with known diffusivity range and supervision of the results with an electronic microscope coupled to PC and Data Acquisition System. The prototype produced at the end of the work is expected to outweigh disadvantages in existing products in terms of sample size, efficiency and time saving.

Precursory signals of the 2014-15 Fogo eruption (Cape Verde) detected by surface CO2 emission and heat flow observations

NASA Astrophysics Data System (ADS)

Pérez, Nemesio M.; Dionis, Samara; Fernandes, Paulo; Barrancos, José; Rodríguez, Fátima; Bandomo, Zuleyka; Hernández, Pedro A.; Melián, Gladys V.; Silva, Sónia; Padilla, Germán; Padrón, Eleazar; Cabral, Jeremias; Calvo, David; Asensio-Ramos, María; Pereira, José Manuel; Gonçalves, António A.; Barros, Inocencio; Semedo, Helio

2015-04-01

On November 23, 2014 a new eruption occurred at Fogo volcano (Cape Verde) after 19 years of the last eruptive event in 1995. In the case of the 1995 Fogo eruption, a volcano monitoring program for the volcanic surveillance of Fogo did not exist. On the contrary, a simple and multidisciplinary volcano monitoring program was initiated since 2007 to detect early warning signals of a new volcanic unrest such as the 2014-15 Fogo eruption. Diffuse CO2 emission surveys at the summit crater of Pico do Fogo volcano were periodically carried out from May 2007 to October 2014 to provide this multidisciplinary approach and to monitor potential volcanic activity changes. During this 7 year period, CO2 efflux ranged from non detectable (< 1.5 g m-2 d-1) up to relatively high (61.9 kg m-2 d-1) values. The observed average δ13C- CO2 values related to these diffuse CO2 emission surveys ranged from -22.1 to 1.6 ‰, and surface heat flux measurements, following the method of Dawson (1964), showed also a wide range of values from 0.1 to 460 W m-2. Areas with the highest observed CO2 efflux values were also characterized by a relatively high soil temperature and an intense surface hydrothermal alteration, which supports that degassing process is primary controlled by an advective mechanism generated by geothermal gradients (convection). Two periods of anomalous diffuse CO2 emission were observed between February 2009 to February 2010 and March to August 2014, respectively. Rest of surveys showed the lowest variability on diffuse CO2 emission, ranging from 23 to 186 t d-1 (average = 86 t d-1). The first anomalous period was characterized by a sharp increase on diffuse CO2 emission, suggesting the first magma intrusion beneath Pico do Fogo volcano. This observation is also supported by a significant change on the δ13C- CO2 signature from May 2009 (-10.2 ‰) to February 2010 (-6.1‰) of the diffuse CO2 degassing, indicating an enrichment on the magmatic CO2 component. On February 2010, the diffuse CO2 emission rate was 219 ± 36 t d-1 (Dionis et al., 2015). The second anomalous period started on March 2014, eight months before the 2014-15 Fogo eruption onset, and reached a relatively high value of 337 ± 119 t d-1 on August 30, 2014. It was likely caused by rising of magmatic gases from a second magma intrusion which ended on an eruption. Heat flow temporal evolution during the observation period also shows a quasi-continuous increase before the eruption onset, with the maximum observed heat flow (16.4 ± 3.4 MW) on March 2014. These geochemical and geophysical evidences are clearly precursory signals of the 2014-15 Fogo eruption. Dawson, G.B. (1964), N Z J Geol Geophys 7:155-171; Dionis S. et al. (2015), Bull. Volcanol., in press

Diffusion of Carbon Dioxide in Cordierite-like Structures: a FTIR Imaging Approach

NASA Astrophysics Data System (ADS)

Radica, F.; Bellatreccia, F.; Della Ventura, G.; Freda, C.; Cinque, G.; Cestelli Guidi, M.

2013-12-01

In the last decades microporous and mesoporous minerals have been recognized to be very important materials from both a geological and a technological viewpoint. In this context, cordierite plays a key role since it represents the only case of a widespread microporous mineral able to trap significant amounts of molecular H2O and CO2 [1] under extreme geological conditions, spanning from the amphibolite facies to ultra-high temperature metamorphism to crustal anatexis [2]. The analysis of volatiles in cordierite can be a very useful tool to define the composition of coexisting fluids during its formation, thus a deeper knowledge of their diffusion mechanism through the structure is crucial in petrologic studies. However, it may have significant implications on technological issues such as the design of new strategies for the permanent sequestration of atmospheric CO2. The incorporation of CO2 into cordierite has been studied by several authors [1, 3], who pointed out the extreme difficulty to reach the sample saturation and homogenization, implying that in experimental studies knowledge of the actual distribution of the volatile molecules in the run samples is crucial to derive any scientific conclusion. In this work, we addressed this problem using FTIR imaging. Our experiments were carried out in tandem on natural cordierite and synthetic CO2-free beryl, a mineral which is isostructural with cordierite. All samples were treated in CO2-saturated atmosphere at different pressure, temperature and time conditions using a non end-load piston-cylinder apparatus at INGV. The run products were oriented using a spindle stage, cut and doubly polished, and analyzed using polarized micro-FTIR spectroscopy at INFN-LNF in order to study the distribution across the sample and quantify the CO2 content. Preliminary data show that both pressure and time play a major role on the diffusion of gaseous CO2 in both cordierite and beryl, whereas the effect of temperature is less noticeable. High-resolution FPA (focal-plane-array of detectors) SR (synchrotron radiation)-FTIR imaging was done at beamline B22, Diamond laboratory (Oxford, UK). The data show that the diffusion of CO2 occurs exclusively along the structural channels running along the c-axis direction. Notably, the diffusion path of CO2 does not exceed 200 μm even after 10 days treatment. Sample cracks formed during the experimental runs speed up the gas diffusion; measured CO2 contents along these cracks are up to 4 times higher. Several CO2-rich samples were heat-treated up to 1200 °C using a Linkam heating stage to investigate the rate of CO2 evacuation as a function of temperature. In situ FTIR spectra have shown that the decarbonation process starts around 800 °C. Continuous heating experiments on 60 μm thick slabs pointed out that the diffusion rates are very low; complete CO2 extraction could not be achieved even after 2 hour heating at 1000 °C. [1] Armbruster and Bloss (1982) Am. Mineral. 67, 284-291. [2] Vry et al. (1990) Am. Mineral. 75, 71-88 [3] Le Breton (1989) Contrib. Mineral. Petrol. 103, 387-396.

Interpreting the sub-linear Kennicutt-Schmidt relationship: the case for diffuse molecular gas

NASA Astrophysics Data System (ADS)

Shetty, Rahul; Clark, Paul C.; Klessen, Ralf S.

2014-08-01

Recent statistical analysis of two extragalactic observational surveys strongly indicate a sub-linear Kennicutt-Schmidt (KS) relationship between the star formation rate (ΣSFR) and molecular gas surface density (Σmol). Here, we consider the consequences of these results in the context of common assumptions, as well as observational support for a linear relationship between ΣSFR and the surface density of dense gas. If the CO traced gas depletion time (τ_dep^CO) is constant, and if CO only traces star-forming giant molecular clouds (GMCs), then the physical properties of each GMC must vary, such as the volume densities or star formation rates. Another possibility is that the conversion between CO luminosity and Σmol, the XCO factor, differs from cloud-to-cloud. A more straightforward explanation is that CO permeates the hierarchical interstellar medium, including the filaments and lower density regions within which GMCs are embedded. A number of independent observational results support this description, with the diffuse gas comprising at least 30 per cent of the total molecular content. The CO bright diffuse gas can explain the sub-linear KS relationship, and consequently leads to an increasing τ_dep^CO with Σmol. If ΣSFR linearly correlates with the dense gas surface density, a sub-linear KS relationship indicates that the fraction of diffuse gas fdiff grows with Σmol. In galaxies where Σmol falls towards the outer disc, this description suggests that fdiff also decreases radially.

Estimation of nocturnal CO2 and N2O soil emissions from changes in surface boundary layer mass storage

NASA Astrophysics Data System (ADS)

Grant, Richard H.; Omonode, Rex A.

2018-04-01

Annual budgets of greenhouse and other trace gases require knowledge of the emissions throughout the year. Unfortunately, emissions into the surface boundary layer during stable, calm nocturnal periods are not measurable using most micrometeorological methods due to non-stationarity and uncoupled flow. However, during nocturnal periods with very light winds, carbon dioxide (CO2) and nitrous oxide (N2O) frequently accumulate near the surface and this mass accumulation can be used to determine emissions. Gas concentrations were measured at four heights (one within and three above canopy) and turbulence was measured at three heights above a mature 2.5 m maize canopy from 23 July to 10 September 2015. Nocturnal CO2 and N2O fluxes from the canopy were determined using the accumulation of mass within a 6.3 m control volume and out the top of the control volume within the nocturnal surface boundary layer. Diffusive fluxes were estimated by flux gradient method. The total accumulative and diffusive fluxes during near-calm nights (friction velocities < 0.05 ms-1) averaged 1.16 µmol m-2 s-1 CO2 and 0.53 nmol m-2 s-1 N2O. Fluxes were also measured using chambers. Daily mean CO2 fluxes determined by the accumulation method were 90 to 130 % of those determined using soil chambers. Daily mean N2O fluxes determined by the accumulation method were 60 to 80 % of that determined using soil chambers. The better signal-to-noise ratios of the chamber method for CO2 over N2O, non-stationary flow, assumed Schmidt numbers, and anemometer tilt were likely contributing reasons for the differences in chambers versus accumulated nocturnal mass flux estimates. Near-surface N2O accumulative flux measurements in more homogeneous regions and with greater depth are needed to confirm the conclusion that mass accumulation can be effectively used to estimate soil emissions during nearly calm nights.

Laser-induced desorption determinations of surface diffusion on Rh(111)

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

Seebauer, E.G.; Schmidt, L.D.

Surface diffusion of hydrogen, deuterium and CO on Rh(111) has been investigated by laser-induced thermal desorption (LITD) and compared with previous results for these species on Pt(111) and on other metals. For deuterium in the coverage range 0.02 < theta < 0.33, the pre-exponential factor D/sub 0/ - 8 x 10/sup -2/ cm/sup 2//s, with a diffusion activation energy 3.7 < E/sub diff/ < 4.3 kcal/mol. For CO, E/sub diff/ = 7 kcal/mol, but D/sub 0/ rises from 10/sup -3/ to 10/sup -2/ cm/sup 2//s between theta = 0.01 and 0.40. Values of E/sub diff/ on different surfaces appear tomore » correlate with differences in heats of adsorption in different binding states which form saddle point configurations in surface diffusion. In addition, oxidation reactions on Rh and on several other transition metal surfaces may be limited to CO or H surface diffusion. 30 refs., 3 figs., 1 tab.« less

Localization of (photo)respiration and CO2 re-assimilation in tomato leaves investigated with a reaction-diffusion model

PubMed Central

Berghuijs, Herman N. C.; Yin, Xinyou; Ho, Q. Tri; Verboven, Pieter; Nicolaï, Bart M.

2017-01-01

The rate of photosynthesis depends on the CO2 partial pressure near Rubisco, Cc, which is commonly calculated by models using the overall mesophyll resistance. Such models do not explain the difference between the CO2 level in the intercellular air space and Cc mechanistically. This problem can be overcome by reaction-diffusion models for CO2 transport, production and fixation in leaves. However, most reaction-diffusion models are complex and unattractive for procedures that require a large number of runs, like parameter optimisation. This study provides a simpler reaction-diffusion model. It is parameterized by both leaf physiological and leaf anatomical data. The anatomical data consisted of the thickness of the cell wall, cytosol and stroma, and the area ratios of mesophyll exposed to the intercellular air space to leaf surfaces and exposed chloroplast to exposed mesophyll surfaces. The model was used directly to estimate photosynthetic parameters from a subset of the measured light and CO2 response curves; the remaining data were used for validation. The model predicted light and CO2 response curves reasonably well for 15 days old tomato (cv. Admiro) leaves, if (photo)respiratory CO2 release was assumed to take place in the inner cytosol or in the gaps between the chloroplasts. The model was also used to calculate the fraction of CO2 produced by (photo)respiration that is re-assimilated in the stroma, and this fraction ranged from 56 to 76%. In future research, the model should be further validated to better understand how the re-assimilation of (photo)respired CO2 is affected by environmental conditions and physiological parameters. PMID:28880924

A reaction-diffusion model of CO2 influx into an oocyte

PubMed Central

Somersalo, Erkki; Occhipinti, Rossana; Boron, Walter F.; Calvetti, Daniela

2012-01-01

We have developed and implemented a novel mathematical model for simulating transients in surface pH (pHS) and intracellular pH (pHi) caused by the influx of carbon dioxide (CO2) into a Xenopus oocyte. These transients are important tools for studying gas channels. We assume that the oocyte is a sphere surrounded by a thin layer of unstirred fluid, the extracellular unconvected fluid (EUF), which is in turn surrounded by the well-stirred bulk extracellular fluid (BECF) that represents an infinite reservoir for all solutes. Here, we assume that the oocyte plasma membrane is permeable only to CO2. In both the EUF and intracellular space, solute concentrations can change because of diffusion and reactions. The reactions are the slow equilibration of the CO2 hydration-dehydration reactions and competing equilibria among carbonic acid (H2CO3)/bicarbonate ( HCO3-) and a multitude of non-CO2/HCO3- buffers. Mathematically, the model is described by a coupled system of reaction-diffusion equations that—assuming spherical radial symmetry—we solved using the method of lines with appropriate stiff solvers. In agreement with experimental data (Musa-Aziz et al, PNAS 2009, 106:5406–5411), the model predicts that exposing the cell to extracellular 1.5% CO2/10 mM HCO3- (pH 7.50) causes pHi to fall and pHS to rise rapidly to a peak and then decay. Moreover, the model provides insights into the competition between diffusion and reaction processes when we change the width of the EUF, membrane permeability to CO2, native extra-and intracellular carbonic anhydrase-like activities, the non-CO2/HCO3- (intrinsic) intracellular buffering power, or mobility of intrinsic intracellular buffers. PMID:22728674

Localization of (photo)respiration and CO2 re-assimilation in tomato leaves investigated with a reaction-diffusion model.

PubMed

Berghuijs, Herman N C; Yin, Xinyou; Ho, Q Tri; Retta, Moges A; Verboven, Pieter; Nicolaï, Bart M; Struik, Paul C

2017-01-01

The rate of photosynthesis depends on the CO2 partial pressure near Rubisco, Cc, which is commonly calculated by models using the overall mesophyll resistance. Such models do not explain the difference between the CO2 level in the intercellular air space and Cc mechanistically. This problem can be overcome by reaction-diffusion models for CO2 transport, production and fixation in leaves. However, most reaction-diffusion models are complex and unattractive for procedures that require a large number of runs, like parameter optimisation. This study provides a simpler reaction-diffusion model. It is parameterized by both leaf physiological and leaf anatomical data. The anatomical data consisted of the thickness of the cell wall, cytosol and stroma, and the area ratios of mesophyll exposed to the intercellular air space to leaf surfaces and exposed chloroplast to exposed mesophyll surfaces. The model was used directly to estimate photosynthetic parameters from a subset of the measured light and CO2 response curves; the remaining data were used for validation. The model predicted light and CO2 response curves reasonably well for 15 days old tomato (cv. Admiro) leaves, if (photo)respiratory CO2 release was assumed to take place in the inner cytosol or in the gaps between the chloroplasts. The model was also used to calculate the fraction of CO2 produced by (photo)respiration that is re-assimilated in the stroma, and this fraction ranged from 56 to 76%. In future research, the model should be further validated to better understand how the re-assimilation of (photo)respired CO2 is affected by environmental conditions and physiological parameters.

Convective Instability and Mass Transport of the Diffusion Layer in CO2 Sequestration

NASA Astrophysics Data System (ADS)

Backhaus, S.

2011-12-01

The long-term fate of supercritical (sc) CO2 in saline aquifers is critical to the security of carbon sequestration, an important option for eliminating or reducing the emissions of this most prevalent greenhouse gas. scCO2 is less dense than brine and floats to the top of the aquifer where it is trapped in a metastable state by a geologic feature such as a low permeability cap rock. Dissolution into the underlying brine creates a CO2-brine mixture that is denser than brine, eliminating buoyancy and removing the threat of CO2 escaping back to the atmosphere. If molecular diffusion were the only dissolution mechanism, the CO2 waste stream from a typical large coal-fired electrical power plant may take upward of 10,000 years to no longer pose a threat, however, a convective instability of the dense diffusion boundary layer between the scCO2 and the brine can dramatically increase the dissolution rates, shortening the lifetime of the scCO2 waste pool. We present results of 2D and 3D similitude-correct, laboratory-scale experiments using an analog fluid system. The experiments and flow visualization reveal the onset of the convective instability, the dynamics of the fluid flows during the convective processes, and the long-term mass transfer rates.

Continuous monitoring of diffuse CO2 degassing at Taal volcano, Philippines

NASA Astrophysics Data System (ADS)

Padron, E.; Hernandez Perez, P. A.; Arcilla, C. A.; Lagmay, A. M. A.; Perez, N. M.; Quina, G.; Padilla, G.; Barrancos, J.; Cótchico, M. A.; Melián, G.

2016-12-01

Observing changes in the composition and discharge rates of volcanic gases is an important part of volcanic monitoring programs, because some gases released by progressive depressurization of magma during ascent are highly mobile and reach the surface well before their parental magma. Among volcanic gases, CO2 is widely used in volcano studies and monitoring because it is one of the earliest released gas species from ascending magma, and it is considered conservative. Taal Volcano in Southwest Luzon, Philippines, lies between a volcanic arc front (facing the subduction zone along the Manila Trench) and a volcanic field formed from extension beyond the arc front. Taal Volcano Island is formed by a main tuff cone surrounded by several smaller tuff cones, tuff rings and scoria cones. This island is located in the center of the 30 km wide Taal Caldera, now filled by Taal Lake. To monitor the volcanic activity of Taal volcano is a priority task in the Philippines, because several million people live within a 20-km radius of Taal's caldera rim. In the period from 2010-2011, during a period of volcanic unrest, the main crater lake of Taal volcano released the highest diffuse CO2 emission rates reported to date by volcanic lakes worldwide. The maximum CO2 emission rate measured in the study period occurred two months before the strongest seismic activity recorded during the unrest period (Arpa et al., 2013, Bull Volcanol 75:747). In the light of the excellent results obtained through diffuse degassing studies, an automatic geochemical station to monitor in a continuous mode the diffuse CO2 degassing in a selected location of Taal, was installed in January 2016 to improve the early warning system at the volcano. The station is located at Daang Kastila, at the northern portion of the main crater rim. It measures hourly the diffuse CO2 efflux, atmospheric CO2 concentration, soil water content and temperature, wind speed and direction, air temperature and humidity, rainfall, and barometric pressure. The first results show a time series of CO2 efflux with values in the range 20-690 gm-2d-1.Soil temperature, heavily influenced by rainfall, ranged between 74 and 96ºC. The detailed analysis of diffuse CO2 degassing measured by this automatic station might be a useful geochemical tool for the seismo-volcanic surveillance of Taal.

Atomistic Modeling of Diffusion and Phase Transformations in Metals and Alloys

NASA Astrophysics Data System (ADS)

Purja Pun, Ganga Prasad

Dissertation consists of multiple works. The first part is devoted to self-diffusion along dislocation cores in aluminum followed by the development of embedded atom method potentials for Co, NiAl, CoAl and CoNi systems. The last part focuses on martensitic phase transformation (MPT) in Ni xAl1--x and Al xCoyNi1-- x--y alloys. New calculation methods were developed to predict diffusion coefficients in metal as functions of temperature. Self-diffusion along screw and edge dislocations in aluminum was studied by molecular dynamic (MD) simulations. Three types of simulations were performed with and without (intrinsic) pre-existing vacancies and interstitials in the dislocation core. We found that the diffusion along the screw dislocation was dominated by the intrinsic mechanism, whereas the diffusion along the edge dislocation was dominated by the vacancy mechanism. The diffusion along the screw dislocation was found to be significantly faster than the diffusion along the edge dislocation, and the both diffusivities were in reasonable agreement with experimental data. The intrinsic diffusion mechanism can be associated with the formation of dynamic Frenkel pairs, possibly activated by thermal jogs and/or kinks. The simulations show that at high temperatures the dislocation core becomes an effective source/sink of point defects and the effect of pre-existing defects on the core diffusivity diminishes. First and the foremost ingredient needed in all atomistic computer simulations is the description of interaction between atoms. Interatomic potentials for Co, NiAl, CoAl and CoNi systems were developed within the Embedded Atom Method (EAM) formalism. The binary potentials were based on previously developed accurate potentials for pure Ni and pure Al and pure Co developed in this work. The binaries constitute a version of EAM potential of AlCoNi ternary system. The NiAl potential accurately reproduces a variety of physical properties of the B2-NiAl and L12--Ni3Al phases. The potential is expected to be especially suitable for simulations of hetero-phase interfaces and mechanical behavior of NiAl alloys. Apart from properties of the HCP Co, the new Co potential is accurate enough to reproduce several properties of the FCC Co which were not included in the potential fit. It shows good transferability property. The CoAl potential was fitted to the properties of B2-CoAl phase as in the NiAl fitting where as the NiCo potential was fitted to the ab initio formation energies of some imaginary phases and structures. Effect of chemical composition and uniaxial mechanical stresses was studied on the martensitic phase transformation in B2 type Ni-rich NiAl and AlCoNi alloys. The martensitic phase has a tetragonal crystal structure and can contain multiple twins arranged in domains and plates. The twinned martensites were always formed under the uniaxial compression where as the single variant martensites were the results of the uniaxial tension. The transformation was reversible and characterized by a significant temperature hysteresis. The magnitude of the hysteresis depends on the chemical composition and stress.

NanoSIMS results from olivine-hosted melt embayments: Modeling ascent rate in explosive basaltic eruptions

NASA Astrophysics Data System (ADS)

Lloyd, A. S.; Plank, T.; Ruprecht, P.; Hauri, E. H.; Gonnermann, H. M.; Rose, W. I.

2012-12-01

A critical parameter governing the explosivity of volcanic eruptions is the rate at which magma ascends and degases, because this affects bubble nucleation, coalescence, and ultimately fragmentation. Although several methods have been used to determine magma ascent rates, it remains a poorly constrained parameter for most eruptions. One promising method employs diffusion modeling of H2O and CO2 concentration gradients in melt embayments/open melt inclusions [1,2]. Here we utilize the fine spatial resolution of the nanoSIMS to obtain concentration gradients for five volatile species, improving upon previous efforts that were more limited in spatial resolution (FTIR, [1]) and in number of volatile analytes (H2O only by BSE, [2]). Focusing on explosive basaltic eruptions, for which very little is known about ascent rates, we chose ash and lapilli samples from the Oct 1974 sub-plinian eruption of Volcán de Fuego. Glassy, olivine-hosted embayments with evidence of outlet bubbles were analyzed by nanoSIMS at a minimum distance between spots of 15 μm. Major element zonation in the embayments was investigated by EMP, and high resolution BSE images were captured to complement the nanoSIMS spot measurements for H2O (as in [2]). We report analyses for 5 embayments that vary in length from 100 to 350 μm. Low-solubility volatiles (CO2, H2O, S) decrease towards the embayment outlet, consistent with diffusive reequilibration with the more-degassed surrounding melt. High-solubility volatiles (Cl, F) increase towards the outlet, apparently behaving as magmaphile elements. Major elements exhibit constant concentrations along the embayment, except for a 20-50 μm wide zone near the embayment outlet, perhaps representing a boundary layer at the outlet bubble, where concentrations vary consistent with olivine and clinopyroxene microlite growth. BSE grayscale values are thus affected by both H2O diffusion and major element zonation at the embayment outlet, and cannot be used to estimate H2O concentration gradients [2]. Forward modeling of CO2 and H2O profiles takes into account temperature- and composition-dependent diffusivities and a closed-system degassing path for the exterior magma (as observed in melt inclusions from the same sample). Assuming a constant decompression rate from 200 MPa and an initial composition of 600 ppm CO2 and 4.3 wt% H2O at 1030°C, models yield preliminary results with very rapid ascent times (100 s, or 2 MPa/s). A two-stage model, however, allows slower decompression during CO2 exsolution (0.1 MPa/s) and faster ascent when H2O begins to exsolve (1.5 MPa/s), for total ascent times on the order of 10 to 20 minutes. This example highlights the additional constraints that come from measuring multiple diffusing species. [1] Liu et al, JGR, 2007 [2] Humphreys et al, EPSL, 2008.

Water-carbon trade-off in China's coal power industry.

PubMed

Zhang, Chao; Anadon, Laura Diaz; Mo, Hongpin; Zhao, Zhongnan; Liu, Zhu

2014-10-07

The energy sector is increasingly facing water scarcity constraints in many regions around the globe, especially in China, where the unprecedented large-scale construction of coal-fired thermal power plants is taking place in its extremely arid northwest regions. As a response to water scarcity, air-cooled coal power plants have experienced dramatic diffusion in China since the middle 2000s. By the end of 2012, air-cooled coal-fired thermal power plants in China amounted to 112 GW, making up 14% of China's thermal power generation capacity. But the water conservation benefit of air-cooled units is achieved at the cost of lower thermal efficiency and consequently higher carbon emission intensity. We estimate that in 2012 the deployment of air-cooled units contributed an additional 24.3-31.9 million tonnes of CO2 emissions (equivalent to 0.7-1.0% of the total CO2 emissions by China's electric power sector), while saving 832-942 million m(3) of consumptive water use (about 60% of the total annual water use of Beijing) when compared to a scenario with water-cooled plants. Additional CO2 emissions from air-cooled plants largely offset the CO2 emissions reduction benefits from Chinese policies of retiring small and outdated coal plants. This water-carbon trade-off is poised to become even more significant by 2020, as air-cooled units are expected to grow by a factor of 2-260 GW, accounting for 22% of China's total coal-fired power generation capacity.

Gas emissions, minerals, and tars associated with three coal fires, Powder River Basin, USA.

PubMed

Engle, Mark A; Radke, Lawrence F; Heffern, Edward L; O'Keefe, Jennifer M K; Hower, James C; Smeltzer, Charles D; Hower, Judith M; Olea, Ricardo A; Eatwell, Robert J; Blake, Donald R; Emsbo-Mattingly, Stephen D; Stout, Scott A; Queen, Gerald; Aggen, Kerry L; Kolker, Allan; Prakash, Anupma; Henke, Kevin R; Stracher, Glenn B; Schroeder, Paul A; Román-Colón, Yomayra; ter Schure, Arnout

2012-03-15

Ground-based surveys of three coal fires and airborne surveys of two of the fires were conducted near Sheridan, Wyoming. The fires occur in natural outcrops and in abandoned mines, all containing Paleocene-age subbituminous coals. Diffuse (carbon dioxide (CO(2)) only) and vent (CO(2), carbon monoxide (CO), methane, hydrogen sulfide (H(2)S), and elemental mercury) emission estimates were made for each of the fires. Additionally, gas samples were collected for volatile organic compound (VOC) analysis and showed a large range in variation between vents. The fires produce locally dangerous levels of CO, CO(2), H(2)S, and benzene, among other gases. At one fire in an abandoned coal mine, trends in gas and tar composition followed a change in topography. Total CO(2) fluxes for the fires from airborne, ground-based, and rate of fire advancement estimates ranged from 0.9 to 780mg/s/m(2) and are comparable to other coal fires worldwide. Samples of tar and coal-fire minerals collected from the mouth of vents provided insight into the behavior and formation of the coal fires. Published by Elsevier B.V.

Spatially Resolved Measurements of CO2 and CH4 Concentration and Gas-Exchange Velocity Highly Influence Carbon-Emission Estimates of Reservoirs

PubMed Central

2017-01-01

The magnitude of diffusive carbon dioxide (CO2) and methane (CH4) emission from man-made reservoirs is uncertain because the spatial variability generally is not well-represented. Here, we examine the spatial variability and its drivers for partial pressure, gas-exchange velocity (k), and diffusive flux of CO2 and CH4 in three tropical reservoirs using spatially resolved measurements of both gas concentrations and k. We observed high spatial variability in CO2 and CH4 concentrations and flux within all three reservoirs, with river inflow areas generally displaying elevated CH4 concentrations. Conversely, areas close to the dam are generally characterized by low concentrations and are therefore not likely to be representative for the whole system. A large share (44–83%) of the within-reservoir variability of gas concentration was explained by dissolved oxygen, pH, chlorophyll, water depth, and within-reservoir location. High spatial variability in k was observed, and kCH4 was persistently higher (on average, 2.5 times more) than kCO2. Not accounting for the within-reservoir variability in concentrations and k may lead to up to 80% underestimation of whole-system diffusive emission of CO2 and CH4. Our findings provide valuable information on how to develop field-sampling strategies to reliably capture the spatial heterogeneity of diffusive carbon fluxes from reservoirs. PMID:29257874

Self and transport diffusivity of CO2 in the metal-organic framework MIL-47(V) explored by quasi-elastic neutron scattering experiments and molecular dynamics simulations.

PubMed

Salles, Fabrice; Jobic, Hervé; Devic, Thomas; Llewellyn, Philip L; Serre, Christian; Férey, Gérard; Maurin, Guillaume

2010-01-26

Quasi-elastic neutron scattering measurements are combined with molecular dynamics simulations to determine the self-diffusivity, corrected diffusivity, and transport diffusivity of CO(2) in the metal-organic framework MIL-47(V) (MIL = Materials Institut Lavoisier) over a wide range of loading. The force field used for describing the host/guest interactions is first validated on the thermodynamics of the MIL-47(V)/CO(2) system, prior to being transferred to the investigations of the dynamics. A decreasing profile is then deduced for D(s) and D(o) whereas D(t) presents a non monotonous evolution with a slight decrease at low loading followed by a sharp increase at higher loading. Such decrease of D(t) which has never been evidenced in any microporous systems comes from the atypical evolution of the thermodynamic correction factor that reaches values below 1 at low loading. This implies that, due to intermolecular interactions, the CO(2) molecules in MIL-47(V) do not behave like an ideal gas. Further, molecular simulations enabled us to elucidate unambiguously a 3D diffusion mechanism within the pores of MIL-47(V).

Molecular dynamic simulations of selective self-diffusion of CH4/CO2/H2O/N2 in coal

NASA Astrophysics Data System (ADS)

Song, Y.; Jiang, B.; Li, F. L.

2017-06-01

The self-diffusion coefficients (D) of CH4/CO2/H2O/N2 at a relatively broad range of temperatures(298.15∼ 458.15K)and pressures (1∼6MPa) under the NPT, NPH, NVE, and NVT ensembles were obtained after the calculations of molecular mechanics(MM), annealing kinetics(AK), giant canonical Monte Carlo(GCMC), and molecular dynamics (MD) based on Wiser bituminous coal model (WM). The Ds of the adsorbates at the saturated adsorption configurations are D CH4418K. The average swelling ratios manifest as H2O (14.7∼35.18%)>CO2 (13.38∼32.25%)>CH4 (15.35∼23.71%)> N2 (11.47∼22.14%) (NPH, 1∼6MPa). There exits differences in D, swelling ratios and E among various ensembles, indicating that the selection of ensembles has an important influence on the MD calculations for self-diffusion coefficients.

Soil Carbon Dioxide Production and Surface Fluxes: Subsurface Physical Controls

NASA Astrophysics Data System (ADS)

Risk, D.; Kellman, L.; Beltrami, H.

Soil respiration is a critical determinant of landscape carbon balance. Variations in soil temperature and moisture patterns are important physical processes controlling soil respiration which need to be better understood. Relationships between soil respi- ration and physical controls are typically addressed using only surface flux data but other methods also exist which permit more rigorous interpretation of soil respira- tion processes. Here we use a combination of subsurface CO_{2} concentrations, surface CO_{2} fluxes and detailed physical monitoring of the subsurface envi- ronment to examine physical controls on soil CO_{2} production at four climate observatories in Eastern Canada. Results indicate that subsurface CO_{2} produc- tion is more strongly correlated to the subsurface thermal environment than the surface CO_{2} flux. Soil moisture was also found to have an important influence on sub- surface CO_{2} production, particularly in relation to the soil moisture - soil profile diffusivity relationship. Non-diffusive profile CO_{2} transport appears to be im- portant at these sites, resulting in a de-coupling of summertime surface fluxes from subsurface processes and violating assumptions that surface CO_{2} emissions are the result solely of diffusion. These results have implications for the study of soil respiration across a broad range of terrestrial environments.

Geochemical monitoring of Taal volcano (Philippines) by means of diffuse CO2 degassing studies

NASA Astrophysics Data System (ADS)

Padrón, Eleazar; Hernández, Pedro A.; Arcilla, Carlo; Pérez, Nemesio M.; Lagmay, Alfredo M.; Rodríguez, Fátima; Quina, Gerald; Alonso, Mar; Padilla, Germán D.; Aurelio, Mario A.

2017-04-01

Observing changes in the discharge rate of CO2 is an important part of volcanic monitoring programs, because it is released by progressive depressurization of magma during ascent and reach the surface well before their parental magma. Taal Volcano in Southwest Luzon, Philippines, lies between a volcanic arc front facing the subduction zone along the Manila Trench and a volcanic field formed from extension beyond the arc front. Taal Volcano Island is formed by a main tuff cone surrounded by several smaller tuff cones, tuff rings and scoria cones. This island is located in the center of the 30 km wide Taal Caldera, now filled by Taal Lake. To monitor the volcanic activity of Taal volcano is a priority task in the Philippines, because several million people live within a 20-km radius of Taal's caldera rim. During the last period of volcanic unrest from 2010 to 2011, the main crater lake of Taal volcano released the highest diffuse CO2 emission rates through the water surface reported to date by volcanic lakes worldwide. The maximum CO2 emission rate measured in the study period occurred two months before the strongest seismic activity recorded during the unrest period (Arpa et al., 2013, Bull Volcanol 75:747). After the unrest period, diffuse CO2 emission has remained in the range 532-860 t/d in the period 2013-2016. In January 2016, an automatic geochemical station to monitor in a continuous mode the diffuse CO2 degassing in a selected location of Taal, was installed in January 2016 to improve the early warning system at the volcano. The station is located at Daang Kastila, at the northern portion of the main crater rim. It measures hourly the diffuse CO2 efflux, atmospheric CO2 concentration, soil water content and temperature, wind speed and direction, air temperature and humidity, rainfall, and barometric pressure. The 2016 time series show CO2 efflux values in the range 20-690 g m-2 d-1.Soil temperature, heavily influenced by rainfall, ranged between 74 and 96oC. Although short-temp fluctuations in the diffuse CO2 emission time series at Daang Kastila were partially driven by meteorological parameters, the main CO2 efflux changes were not driven by fluctuations of meteorological variables such as wind speed or barometric pressure and seem clearly to be associated with fluid pressure fluctuations in the volcanic system. These results showed the potential of applying continuous and discrete monitoring of soil CO2 efflux to improve and optimize the detection of early warning signals of future volcanic unrest at Taal volcano.

Site-specific hydration and dehydration of San Carlos olivine

NASA Astrophysics Data System (ADS)

Ferriss, E.; Plank, T. A.; Walker, D.

2016-12-01

Hydrogen incorporation and diffusion in olivine is critical to understanding fundamental Earth processes such as mantle rheology, plate tectonics, melt generation and magma ascent. Interpreting measured H profiles in olivine requires a more comprehensive understanding of H point defect reactions than currently exists because H diffusivity (D) ranges over 6 orders of magnitude, from slow diffusing H incorporated as (4H+)Si­ [1] to rapid `proton-polaron' bulk H diffusion [2]. Here we present the first experiments on H diffusing into and then out of Fe-bearing olivine using the whole-block method [3], which allows a finely-resolved time series of H profiles in 3 crystallographic directions using the same sample for all dehydration steps. A piece of nearly-dry, oriented San Carlos olivine was hydrated in a piston cylinder apparatus using H2O and solid buffers of Ni/NiO and San Carlos olivine and enstatite at 800 °C and 10 kbar for 17.5 hours, just long enough to saturate the `proton-polaron' mechanism. The sample was then dehydrated in a CO/CO2 gas-mixing furnace at 800°C and 10-14 bar fO2 for total heating times of 1, 3, 7, 13, 19, 43, and 68 hrs, at which point most, but not all, of the H had left the crystal. FTIR profiles at 1, 3, and 7 hours show bulk H profiles consistent with `proton-polaron' diffusion. Later the pace of dehydration slowed, and in several cases the bulk H profile shape differed from what would be expected during simple diffusive loss. The small peak at 3600 cm-1, (4H+)Si, remained essentially unchanged throughout all experiments. The peak at 3573 cm-1, (Ti4+)Mg(2H+)Mg, was initially present but tiny, grew to become the largest peak after hydration, and then during dehydration returned to its initial height. The apparent diffusivity of this peak during hydration and the initial stages of dehydration is 4 orders of magnitude faster than the same peak in synthetic forsterite [2]. Peaks at 3542, 3525, 3489, and 3480 cm-1 were not present initially, grew during hydration, and were removed completely during dehydration. No lower-wavenumber H peaks were observed. These results represent a major step toward reconciling the peak-specific understanding of H diffusion [1] with the 2-mechanism H bulk diffusion model [2]. [1] Padrón-Navarta et al. 2014 [2] Kohlstedt & Mackwell 1998 [3] Ferriss et al. 2015

Using a simple apparatus to measure direct and diffuse photosynthetically active radiation at remote locations.

PubMed

Cruse, Michael J; Kucharik, Christopher J; Norman, John M

2015-01-01

Plant canopy interception of photosynthetically active radiation (PAR) drives carbon dioxide (CO2), water and energy cycling in the soil-plant-atmosphere system. Quantifying intercepted PAR requires accurate measurements of total incident PAR above canopies and direct beam and diffuse PAR components. While some regional data sets include these data, e.g. from Atmospheric Radiation Measurement (ARM) Program sites, they are not often applicable to local research sites because of the variable nature (spatial and temporal) of environmental variables that influence incoming PAR. Currently available instrumentation that measures diffuse and direct beam radiation separately can be cost prohibitive and require frequent adjustments. Alternatively, generalized empirical relationships that relate atmospheric variables and radiation components can be used but require assumptions that increase the potential for error. Our goal here was to construct and test a cheaper, highly portable instrument alternative that could be used at remote field sites to measure total, diffuse and direct beam PAR for extended time periods without supervision. The apparatus tested here uses a fabricated, solar powered rotating shadowband and other commercially available parts to collect continuous hourly PAR data. Measurements of total incident PAR had nearly a one-to-one relationship with total incident radiation measurements taken at the same research site by an unobstructed point quantum sensor. Additionally, measurements of diffuse PAR compared favorably with modeled estimates from previously published data, but displayed significant differences that were attributed to the important influence of rapidly changing local environmental conditions. The cost of the system is about 50% less than comparable commercially available systems that require periodic, but not continual adjustments. Overall, the data produced using this apparatus indicates that this instrumentation has the potential to support ecological research via a relatively inexpensive method to collect continuous measurements of total, direct beam and diffuse PAR in remote locations.

Using a Simple Apparatus to Measure Direct and Diffuse Photosynthetically Active Radiation at Remote Locations

PubMed Central

Cruse, Michael J.; Kucharik, Christopher J.; Norman, John M.

2015-01-01

Plant canopy interception of photosynthetically active radiation (PAR) drives carbon dioxide (CO2), water and energy cycling in the soil-plant-atmosphere system. Quantifying intercepted PAR requires accurate measurements of total incident PAR above canopies and direct beam and diffuse PAR components. While some regional data sets include these data, e.g. from Atmospheric Radiation Measurement (ARM) Program sites, they are not often applicable to local research sites because of the variable nature (spatial and temporal) of environmental variables that influence incoming PAR. Currently available instrumentation that measures diffuse and direct beam radiation separately can be cost prohibitive and require frequent adjustments. Alternatively, generalized empirical relationships that relate atmospheric variables and radiation components can be used but require assumptions that increase the potential for error. Our goal here was to construct and test a cheaper, highly portable instrument alternative that could be used at remote field sites to measure total, diffuse and direct beam PAR for extended time periods without supervision. The apparatus tested here uses a fabricated, solar powered rotating shadowband and other commercially available parts to collect continuous hourly PAR data. Measurements of total incident PAR had nearly a one-to-one relationship with total incident radiation measurements taken at the same research site by an unobstructed point quantum sensor. Additionally, measurements of diffuse PAR compared favorably with modeled estimates from previously published data, but displayed significant differences that were attributed to the important influence of rapidly changing local environmental conditions. The cost of the system is about 50% less than comparable commercially available systems that require periodic, but not continual adjustments. Overall, the data produced using this apparatus indicates that this instrumentation has the potential to support ecological research via a relatively inexpensive method to collect continuous measurements of total, direct beam and diffuse PAR in remote locations. PMID:25668208

The CO Transition from Diffuse Molecular Gas to Dense Clouds

NASA Astrophysics Data System (ADS)

Rice, Johnathan S.; Federman, Steven

2017-06-01

The atomic to molecular transitions occurring in diffuse interstellar gas surrounding molecular clouds are affected by the local physical conditions (density and temperature) and the radiation field penetrating the material. Our optical observations of CH, CH^{+}, and CN absorption from McDonald Observatory and the European Southern Observatory are useful tracers of this gas and provide the velocity structure needed for analyzing lower resolution ultraviolet observations of CO and H_{2} absorption from Far Ultraviolet Spectroscopic Explorer. We explore the changing environment between diffuse and dense gas by using the column densities and excitation temperatures from CO and H_{2} to determine the gas density. The resulting gas densities from this method are compared to densities inferred from other methods such as C_{2} and CN chemistry. The densities allow us to interpret the trends from the combined set of tracers. Groupings of sight lines, such as those toward h and χ Persei or Chameleon provide a chance for further characterization of the environment. The Chameleon region in particular helps illuminate CO-dark gas, which is not associated with emission from H I at 21 cm or from CO at 2.6 mm. Expanding this analysis to include emission data from the GOT C+ survey allows the further characterization of neutral diffuse gas, including CO-dark gas.

Full Characterization of CO2-Oil Properties On-Chip: Solubility, Diffusivity, Extraction Pressure, Miscibility, and Contact Angle.

PubMed

Sharbatian, Atena; Abedini, Ali; Qi, ZhenBang; Sinton, David

2018-02-20

Carbon capture, storage, and utilization technologies target a reduction in net CO 2 emissions to mitigate greenhouse gas effects. The largest such projects worldwide involve storing CO 2 through enhanced oil recovery-a technologically and economically feasible approach that combines both storage and oil recovery. Successful implementation relies on detailed measurements of CO 2 -oil properties at relevant reservoir conditions (P = 2.0-13.0 MPa and T = 23 and 50 °C). In this paper, we demonstrate a microfluidic method to quantify the comprehensive suite of mutual properties of a CO 2 and crude oil mixture including solubility, diffusivity, extraction pressure, minimum miscibility pressure (MMP), and contact angle. The time-lapse oil swelling/extraction in response to CO 2 exposure under stepwise increasing pressure was quantified via fluorescence microscopy, using the inherent fluorescence property of the oil. The CO 2 solubilities and diffusion coefficients were determined from the swelling process with measurements in strong agreement with previous results. The CO 2 -oil MMP was determined from the subsequent oil extraction process with measurements within 5% of previous values. In addition, the oil-CO 2 -silicon contact angle was measured throughout the process, with contact angle increasing with pressure. In contrast with conventional methods, which require days and ∼500 mL of fluid sample, the approach here provides a comprehensive suite of measurements, 100-fold faster with less than 1 μL of sample, and an opportunity to better inform large-scale CO 2 projects.

Enzyme-aided extraction of lycopene from high-pigment tomato cultivars by supercritical carbon dioxide.

PubMed

Lenucci, Marcello Salvatore; De Caroli, Monica; Marrese, Pier Paolo; Iurlaro, Andrea; Rescio, Leonardo; Böhm, Volker; Dalessandro, Giuseppe; Piro, Gabriella

2015-03-01

This work reports a novel enzyme-assisted process for lycopene concentration into a freeze-dried tomato matrix and describes the results of laboratory scale lycopene supercritical CO2 (SC-CO2) extractions carried out with untreated (control) and enzyme-digested matrices. The combined use of food-grade commercial plant cell-wall glycosidases (Celluclast/Novozyme plus Viscozyme) allows to increase lycopene (∼153%) and lipid (∼137%) concentration in the matrix and rises substrate load onto the extraction vessel (∼46%) compared to the control. The addition of an oleaginous co-matrix (hazelnut seeds) to the tomato matrix (1:1 by weight) increases CO2 diffusion through the highly dense enzyme-treated matrix bed and provides lipids that are co-extracted increasing lycopene yield. Under the same operative conditions (50 MPa, 86 °C, 4 mL min(-1) SC-CO2 flow) extraction yield from control and Celluclast/Novozyme+Viscozyme-treated tomato matrix/co-matrix mixtures was similar, exceeding 75% after 4.5h of extraction. However, the total extracted lycopene was ∼3 times higher in enzyme-treated matrix than control. Copyright © 2014 Elsevier Ltd. All rights reserved.

Constraining Gas Diffusivity-Soil Water Content Relationships in Forest Soils Using Surface Chamber Fluxes and Depth Profiles of Multiple Trace Gases

NASA Astrophysics Data System (ADS)

Dore, J. E.; Kaiser, K.; Seybold, E. C.; McGlynn, B. L.

2012-12-01

Forest soils are sources of carbon dioxide (CO2) to the atmosphere and can act as either sources or sinks of methane (CH4) and nitrous oxide (N2O), depending on redox conditions and other factors. Soil moisture is an important control on microbial activity, redox conditions and gas diffusivity. Direct chamber measurements of soil-air CO2 fluxes are facilitated by the availability of sensitive, portable infrared sensors; however, corresponding CH4 and N2O fluxes typically require the collection of time-course physical samples from the chamber with subsequent analyses by gas chromatography (GC). Vertical profiles of soil gas concentrations may also be used to derive CH4 and N2O fluxes by the gradient method; this method requires much less time and many fewer GC samples than the direct chamber method, but requires that effective soil gas diffusivities are known. In practice, soil gas diffusivity is often difficult to accurately estimate using a modeling approach. In our study, we apply both the chamber and gradient methods to estimate soil trace gas fluxes across a complex Rocky Mountain forested watershed in central Montana. We combine chamber flux measurements of CO2 (by infrared sensor) and CH4 and N2O (by GC) with co-located soil gas profiles to determine effective diffusivity in soil for each gas simultaneously, over-determining the diffusion equations and providing constraints on both the chamber and gradient methodologies. We then relate these soil gas diffusivities to soil type and volumetric water content in an effort to arrive at empirical parameterizations that may be used to estimate gas diffusivities across the watershed, thereby facilitating more accurate, frequent and widespread gradient-based measurements of trace gas fluxes across our study system. Our empirical approach to constraining soil gas diffusivity is well suited for trace gas flux studies over complex landscapes in general.

Gross CO2 and CH4 emissions from the Nam Ngum and Nam Leuk sub-tropical reservoirs in Lao PDR.

PubMed

Chanudet, Vincent; Descloux, Stéphane; Harby, Atle; Sundt, Håkon; Hansen, Bjørn Henrik; Brakstad, Odd; Serça, Dominique; Guerin, Frédéric

2011-11-15

Gross CO2 and CH4 emissions (degassing and diffusion from the reservoir) and the carbon balance were assessed in 2009-2010 in two Southeast Asian sub-tropical reservoirs: the Nam Ngum and Nam Leuk Reservoirs (Lao PDR). These two reservoirs are within the same climatic area but differ mainly in age, size, residence time and initial biomass stock. The Nam Leuk Reservoir was impounded in 1999 after partial vegetation clearance and burning. However, GHG emissions are still significant 10 years after impoundment. CH4 diffusive flux ranged from 0.8 (January 2010) to 11.9 mmol m(-2) d(-1) (April 2009) and CO2 diffusive flux ranged from -10.6 (October 2009) to 38.2 mmol m(-2) d(-1) (April 2009). These values are comparable to other tropical reservoirs. Moreover, degassing fluxes at the outlet of the powerhouse downstream of the turbines were very low. The tentative annual carbon balance calculation indicates that this reservoir was a carbon source with an annual carbon export (atmosphere+downstream river) of about 2.2±1.0 GgC yr(-1). The Nam Ngum Reservoir was impounded in 1971 without any significant biomass removal. Diffusive and degassing CO2 and CH4 fluxes were lower than for other tropical reservoirs. Particularly, CO2 diffusive fluxes were always negative with values ranging from -21.2 (April 2009) to -2.7 mmol m(-2) d(-1) (January 2010). CH4 diffusive flux ranged from 0.1 (October 2009) to 0.6 mmol m(-2) d(-1) (April 2009) and no degassing downstream of the turbines was measured. As a consequence of these low values, the reservoir was a carbon sink with an estimated annual uptake of - 53±35 GgC yr(-1). Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of fuel composition and differential diffusion on flame stabilization in reacting syngas jets in turbulent cross-flow

DOE PAGES

Minamoto, Yuki; Kolla, Hemanth; Grout, Ray W.; ...

2015-07-24

Here, three-dimensional direct numerical simulation results of a transverse syngas fuel jet in turbulent cross-flow of air are analyzed to study the influence of varying volume fractions of CO relative to H 2 in the fuel composition on the near field flame stabilization. The mean flame stabilizes at a similar location for CO-lean and CO-rich cases despite the trend suggested by their laminar flame speed, which is higher for the CO-lean condition. To identify local mixtures having favorable mixture conditions for flame stabilization, explosive zones are defined using a chemical explosive mode timescale. The explosive zones related to flame stabilizationmore » are located in relatively low velocity regions. The explosive zones are characterized by excess hydrogen transported solely by differential diffusion, in the absence of intense turbulent mixing or scalar dissipation rate. The conditional averages show that differential diffusion is negatively correlated with turbulent mixing. Moreover, the local turbulent Reynolds number is insufficient to estimate the magnitude of the differential diffusion effect. Alternatively, the Karlovitz number provides a better indicator of the importance of differential diffusion. A comparison of the variations of differential diffusion, turbulent mixing, heat release rate and probability of encountering explosive zones demonstrates that differential diffusion predominantly plays an important role for mixture preparation and initiation of chemical reactions, closely followed by intense chemical reactions sustained by sufficient downstream turbulent mixing. The mechanism by which differential diffusion contributes to mixture preparation is investigated using the Takeno Flame Index. The mean Flame Index, based on the combined fuel species, shows that the overall extent of premixing is not intense in the upstream regions. However, the Flame Index computed based on individual contribution of H 2 or CO species reveals that hydrogen contributes significantly to premixing, particularly in explosive zones in the upstream leeward region, i.e. at the preferred flame stabilization location. Therefore, a small amount of H 2 diffuses much faster than CO, creating relatively homogeneous mixture pockets depending on the competition with turbulent mixing. These pockets, together with high H 2 reactivity, contribute to stabilizing the flame at a consistent location regardless of the CO concentration in the fuel for the present range of DNS conditions.« less

Composition and stability of the condensate observed at the Viking Lander 2 site on Mars

NASA Astrophysics Data System (ADS)

Hart, H. M.; Jakosky, B. M.

1986-04-01

Surface energy balance and near-surface temperature data from the Viking Lander 2 site taken during the first winter that condensated were observed and analyzed to determine the relative stability of CO2 and H2O frosts. The CO2 frost stability is calculated with an equilibrium surface energy balance model, i.e., the total energy incident on a frost surface is compared with the blackbody energy emitted by the surface. The energy sources considered were IR emission from the atmosphere, sunlight, and the sensible heat flux from the atmosphere. H2O stability was examined as a function of buoyant diffusion and turbulent mixing processes which could remove saturated near-surface gases. The CO2 frost is found to be sufficiently unstable at the time the condensate was observed on the ground, so all CO2 ice deposited at night would boil away in a few hours of sunlight. CO2 ice would not form during a dust storm. Water frost would be stable during the condensate observations, since sublimation would occur at a rate below 1 micron/day. A stable winter thickness of 10 microns is projected for the water ice.

Composition and stability of the condensate observed at the Viking Lander 2 site on Mars

NASA Technical Reports Server (NTRS)

Hart, H. M.; Jakosky, B. M.

1986-01-01

Surface energy balance and near-surface temperature data from the Viking Lander 2 site taken during the first winter that condensated were observed and analyzed to determine the relative stability of CO2 and H2O frosts. The CO2 frost stability is calculated with an equilibrium surface energy balance model, i.e., the total energy incident on a frost surface is compared with the blackbody energy emitted by the surface. The energy sources considered were IR emission from the atmosphere, sunlight, and the sensible heat flux from the atmosphere. H2O stability was examined as a function of buoyant diffusion and turbulent mixing processes which could remove saturated near-surface gases. The CO2 frost is found to be sufficiently unstable at the time the condensate was observed on the ground, so all CO2 ice deposited at night would boil away in a few hours of sunlight. CO2 ice would not form during a dust storm. Water frost would be stable during the condensate observations, since sublimation would occur at a rate below 1 micron/day. A stable winter thickness of 10 microns is projected for the water ice.

Imaging diffuse clouds: bright and dark gas mapped in CO

NASA Astrophysics Data System (ADS)

Liszt, H. S.; Pety, J.

2012-05-01

Aims: We wish to relate the degree scale structure of galactic diffuse clouds to sub-arcsecond atomic and molecular absorption spectra obtained against extragalactic continuum background sources. Methods: We used the ARO 12 m telescope to map J = 1-0 CO emission at 1' resolution over 30' fields around the positions of 11 background sources occulted by 20 molecular absorption line components, of which 11 had CO emission counterparts. We compared maps of CO emission to sub-arcsec atomic and molecular absorption spectra and to the large-scale distribution of interstellar reddening. Results: 1) The same clouds, identified by their velocity, were seen in absorption and emission and atomic and molecular phases, not necessarily in the same direction. Sub-arcsecond absorption spectra are a preview of what is seen in CO emission away from the continuum. 2) The CO emission structure was amorphous in 9 cases, quasi-periodic or wave-like around B0528+134 and tangled and filamentary around BL Lac. 3) Strong emission, typically 4-5 K at EB - V ≤ 0.15 mag and up to 10-12 K at EB - V ≲ 0.3 mag was found, much brighter than toward the background targets. Typical covering factors of individual features at the 1 K km s-1 level were 20%. 4) CO-H2 conversion factors as much as 4-5 times below the mean value N(H2)/WCO = 2 × 1020 H2 cm-2 (K km s-1)-1 are required to explain the luminosity of CO emission at/above the level of 1 K km s-1. Small conversion factors and sharp variability of the conversion factor on arcminute scales are due primarily to CO chemistry and need not represent unresolved variations in reddening or total column density. Conclusions: Like Fermi and Planck we see some gas that is dark in CO and other gas in which CO is overluminous per H2. A standard CO-H2 conversion factor applies overall owing to balance between the luminosities per H2 and surface covering factors of bright and dark CO, but with wide variations between sightlines and across the faces of individual clouds. Based on observations obtained with the ARO Kitt Peak 12 m telescope.Appendices are available in electronic form at http://www.aanda.org

Modeling the key factors that could influence the diffusion of CO2 from a wellbore blowout in the Ordos Basin, China.

PubMed

Li, Qi; Shi, Hui; Yang, Duoxing; Wei, Xiaochen

2017-02-01

Carbon dioxide (CO 2 ) blowout from a wellbore is regarded as a potential environment risk of a CO 2 capture and storage (CCS) project. In this paper, an assumed blowout of a wellbore was examined for China's Shenhua CCS demonstration project. The significant factors that influenced the diffusion of CO 2 were identified by using a response surface method with the Box-Behnken experiment design. The numerical simulations showed that the mass emission rate of CO 2 from the source and the ambient wind speed have significant influence on the area of interest (the area of high CO 2 concentration above 30,000 ppm). There is a strong positive correlation between the mass emission rate and the area of interest, but there is a strong negative correlation between the ambient wind speed and the area of interest. Several other variables have very little influence on the area of interest, e.g., the temperature of CO 2 , ambient temperature, relative humidity, and stability class values. Due to the weather conditions at the Shenhua CCS demonstration site at the time of the modeled CO 2 blowout, the largest diffusion distance of CO 2 in the downwind direction did not exceed 200 m along the centerline. When the ambient wind speed is in the range of 0.1-2.0 m/s and the mass emission rate is in the range of 60-120 kg/s, the range of the diffusion of CO 2 is at the most dangerous level (i.e., almost all Grade Four marks in the risk matrix). Therefore, if the injection of CO 2 takes place in a region that has relatively low perennial wind speed, special attention should be paid to the formulation of pre-planned, emergency measures in case there is a leakage accident. The proposed risk matrix that classifies and grades blowout risks can be used as a reference for the development of appropriate regulations. This work may offer some indicators in developing risk profiles and emergency responses for CO 2 blowouts.

Carbon dioxide emissions from vegetation-kill zones around the resurgent dome of Long Valley caldera, eastern California, USA

USGS Publications Warehouse

Bergfeld, Deborah; Evans, William C.; Howle, James F.; Farrar, Christopher D.

2006-01-01

A survey of diffuse CO2 efflux, soil temperature and soil-gas chemistry over areas of localized vegetation-kill on and around the resurgent dome of Long Valley caldera California was performed to evaluate the premise that gaseous and thermal anomalies are related to renewed intrusion of magma. Some kill sites are long-lived features and others have developed in the past few years. Total anomalous CO2 emissions from the thirteen areas average around 8.7 t per day; but the majority of the emissions come from four sites west of the Casa Diablo geothermal power plant. Geochemical analyses of the soil-gases from locations west and east of the plant revealed the presence of isobutane related to plant operations. The δ13C values of diffuse CO2 range from − 5.7‰ to − 3.4‰, similar to values previously reported for CO2 from hot springs and thermal wells around Long Valley.At many of the vegetation-kill sites soil temperatures reach boiling at depths ≤ 20 cm. Soil temperature/depth profiles at two of the high-emissions areas indicate that the conductive thermal gradient in the center of the areas is around 320 °C m− 1. We estimate total heat loss from the two areas to be about 6.1 and 2.3 MW. Given current thinking on the rate of hydrothermal fluid flow across the caldera and using the CO2 concentration in the thermal fluids, the heat and CO2 loss from the kill areas is easily provided by the shallow hydrothermal system, which is sourced to the west of the resurgent dome. We find no evidence that the development of new areas of vegetation kill across the resurgent dome are related to new input of magma or magmatic fluids from beneath the resurgent dome. Our findings indicate that the areas have developed as a response to changes in the shallow hydrologic system. Some of the changes are likely related to fluid production at the power plant, but at distal sites the changes are more likely related to seismicity and uplift of the dome.

Diffuse radiation increases global ecosystem-level water-use efficiency

NASA Astrophysics Data System (ADS)

Moffat, A. M.; Reichstein, M.; Cescatti, A.; Knohl, A.; Zaehle, S.

2012-12-01

Current environmental changes lead not only to rising atmospheric CO2 levels and air temperature but also to changes in air pollution and thus the light quality of the solar radiation reaching the land-surface. While rising CO2 levels are thought to enhance photosynthesis and closure of stomata, thus leading to relative water savings, the effect of diffuse radiation on transpiration by plants is less clear. It has been speculated that the stimulation of photosynthesis by increased levels of diffuse light may be counteracted by higher transpiration and consequently water depletion and drought stress. Ultimately, in water co-limited systems, the overall effect of diffuse radiation will depend on the sensitivity of canopy transpiration versus photosynthesis to diffuse light, i.e. whether water-use efficiency changes with relative levels of diffuse light. Our study shows that water-use efficiency increases significantly with higher fractions of diffuse light. It uses the ecosystem-atmosphere gas-exchange observations obtained with the eddy covariance method at 29 flux tower sites. In contrast to previous global studies, the analysis is based directly on measurements of diffuse radiation. Its effect on water-use efficiency was derived by analyzing the multivariate response of carbon and water fluxes to radiation and air humidity using a purely empirical approach based on artificial neural networks. We infer that per unit change of diffuse fraction the water-use efficiency increases up to 40% depending on diffuse fraction levels and ecosystem type. Hence, in regions with increasing diffuse radiation positive effects on primary production are expected even under conditions where water is co-limiting productivity.

Use of Inert Gases and Carbon Monoxide to Study the Possible Influence of Countercurrent Exchange on Passive Absorption from the Small Bowel

PubMed Central

Bond, John H.; Levitt, David G.; Levitt, Michael D.

1974-01-01

The purpose of the present study was to quantitate the influence of countercurrent exchange on passive absorption of highly diffusible substances from the small intestine of the rabbit. The absorption of carbon monoxide, which is tightly bound to hemoglobin and therefore cannot exchange, was compared to the absorption of four unbound gases (H2, He, CH4, and 133Xe), which should exchange freely. The degree to which the observed absorption of the unbound gases falls below that predicted from CO absorption should provide a quantitative measure of countercurrent exchange. CO uptake at high luminal Pco is flow-limited and, assuming that villus and central hemoglobin concentrations are equal, the flow that equilibrates with CO (Fco) was calculated to equal 7.24 ml/min/100 g. The observed absorption rate of the unbound gases was from two to four times greater than would have been predicted had their entire uptake been accounted for by equilibration with Fco. This is the opposite of what would occur if countercurrent exchange retarded absorption of the unbound gases. The unbound gases have both flow- and diffusion-limited components, and Fco should account for only the fraction of absorption that is flow limited. A simple model of perfusion and diffusion made it possible to calculate the fraction of the total uptake of unbound gases that was flow limited. This fraction of the total observed absorption rate was still about 1.8 times greater than predicted by CO absorption. A possible explanation for this discrepancy is that plasma skimming reduces the hemoglobin of villus blood to about 60% of that of central blood. Thus, Fco is actually about 1.7 times greater than initially calculated, and with this correction, there is close agreement between the predicted and observed rates of absorption of each of the unbound gases. We conclude that countercurrent exchange does not influence passive absorption under the conditions of this study. PMID:4436431

Izu-Oshima volcano, Japan: ten years of geochemical monitoring by means of CO2 soil diffuse degassing

NASA Astrophysics Data System (ADS)

Hernandez Perez, P. A.; Mori, T.; Notsu, K.; Morita, M.; Padron, E.; Onizawa, S.; Melián, G.; Sumino, H.; Asensio-Ramos, M.; Nogami, K.; Yamane, K.; Perez, N. M.

2016-12-01

Izu-Oshima is an active volcanic island located around 100 km SSW of Tokyo. The centre of the island is occupied by a caldera complex with a diameter of 3 km. A large post-caldera cone known as Mt. Mihara is located at the south-western quadrant of the caldera. Izu-Oshima has erupted 74 times, consisting mainly in fissure eruptions, both inside and outside of the caldera. The last eruption of Izu-Oshima occurred in 1986. Since 2007, eight soil gas surveys have been carried out to investigate the spatial and temporal evolution of diffuse CO2 emission from this volcanic system and to identify those structures controlling the degassing process. Diffuse CO2 emission surveys were always carried out following the accumulation chamber method. Spatial distribution maps were constructed following the sequential Gaussian simulation (sGs) procedure. The location of the CO2 anomalies has always shown a close relationship with the structural characteristics of Miharayama, with most of the gas discharged from the rim of the summit crater. Temporal evolution of diffuse CO2 emission rate from Mt. Miharayama has shown a good temporal correlation with the main two peaks of seismic activity occur when highest CO diffuse emissions were computed, March 2007, August 2010 and July 2011, may be associated with fluid pressure fluctuations in the volcanic system due stress changes at depth. In order to strength the contribution of deep seated gases, we performed carbon isotopic analysis of soil gas samples at selected sites during 2010, 2013, 2015 and 2016 surveys. At isotopic compositions lighter than - 6‰, the soil CO2 effluxes were always low, while at heavier isotopic compositions an increasing number of points are characterized by relatively high soil CO efflux. Soil CO2 efflux peak values (xB) showed also a good correlation with the observed seismicity, with the largest value computed on June 2013. This parameter is a geochemical expression of the magnitude of the anomalous degassing, and the observed change in the trend may indicate an increase of the seismic-volcanic activity in the next future. Therefore, performing regularly soil CO2 efflux surveys seems to be an effective geochemical surveillance tool Izu-Oshima volcano in order to detect a change in the tendency of the CO2 emission rate in case of future episodes of volcanic unrest.

Efficient CO2 capture by functionalized graphene oxide nanosheets as fillers to fabricate multi-permselective mixed matrix membranes.

PubMed

Li, Xueqin; Cheng, Youdong; Zhang, Haiyang; Wang, Shaofei; Jiang, Zhongyi; Guo, Ruili; Wu, Hong

2015-03-11

A novel multi-permselective mixed matrix membrane (MP-MMM) is developed by incorporating versatile fillers functionalized with ethylene oxide (EO) groups and an amine carrier into a polymer matrix. The as-prepared MP-MMMs can separate CO2 efficiently because of the simultaneous enhancement of diffusivity selectivity, solubility selectivity, and reactivity selectivity. To be specific, MP-MMMs were fabricated by incorporating polyethylene glycol- and polyethylenimine-functionalized graphene oxide nanosheets (PEG-PEI-GO) into a commercial low-cost Pebax matrix. The PEG-PEI-GO plays multiple roles in enhancing membrane performance. First, the high-aspect ratio GO nanosheets in a polymer matrix increase the length of the tortuous path of gas diffusion and generate a rigidified interface between the polymer matrix and fillers, enhancing the diffusivity selectivity. Second, PEG consisting of EO groups has excellent affinity for CO2 to enhance the solubility selectivity. Third, PEI with abundant primary, secondary, and tertiary amine groups reacts reversibly with CO2 to enhance reactivity selectivity. Thus, the as-prepared MP-MMMs exhibit excellent CO2 permeability and CO2/gas selectivity. The MP-MMM doped with 10 wt % PEG-PEI-GO displays optimal gas separation performance with a CO2 permeability of 1330 Barrer, a CO2/CH4 selectivity of 45, and a CO2/N2 selectivity of 120, surpassing the upper bound lines of the Robeson study of 2008 (1 Barrer = 10(-10) cm(3) (STP) cm(-2) s(-1) cm(-1) Hg).

Quantitative MRI of the spinal cord and brain in adrenomyeloneuropathy: in vivo assessment of structural changes.

PubMed

Castellano, Antonella; Papinutto, Nico; Cadioli, Marcello; Brugnara, Gianluca; Iadanza, Antonella; Scigliuolo, Graziana; Pareyson, Davide; Uziel, Graziella; Köhler, Wolfgang; Aubourg, Patrick; Falini, Andrea; Henry, Roland G; Politi, Letterio S; Salsano, Ettore

2016-06-01

Adrenomyeloneuropathy is the late-onset form of X-linked adrenoleukodystrophy, and is considered the most frequent metabolic hereditary spastic paraplegia. In adrenomyeloneuropathy the spinal cord is the main site of pathology. Differently from quantitative magnetic resonance imaging of the brain, little is known about the feasibility and utility of advanced neuroimaging in quantifying the spinal cord abnormalities in hereditary diseases. Moreover, little is known about the subtle pathological changes that can characterize the brain of adrenomyeloneuropathy subjects in the early stages of the disease. We performed a cross-sectional study on 13 patients with adrenomyeloneuropathy and 12 age-matched healthy control subjects who underwent quantitative magnetic resonance imaging to assess the structural changes of the upper spinal cord and brain. Total cord areas from C2-3 to T2-3 level were measured, and diffusion tensor imaging metrics, i.e. fractional anisotropy, mean, axial and radial diffusivity values were calculated in both grey and white matter of spinal cord. In the brain, grey matter regions were parcellated with Freesurfer and average volume and thickness, and mean diffusivity and fractional anisotropy from co-registered diffusion maps were calculated in each region. Brain white matter diffusion tensor imaging metrics were assessed using whole-brain tract-based spatial statistics, and tractography-based analysis on corticospinal tracts. Correlations among clinical, structural and diffusion tensor imaging measures were calculated. In patients total cord area was reduced by 26.3% to 40.2% at all tested levels (P < 0.0001). A mean 16% reduction of spinal cord white matter fractional anisotropy (P ≤ 0.0003) with a concomitant 9.7% axial diffusivity reduction (P < 0.009) and 34.5% radial diffusivity increase (P < 0.009) was observed, suggesting co-presence of axonal degeneration and demyelination. Brain tract-based spatial statistics showed a marked reduction of fractional anisotropy, increase of radial diffusivity (P < 0.001) and no axial diffusivity changes in several white matter tracts, including corticospinal tracts and optic radiations, indicating predominant demyelination. Tractography-based analysis confirmed the results within corticospinal tracts. No significant cortical volume and thickness reduction or grey matter diffusion tensor imaging values alterations were observed in patients. A correlation between radial diffusivity and disease duration along the corticospinal tracts (r = 0.806, P < 0.01) was found. In conclusion, in adrenomyeloneuropathy patients quantitative magnetic resonance imaging-derived measures identify and quantify structural changes in the upper spinal cord and brain which agree with the expected histopathology, and suggest that the disease could be primarily caused by a demyelination rather than a primitive axonal damage. The results of this study may also encourage the employment of quantitative magnetic resonance imaging in other hereditary diseases with spinal cord involvement. © The Author (2016). Published by Oxford University Press on behalf of the Guarantors of Brain. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Mesophyll conductance and reaction-diffusion models for CO2 transport in C3 leaves; needs, opportunities and challenges.

PubMed

Berghuijs, Herman N C; Yin, Xinyou; Ho, Q Tri; Driever, Steven M; Retta, Moges A; Nicolaï, Bart M; Struik, Paul C

2016-11-01

One way to increase potential crop yield could be increasing mesophyll conductance g m . This variable determines the difference between the CO 2 partial pressure in the intercellular air spaces (C i ) and that near Rubisco (C c ). Various methods can determine g m from gas exchange measurements, often combined with measurements of chlorophyll fluorescence or carbon isotope discrimination. g m lumps all biochemical and physical factors that cause the difference between C c and C i . g m appears to vary with C i . This variability indicates that g m does not satisfy the physical definition of a conductance according to Fick's first law and is thus an apparent parameter. Uncertainty about the mechanisms that determine g m can be limited to some extent by using analytical models that partition g m into separate conductances. Such models are still only capable of describing the CO 2 diffusion pathway to a limited extent, as they make implicit assumptions about the position of mitochondria in the cells, which affect the re-assimilation of (photo)respired CO 2 . Alternatively, reaction-diffusion models may be used. Rather than quantifying g m , these models explicitly account for factors that affect the efficiency of CO 2 transport in the mesophyll. These models provide a better mechanistic description of the CO 2 diffusion pathways than mesophyll conductance models. Therefore, we argue that reaction-diffusion models should be used as an alternative to mesophyll conductance models, in case the aim of such a study is to identify traits that can be improved to increase g m . Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Molecular Dynamics Study of the Solution Structure, Clustering, and Diffusion of Four Aqueous Alkanolamines.

PubMed

Melnikov, Sergey M; Stein, Matthias

2018-03-15

CO 2 sequestration from anthropogenic resources is a challenge to the design of environmental processes at a large scale. Reversible chemical absorption by amine-based solvents is one of the most efficient methods of CO 2 removal. Molecular simulation techniques are very useful tools to investigate CO 2 binding by aqueous alkanolamine molecules for further technological application. In the present work, we have performed detailed atomistic molecular dynamics simulations of aqueous solutions of three prototype amines: monoethanolamine (MEA) as a standard, 3-aminopropanol (MPA), 2-methylaminoethanol (MMEA), and 4-diethylamino-2-butanol (DEAB) as potential novel CO 2 absorptive solvents. Solvent densities, radial distribution functions, cluster size distributions, hydrogen-bonding statistics, and diffusion coefficients for a full range of mixture compositions have been obtained. The solvent densities and diffusion coefficients from simulations are in good agreement with those in the experiment. In aqueous solution, MEA, MPA, and MMEA molecules prefer to be fully solvated by water molecules, whereas DEAB molecules tend to self-aggregate. In a range from 30/70-50/50 (w/w) alkanolamine/water mixtures, they form a bicontinuous phase (both alkanolamine and water are organized in two mutually percolating clusters). Among the studied aqueous alkanolamine solutions, the diffusion coefficients decrease in the following order MEA > MPA = MMEA > DEAB. With an increase of water content, the diffusion coefficients increase for all studied alkanolamines. The presented results are a first step for process-scale simulation and provide important qualitative and quantitative information for the design and engineering of efficient new CO 2 removal processes.

Measurements of the Activation Energies for Atomic Hydrogen Diffusion on Pure Solid CO

NASA Astrophysics Data System (ADS)

Kimura, Y.; Tsuge, M.; Pirronello, V.; Kouchi, A.; Watanabe, N.

2018-05-01

The diffusion of hydrogen atoms on dust grains is a key process in the formation of interstellar H2 and some hydrogenated molecules such as formaldehyde and methanol. We investigate the adsorption and diffusion of H atoms on pure solid CO as an analog of dust surfaces observed toward some cold interstellar regions. Using a combination of photostimulated desorption and resonance-enhanced multiphoton ionization methods to detect H atoms directly, the relative adsorption probabilities and diffusion coefficients of the H atoms are measured on pure solid CO at 8, 12, and 15 K. There is little difference between the diffusion coefficients of the hydrogen and deuterium atoms, indicating that the diffusion is limited by thermal hopping. The activation energies controlling the H-atom diffusion depend on the surface temperature, and values of 22, 30, and ∼37 meV were obtained for 8, 12, and 15 K, respectively.

A joint global carbon inversion system using both CO2 and 13CO2 atmospheric concentration data

NASA Astrophysics Data System (ADS)

Chen, Jing M.; Mo, Gang; Deng, Feng

2017-03-01

Observations of 13CO2 at 73 sites compiled in the GLOBALVIEW database are used for an additional constraint in a global atmospheric inversion of the surface CO2 flux using CO2 observations at 210 sites (62 collocated with 13CO2 sites) for the 2002-2004 period for 39 land regions and 11 ocean regions. This constraint is implemented using prior CO2 fluxes estimated with a terrestrial ecosystem model and an ocean model. These models simulate 13CO2 discrimination rates of terrestrial photosynthesis and ocean-atmosphere diffusion processes. In both models, the 13CO2 disequilibrium between fluxes to and from the atmosphere is considered due to the historical change in atmospheric 13CO2 concentration. This joint inversion system using both13CO2 and CO2 observations is effectively a double deconvolution system with consideration of the spatial variations of isotopic discrimination and disequilibrium. Compared to the CO2-only inversion, this 13CO2 constraint on the inversion considerably reduces the total land carbon sink from 3.40 ± 0.84 to 2.53 ± 0.93 Pg C year-1 but increases the total oceanic carbon sink from 1.48 ± 0.40 to 2.36 ± 0.49 Pg C year-1. This constraint also changes the spatial distribution of the carbon sink. The largest sink increase occurs in the Amazon, while the largest source increases are in southern Africa, and Asia, where CO2 data are sparse. Through a case study, in which the spatial distribution of the annual 13CO2 discrimination rate over land is ignored by treating it as a constant at the global average of -14. 1 ‰, the spatial distribution of the inverted CO2 flux over land was found to be significantly modified (up to 15 % for some regions). The uncertainties in our disequilibrium flux estimation are 8.0 and 12.7 Pg C year-1 ‰ for land and ocean, respectively. These uncertainties induced the unpredictability of 0.47 and 0.54 Pg C year-1 in the inverted CO2 fluxes for land and ocean, respectively. Our joint inversion system is therefore useful for improving the partitioning between ocean and land sinks and the spatial distribution of the inverted carbon flux.

Red blood cell thickness is evolutionarily constrained by slow, hemoglobin-restricted diffusion in cytoplasm

PubMed Central

Richardson, Sarah L.; Swietach, Pawel

2016-01-01

During capillary transit, red blood cells (RBCs) must exchange large quantities of CO2 and O2 in typically less than one second, but the degree to which this is rate-limited by diffusion through cytoplasm is not known. Gas diffusivity is intuitively assumed to be fast and this would imply that the intracellular path-length, defined by RBC shape, is not a factor that could meaningfully compromise physiology. Here, we evaluated CO2 diffusivity (DCO2) in RBCs and related our results to cell shape. DCO2 inside RBCs was determined by fluorescence imaging of [H+] dynamics in cells under superfusion. This method is based on the principle that H+ diffusion is facilitated by CO2/HCO3− buffer and thus provides a read-out of DCO2. By imaging the spread of H+ ions from a photochemically-activated source (6-nitroveratraldehyde), DCO2 in human RBCs was calculated to be only 5% of the rate in water. Measurements on RBCs containing different hemoglobin concentrations demonstrated a halving of DCO2 with every 75 g/L increase in mean corpuscular hemoglobin concentration (MCHC). Thus, to compensate for highly-restricted cytoplasmic diffusion, RBC thickness must be reduced as appropriate for its MCHC. This can explain the inverse relationship between MCHC and RBC thickness determined from >250 animal species. PMID:27777410

Double, Double Toil and Trouble: The Melt Inclusion Bubble

NASA Astrophysics Data System (ADS)

Rasmussen, D. J.; Plank, T. A.

2017-12-01

Melt inclusions provide a powerful means for probing the depth of magmatic processes and volatile budgets of magmas. Both objectives require that the inclusions accurately record the volatile content of the entrapped melt. However, post-entrapment cooling and diffusive loss of water lead to a decrease in internal pressure, resulting in volatile exsolution (importantly CO2) and vapor bubble growth in inclusions. Several methods have been developed recently that attempt to reconstruct the entrapped CO2 contents, but the methods yield inconsistent results. Here we report on new homogenization experiments and attempt to reconcile inconsistencies in CO2 reconstruction methods. Experiments were conducted on olivine-hosted melt inclusions from Seguam volcano using a piston cylinder apparatus at 500 MPa, 1150-1170 °C, hydrous conditions, and a run duration of 1-2 hours. FTIR analyses of the homogenized inclusions show some diffusive water gain (≤1 wt% excess) relative to unheated inclusions (most 4 wt%). Inclusions from this same sample were previously reconstructed using Raman addition (RA; Moore et al., 2015), and we have constituted the CO2 with two different computational approaches: the ideal gas law (IGL; Shaw et al., 2010) and a bubble growth model (BG; Riker, 2005). CO2 and S contents of heated inclusions are correlated, defining a S-CO2 degassing path. Relative to this empirical degassing path, IGL results are offset to higher CO2 (100s-1000s of ppm) or lower S (100s of ppm), while RA and BG results overlap and are offset to lower CO2 (≤100s of ppm) or higher S (≤100s of ppm). Because S contents of heated and unheated inclusions have similar ranges, we attribute the discrepancy to CO2. High values of CO2 from the IGL correction may be because CO2 diffusion cannot keep pace with bubble growth during rapid cooling upon eruption. Mass balance calculations indicate that a minute amount of carbonate, which could escape detection by Raman, would affect CO2 content, providing an explanation for low values of CO2 determined by RA. The discrepancy in the BG results might relate to diffusive loss of H+ and uncertainties (e.g., temperature) involved with the calculation. Thus, homogenization via heating has advantages over other techniques in constituting the CO2 of inclusions, and may lead to a more accurate computational method.

Mind the gap: non-biological processes contributing to soil CO2 efflux.

PubMed

Rey, Ana

2015-05-01

Widespread recognition of the importance of soil CO2 efflux as a major source of CO2 to the atmosphere has led to active research. A large soil respiration database and recent reviews have compiled data, methods, and current challenges. This study highlights some deficiencies for a proper understanding of soil CO2 efflux focusing on processes of soil CO2 production and transport that have not received enough attention in the current soil respiration literature. It has mostly been assumed that soil CO2 efflux is the result of biological processes (i.e. soil respiration), but recent studies demonstrate that pedochemical and geological processes, such as geothermal and volcanic CO2 degassing, are potentially important in some areas. Besides the microbial decomposition of litter, solar radiation is responsible for photodegradation or photochemical degradation of litter. Diffusion is considered to be the main mechanism of CO2 transport in the soil, but changes in atmospheric pressure and thermal convection may also be important mechanisms driving soil CO2 efflux greater than diffusion under certain conditions. Lateral fluxes of carbon as dissolved organic and inorganic carbon occur and may cause an underestimation of soil CO2 efflux. Traditionally soil CO2 efflux has been measured with accumulation chambers assuming that the main transport mechanism is diffusion. New techniques are available such as improved automated chambers, CO2 concentration profiles and isotopic techniques that may help to elucidate the sources of carbon from soils. We need to develop specific and standardized methods for different CO2 sources to quantify this flux on a global scale. Biogeochemical models should include biological and non-biological CO2 production processes before we can predict the response of soil CO2 efflux to climate change. Improving our understanding of the processes involved in soil CO2 efflux should be a research priority given the importance of this flux in the global carbon budget. © 2014 John Wiley & Sons Ltd.

How thin barrier metal can be used to prevent Co diffusion in the modern integrated circuits?

NASA Astrophysics Data System (ADS)

Dixit, Hemant; Konar, Aniruddha; Pandey, Rajan; Ethirajan, Tamilmani

2017-11-01

In modern integrated circuits (ICs), billions of transistors are connected to each other via thin metal layers (e.g. copper, cobalt, etc) known as interconnects. At elevated process temperatures, inter-diffusion of atomic species can occur among these metal layers, causing sub-optimal performance of interconnects, which may lead to the failure of an IC. Thus, typically a thin barrier metal layer is used to prevent the inter-diffusion of atomic species within interconnects. For ICs with sub-10 nm transistors (10 nm technology node), the design rule (thickness scaling) demands the thinnest possible barrier layer. Therefore, here we investigate the critical thickness of a titanium-nitride (TiN) barrier that can prevent the cobalt diffusion using multi-scale modeling and simulations. First, we compute the Co diffusion barrier in crystalline and amorphous TiN with the nudged elastic band method within first-principles density functional theory simulations. Later, using the calculated activation energy barriers, we quantify the Co diffusion length in the TiN metal layer with the help of kinetic Monte Carlo simulations. Such a multi-scale modelling approach yields an exact critical thickness of the metal layer sufficient to prevent the Co diffusion in IC interconnects. We obtain a diffusion length of a maximum of 2 nm for a typical process of thermal annealing at 400 °C for 30 min. Our study thus provides useful physical insights for the Co diffusion in the TiN layer and further quantifies the critical thickness (~2 nm) to which the metal barrier layer can be thinned down for sub-10 nm ICs.

Kinetic analysis of an anion exchange absorbent for CO2 capture from ambient air.

PubMed

Shi, Xiaoyang; Li, Qibin; Wang, Tao; Lackner, Klaus S

2017-01-01

This study reports a preparation method of a new moisture swing sorbent for CO2 capture from air. The new sorbent components include ion exchange resin (IER) and polyvinyl chloride (PVC) as a binder. The IER can absorb CO2 when surrounding is dry and release CO2 when surrounding is wet. The manuscript presents the studies of membrane structure, kinetic model of absorption process, performance of desorption process and the diffusivity of water molecules in the CO2 absorbent. It has been proved that the kinetic performance of CO2 absorption/desorption can be improved by using thin binder and hot water treatment. The fast kinetics of P-100-90C absorbent is due to the thin PVC binder, and high diffusion rate of H2O molecules in the sample. The impressive is this new CO2 absorbent has the fastest CO2 absorption rate among all absorbents which have been reported by other up-to-date literatures.

Kinetic analysis of an anion exchange absorbent for CO2 capture from ambient air

PubMed Central

Shi, Xiaoyang; Li, Qibin; Lackner, Klaus S.

2017-01-01

This study reports a preparation method of a new moisture swing sorbent for CO2 capture from air. The new sorbent components include ion exchange resin (IER) and polyvinyl chloride (PVC) as a binder. The IER can absorb CO2 when surrounding is dry and release CO2 when surrounding is wet. The manuscript presents the studies of membrane structure, kinetic model of absorption process, performance of desorption process and the diffusivity of water molecules in the CO2 absorbent. It has been proved that the kinetic performance of CO2 absorption/desorption can be improved by using thin binder and hot water treatment. The fast kinetics of P-100-90C absorbent is due to the thin PVC binder, and high diffusion rate of H2O molecules in the sample. The impressive is this new CO2 absorbent has the fastest CO2 absorption rate among all absorbents which have been reported by other up-to-date literatures. PMID:28640914

Are there sex differences in the capillary blood volume and diffusing capacity response to exercise?

PubMed

Bouwsema, Melissa M; Tedjasaputra, Vincent; Stickland, Michael K

2017-03-01

Previous work suggests that women may exhibit a greater respiratory limitation in exercise compared with height-matched men. Diffusion capacity (Dl CO ) increases with incremental exercise, and the smaller lungs of women may limit membrane diffusing capacity (Dm) and pulmonary capillary blood volume (Vc) in response to the increased oxygen demand. We hypothesized that women would have lower Dl CO , Dl CO relative to cardiac output (Dl CO /Q̇), Dm, Vc, and pulmonary transit time, secondary to lower Vc at peak exercise. Sixteen women (112 ± 12% predicted relative V̇o 2peak ) and sixteen men (118 ± 22% predicted relative V̇o 2peak ) were matched for height and weight. Hemoglobin-corrected diffusing capacity (Dl CO ), Vc, and Dm were determined via the multiple-[Formula: see text] Dl CO technique at rest and during incremental exercise up to 90% of V̇o 2peak Both groups increased Dl CO , Vc, and Dm with exercise intensity, but women had 20% lower Dl CO ( P < 0.001), 18% lower Vc ( P = 0.002), and 22% lower Dm ( P < 0.001) compared with men across all workloads, and neither group exhibited a plateau in Vc. When expressed relative to alveolar volume (Va), the between-sex difference was eliminated. The drop in Dl CO /Q̇ was proportionally less in women than men, and mean pulmonary transit time did not drop below 0.3 s in either group. Women demonstrate consistently lower Dl CO , Vc, and Dm compared with height-matched men during exercise; however, these differences disappear with correction for lung size. These results suggest that after differences in lung volume are accounted for there is no intrinsic sex difference in the Dl CO , Vc, or Dm response to exercise. NEW & NOTEWORTHY Women demonstrate lower diffusing capacity-to-cardiac output ratio (Dl CO /Q̇), pulmonary capillary blood volume (Vc), and membrane diffusing capacity (Dm) compared with height-matched men during exercise. However, these differences disappear after correction for lung size. The drop in Dl CO /Q̇ was proportionally less in women, and pulmonary transit time did not drop below 0.3 s in either group. After differences in lung volume are accounted for, there is no intrinsic sex difference in Dl CO , Vc, or Dm response to exercise. Copyright © 2017 the American Physiological Society.

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.

Constraints on the magnitude and rate of CO2 dissolution at Bravo Dome natural gas field

PubMed Central

Sathaye, Kiran J.; Hesse, Marc A.; Cassidy, Martin; Stockli, Daniel F.

2014-01-01

The injection of carbon dioxide (CO2) captured at large point sources into deep saline aquifers can significantly reduce anthropogenic CO2 emissions from fossil fuels. Dissolution of the injected CO2 into the formation brine is a trapping mechanism that helps to ensure the long-term security of geological CO2 storage. We use thermochronology to estimate the timing of CO2 emplacement at Bravo Dome, a large natural CO2 field at a depth of 700 m in New Mexico. Together with estimates of the total mass loss from the field we present, to our knowledge, the first constraints on the magnitude, mechanisms, and rates of CO2 dissolution on millennial timescales. Apatite (U-Th)/He thermochronology records heating of the Bravo Dome reservoir due to the emplacement of hot volcanic gases 1.2–1.5 Ma. The CO2 accumulation is therefore significantly older than previous estimates of 10 ka, which demonstrates that safe long-term geological CO2 storage is possible. Integrating geophysical and geochemical data, we estimate that 1.3 Gt CO2 are currently stored at Bravo Dome, but that only 22% of the emplaced CO2 has dissolved into the brine over 1.2 My. Roughly 40% of the dissolution occurred during the emplacement. The CO2 dissolved after emplacement exceeds the amount expected from diffusion and provides field evidence for convective dissolution with a rate of 0.1 g/(m2y). The similarity between Bravo Dome and major US saline aquifers suggests that significant amounts of CO2 are likely to dissolve during injection at US storage sites, but that convective dissolution is unlikely to trap all injected CO2 on the 10-ky timescale typically considered for storage projects. PMID:25313084

Radial diffusion, vertical transport, and refixation of labeled bicarbonate in scots pine stems

NASA Astrophysics Data System (ADS)

Marshall, J. D.; Tarvainen, L.; Wallin, G.

2016-12-01

The CO2 produced by a respiring stem provides an index of metabolic activity in the stem and a quantitative estimate of an important component of the forest carbon budget. Production of CO2 by a given stem volume is lost by three competing processes. First, some diffuses radially outward through the bark. Second, some is dissolved and vertically transported upward out of the control volume by the xylem stream. Third, some is refixed by photosynthesis under the bark. The relative balance among these pathways was quantified in 17-m Scots pine trees by 13C-bicarbonate labeling of the xylem stream and monitoring of the 13CO2 in the xylem water, along with continuous monitoring of the radial diffusive flux at four canopy heights and in transpiration from leaves. Most of the label diffused out radially, as 13CO2, immediately above the labeling site, over about a week. The pulse was weakly and briefly detected 4 m above that height. Further up the stem it was not detected at all. We detected significant refixation of CO2 in the stems at all heights above 4 m, where the bark becomes papery and thin, but the label was so weak at this height that refixation had little influence on the pulse chase. We conclude that the vertical flux is negligible in Scots pine, but that the refixation flux must be accounted for in estimates of whole-stem CO2 efflux.

Investigation of Reaction Mechanism on the Lime-Free Roasting of Chromium-Containing Slag

NASA Astrophysics Data System (ADS)

Yu, Kai-ping; Zhang, Hong-ling; Chen, Bo; Xu, Hong-bin; Zhang, Yi

2015-12-01

The lime-free roasting process of trivalent chromium-containing slag was investigated. The effect of Fe and liquid phase on the conversion reaction of chromium was discussed. The oxidation of trivalent chromium depends greatly on the diffusion of Na+ and O2. Both the raw material Na2CO3 and the intermediate product NaFeO2 serve as the carriers of Na+. The Na+ diffusion is improved by the binary liquid phase of Na2CrO4-Na2CO3, whereas excess liquid phase results in a low conversion rate of chromium by hindering the diffusion of oxygen towards the reaction interface. With the increasing of liquid volume, the controlled step of chromium oxidation changes from Na+ diffusion to oxygen diffusion. The mechanism study showed that the volume of liquid phase increased while raising the reaction temperature or prolonging the reaction time. Based on the role of both liquid phase and Fe, the oxidation process of chromium was summarized as a three-stage model: the Na+ diffusion-controlled stage, the O2 diffusion-controlled stage, and the oxidation reaction halted stage.

Abiotic and seasonal control of soil-produced CO2 efflux in karstic ecosystems located in Oceanic and Mediterranean climates

NASA Astrophysics Data System (ADS)

Garcia-Anton, Elena; Cuezva, Soledad; Fernandez-Cortes, Angel; Alvarez-Gallego, Miriam; Pla, Concepcion; Benavente, David; Cañaveras, Juan Carlos; Sanchez-Moral, Sergio

2017-09-01

This study characterizes the processes involved in seasonal CO2 exchange between soils and shallow underground systems and explores the contribution of the different biotic and abiotic sources as a function of changing weather conditions. We spatially and temporally investigated five karstic caves across the Iberian Peninsula, which presented different microclimatic, geologic and geomorphologic features. The locations present Mediterranean and Oceanic climates. Spot air sampling of CO2 (g) and δ13CO2 in the caves, soils and outside atmospheric air was periodically conducted. The isotopic ratio of the source contribution enhancing the CO2 concentration was calculated using the Keeling model. We compared the isotopic ratio of the source in the soil (δ13Cs-soil) with that in the soil-underground system (δ13Cs-system). Although the studied field sites have different features, we found common seasonal trends in their values, which suggests a climatic control over the soil air CO2 and the δ13CO2 of the sources of CO2 in the soil (δ13Cs-soil) and the system (δ13Cs-system). The roots respiration and soil organic matter degradation are the main source of CO2 in underground environments, and the inlet of the gas is mainly driven by diffusion and advection. Drier and warmer conditions enhance soil-exterior CO2 interchange, reducing the CO2 concentration and increasing the δ13CO2 of the soil air. Moreover, the isotopic ratio of the source of CO2 in both the soil and the system tends to heavier values throughout the dry and warm season. We conclude that seasonal variations of soil CO2 concentration and its 13C/12C isotopic ratio are mainly regulated by thermo-hygrometric conditions. In cold and wet seasons, the increase of soil moisture reduces soil diffusivity and allows the storage of CO2 in the subsoil. During dry and warm seasons, the evaporation of soil water favours diffusive and advective transport of soil-derived CO2 to the atmosphere. The soil CO2 diffusion is enough important during this season to modify the isotopic ratio of soil produced CO2 (3-6‰ heavier). Drought induces release of CO2 with an isotopic ratio heavier than produced by organic sources. Consequently, climatic conditions drive abiotic processes that turn regulate a seasonal storage of soil-produced CO2 within soil and underground systems. The results here obtained imply that abiotic emissions of soil-produced CO2 must be an inherent consequence of droughts, which intensification has been forecasted at global scale in the next 100 years.

Investigation of defect clusters in ion-irradiated Ni and NiCo using diffuse X-ray scattering and electron microscopy

DOE PAGES

Olsen, Raina J.; Jin, Ke; Lu, Chenyang; ...

2015-11-23

The nature of defect clusters in Ni and Nimore » $$_{50}$$Co$$_{50}$$ (NiCo) irradiated at room temperature with 2–16 MeV Ni ions is studied using asymptotic diffuse X-ray scattering and transmission electron microscopy (TEM). Analysis of the scattering data provides separate size distributions for vacancy and interstitial type defect clusters, showing that both types of defect clusters have a smaller size and higher density in NiCo than in Ni. Diffuse scattering results show good quantitative agreement with TEM results for cluster sizes greater than 4 nm diameter, but find that the majority of vacancy clusters are under 2 nm in NiCo, which, if not detected, would lead to the conclusion that defect density was actually lower in the alloy. Interstitial dislocation loops and stacking fault tetrahedra are identified by TEM. Lastly comparison of diffuse scattering lineshapes to those calculated for dislocation loops and SFTs indicates that most of the vacancy clusters are SFTs.« less

The usefulness of diffusion-weighted magnetic resonance imaging performed in the acute phase as an early predictor of delayed neuropsychiatric sequelae in acute carbon monoxide poisoning.

PubMed

Kim, Y S; Cha, Y S; Kim, M S; Kim, H J; Lee, Y S; Youk, H; Kim, H I; Kim, O H; Cha, K-C; Kim, H; Lee, K H; Hwang, S O

2018-06-01

Delayed onset of neuropsychiatric symptoms after apparent recovery from acute carbon monoxide (CO) poisoning has been described as delayed neuropsychiatric sequelae (DNS). No previous study has determined whether early use of diffusion-weighted magnetic resonance imaging (DWI) can predict which patients will develop DNS in the acute CO poisoning. This retrospective observational study was performed on adult patients with acute CO poisoning consecutively treated over a 17-month period. All included patients with acute CO poisoning underwent DWI to evaluate brain injury within 72 h after CO exposure. DWI was evaluated as follows: (1) presence of pathology, (2) number of pathologies, (3) asymmetry, and (4) location of pathology. Patients were divided into two groups. The DNS group was composed of patients with delayed sequelae, while the non-DNS group included patients with no sequelae. A total of 102 patients with acute CO poisoning were finally enrolled in this study. DNS developed in 10 patients (9.8%). Between the DNS group and the non-DNS group, presence of pathology on DWI and initial Glasgow Coma Scale (GCS) showed significant difference. There was also a statistical difference between the non-DNS group and DNS group in terms of CO exposure time, troponin I, rhabdomyolysis, acute kidney injury, and pneumonia. The presence of pathology in DWI and initial GCS (cutoff: <12) at the emergency department served as an early predictors of DNS.

Stomata of the CAM plant Tillandsia recurvata respond directly to humidity.

PubMed

Lange, O L; Medina, E

1979-01-01

Under controlled conditions, CO 2 exchange of Tillandsia recurvata showed all characteristics of CAM. During the phase of nocturnal CO 2 fixation stomata of the plant responded sensitively to changes in ambient air humidity. Dry air resulted in an increase, moist air in a decrease of diffusion resistance. The evaporative demand of the air affected the level of stomatal resistance during the entire night period. Due to stomatal closure, the total nocturnal water loss of T. recurvata was less at low than at high humidity. It is concluded that stomata respond directly to humidity and not via bulk tissue water conditions of the leaves. Such control of transpiration may optimize water use efficiency for this almost rootless, extreme epiphyte.

Observed anomalous changes on diffuse CO2 emission at the summit crater of Teide volcano (Tenerife, Canary Islands, Spain): a geochemical evidence of volcanic unrest?

NASA Astrophysics Data System (ADS)

Perez, N. M.; Melián, G.; Asensio-Ramos, M.; Padrón, E.; Alonso Cótchico, M.; Hernández, P. A.; Rodríguez, F.; D'Auria, L.; García-Merino, M.; Padilla, G. D.; Burns, F.; Amonte, C.; García, E.; García-Hernández, R.; Barrancos, J.; Morales-Ocaña, C.; Calvo, D.; Vela, V.; Pérez, A.

2017-12-01

Tenerife (2034 km2) is the largest of the Canary Islands and hosts a central volcanic complex, Las Cañadas, which is characterized by the eruption of differentiated magmas. Laying inside Las Cañadas a twin stratovolcanoes system Pico Viejo and Teide, has been developed. Although Teide volcano shows weak fumarolic system, volcanic gas emissions observed in the summit area are mainly controlled by high rates of diffuse CO2 degassing. Soil CO2 efflux surveys have been performed at the summit crater of Teide volcano since 1999 according to the accumulation chamber method to monitor changes of volcanic activity. Soil CO2 efflux and soil temperature have been measured in sites homogeneously distributed within an area of about 6,972 m2 inside the summit crater. Historical seismic activity in Tenerife has been mainly characterized by low- to moderate-magnitude events (M <2.5), and most of epicenters clustered in an offshore area SE of Tenerife. Very few earthquakes have occurred in other areas, including Teide volcano. Since November 2016 more than 100 small magnitude earthquakes, with typical features of the microseismicity of hydrothermal systems, at depths usually ranging between 5 and 15 km located beneath Teide volcano have been recorded. On January 6th 2017 a M=2.5 earthquake was recorded in the area, being one of the strongest events recorded since 2004. Between October 11 and December 13, 2016, a continuous increase on the diffuse CO2 emission was registered preceding the occurrence of the 2.5 seismic event, from 21.3±2.0 to 101.7±20.7 t d-1. In Febraury 2017, the diffuse CO2 emission rate showed a maximum value (176±35 t/d) and has remained at relatively high values in the range 67-176 t/d. The observed increase on the diffuse CO2 emission, likely due to the increase of fluid pressure in the hydrothermal-magmatic system of Tenerife, might be a geochemical evidence of a future volcanic unrest at Tenerife Island.

Numerical investigation of biogas diffusion flames characteristics under several operation conditions in counter-flow configuration with an emphasis on thermal and chemical effects of CO2 in the fuel mixture

NASA Astrophysics Data System (ADS)

Mameri, A.; Tabet, F.; Hadef, A.

2017-08-01

This study addresses the influence of several operating conditions (composition and ambient pressure) on biogas diffusion flame structure and NO emissions with particular attention on thermal and chemical effect of CO2. The biogas flame is modeled by a counter flow diffusion flame and analyzed in mixture fraction space using flamelet approach. The GRI Mech-3.0 mechanism that involves 53 species and 325 reactions is adopted for the oxidation chemistry. It has been observed that flame properties are very sensitive to biogas composition and pressure. CO2 addition decreases flame temperature by both thermal and chemical effects. Added CO2 may participate in chemical reaction due to thermal dissociation (chemical effect). Excessively supplied CO2 plays the role of pure diluent (thermal effect). The ambient pressure rise increases temperature and reduces flame thickness, radiation losses and dissociation amount. At high pressure, recombination reactions coupled with chain carrier radicals reduction, diminishes NO mass fraction.

Theoretical insight into Cobalt subnano-clusters adsorption on α-Al{sub 2}O{sub 3} (0001)

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

Gao, Fen-e; Ren, Jun, E-mail: jun.ren@nuc.edu.cn; Wang, Qiang

The investigation on the structural stability, nucleation, growth and interaction of cobalt cluster Con(n=2–7) on the α-Al{sub 2}O{sub 3}(0001) surface by using density functional theory methods has been reported. Energetically, the most favorable adsorption sites were identified and the strongest adsorption energy cluster is the tetrahedral Co{sub 4} cluster. On the other hand, the nucleation of Con(n=2–7) clusters on the surface is exothermic and thermodynamically favorable. Moreover, even-odd alternation was found with respect to clusters nucleation as a function of the number of cobalt atoms (for n=1–7). Meanwhile, the Co{sub n} clusters can be adsorbed on the surface stably owingmore » to the charge transfer from Co atoms to Al and O atoms of the Al{sub 2}O{sub 3} substrate. In addition, we establish the crucial importance of monomer, dimer and trimer diffusion on the surface. The diffusion of the monomer cobalt from Al{sup (3)} to O{sup (5)} or O{sup (5)} to Al{sup (4)} site is quite easy on the Al{sub 2}O{sub 3}(0001) surface, whereas the diffusion of the Co{sub 2} dimer is thermodynamically unfavorable by compared with that of the Co adatom and Co{sub 3} trimer. - Graphical abstract: Diffusion process of Co adatom on the α-Al{sub 2}O{sub 3} (0001) surface, Al{sup (3)} site→O{sup (5)} site→Al{sup (4)} site. Potential energy surface for diffusion of a single Co atom from Al{sup (3)} to O{sup (5)} site, and from O{sup (5)} to Al{sup (4)} site on the surface. The activation energy of the two migration processes from Al{sup (3)} to O{sup (5)} and O{sup (5)} to Al{sup (4)} are 0.06 and 0.09 eV, respectively. This implies the monomer is quite mobile on the surface under typical growth conditions.« less

Stomatal control of leaf fluxes of carbonyl sulfide and CO2 in a Typha freshwater marsh

NASA Astrophysics Data System (ADS)

Sun, Wu; Maseyk, Kadmiel; Lett, Céline; Seibt, Ulli

2018-06-01

Carbonyl sulfide (COS) is an emerging tracer to constrain land photosynthesis at canopy to global scales, because leaf COS and CO2 uptake processes are linked through stomatal diffusion. The COS tracer approach requires knowledge of the concentration normalized ratio of COS uptake to photosynthesis, commonly known as the leaf relative uptake (LRU). LRU is known to increase under low light, but the environmental controls over LRU variability in the field are poorly understood due to scant leaf scale observations. Here we present the first direct observations of LRU responses to environmental variables in the field. We measured leaf COS and CO2 fluxes at a freshwater marsh in summer 2013. Daytime leaf COS and CO2 uptake showed similar peaks in the mid-morning and late afternoon separated by a prolonged midday depression, highlighting the common stomatal control on diffusion. At night, in contrast to CO2, COS uptake continued, indicating partially open stomata. LRU ratios showed a clear relationship with photosynthetically active radiation (PAR), converging to 1.0 at high PAR, while increasing sharply at low PAR. Daytime integrated LRU (calculated from daytime mean COS and CO2 uptake) ranged from 1 to 1.5, with a mean of 1.2 across the campaign, significantly lower than the previously reported laboratory mean value (˜ 1.6). Our results indicate two major determinants of LRU - light and vapor deficit. Light is the primary driver of LRU because CO2 assimilation capacity increases with light, while COS consumption capacity does not. Superimposed upon the light response is a secondary effect that high vapor deficit further reduces LRU, causing LRU minima to occur in the afternoon, not at noon. The partial stomatal closure induced by high vapor deficit suppresses COS uptake more strongly than CO2 uptake because stomatal resistance is a more dominant component in the total resistance of COS. Using stomatal conductance estimates, we show that LRU variability can be explained in terms of different patterns of stomatal vs. internal limitations on COS and CO2 uptake. Our findings illustrate the stomata-driven coupling of COS and CO2 uptake during the most photosynthetically active period in the field and provide an in situ characterization of LRU - a key parameter required for the use of COS as a photosynthetic tracer.

Increased diffuse radiation fraction does not significantly accelerate plant growth

NASA Astrophysics Data System (ADS)

Angert, Alon; Krakauer, Nir

2010-05-01

A recent modelling study (Mercado et al., 2009) claims that increased numbers of scattering aerosols are responsible for a substantial fraction of the terrestrial carbon sink in recent decades because higher diffuse light fraction enhances plant net primary production (NPP). Here we show that observations of atmospheric CO2 seasonal cycle and tree ring data indicate that the relation between diffuse light and NPP is actually quite weak on annual timescales. The inconsistency of these data with the modelling results may arise because the relationships used to quantify the enhancement of NPP were calibrated with eddy covariance measurements of hourly carbon uptake. The effect of diffuse-light fraction on carbon uptake could depend on timescale, since this effect varies rapidly as sun angle and cloudiness change, and since plants can respond dynamically over various timescales to change in incoming radiation. Volcanic eruptions, such as the eruption of Mount Pinatubo in 1991, provide the best available tests for the effect of an annual-scale increase in the diffuse light fraction. Following the Pinatubo Eruption, in 1992 and 1993, a sharp decrease in the atmospheric CO2 growth rate was observed. This could have resulted from enhanced plant carbon uptake. Mercado et al. (2009) argue that largely as a result of the (volcanic aerosol driven) increase in diffuse light fraction, NPP was elevated in 1992, particularly between 25° N-45° N where annual NPP was modelled to be ~0.8 PgC (~10%) above average. In a previous study (Angert et al., 2004) a biogeochemical model (CASA) linked to an atmospheric tracer model (MATCH), was used to show that a diffuse-radiation driven increase in NPP in the extratropics will enhance carbon uptake mostly in summer, leading to a lower CO2 seasonal minimum. Here we use a 'toy model' to show that this conclusion is general and model-independent. The model shows that an enhanced sink of 0.8 PgC, similar to that modelled by Mercado et al. (2009), will result in a measurable decrease (~0.6ppm) in the seasonal CO2 minimum. This holds regardless of whether the sink is the result of 1) An increase in NPP, or 2) The combined effect of a temperature-driven decrease in heterotrophic respiration (Rh) and no change in NPP. This is since both NPP and Rh peak in summer. By contrast, observations from the NOAA global CO2 monitoring network show the opposite change in the seasonal minimum in 1992 and 1993 (~0.2ppm increase) both at Mauna Loa, and in the Marine Boundary Layer mean (>20° N), which is hard to reconcile with increased NPP in northern summer. Another indicator of annual NPP is tree wood increment. Previous work (Krakauer et al., 2003) showed that the average response in tree ring series after past Pinatubo-size volcanic eruptions implied lower NPP north of 45° N, presumably as a result of shorter growing season and lower total irradiance induced by scattering aerosols, and no significant change in NPP at lower latitudes. Here we show that In 1992, after the Pinatubo eruption, ring width in the 25° N-45° N band was 99.3±2.9% of average (n=351 sites), similar to the average of 100.4±2.2% over past eruptions (n=15 eruptions) (Uncertainty is given as 2 SE.). These results are also inconsistent with substantial NPP enhancement, although a limitation of the tree-ring approach is that available measurements do not uniformly sample the latitude band. The combined evidence of tree rings and the CO2 seasonal cycle shows that the enhancement of NPP by scattering aerosols on annual timescales is weak. This result suggests that reducing aerosols through stricter pollution controls may strengthen the land carbon sink, while geo-engineering schemes which aim to mitigate global warming by spreading scattering aerosols in the stratosphere may weaken it.

How does natural groundwater flow affect CO2 dissolution in saline aquifers?

NASA Astrophysics Data System (ADS)

Rosenzweig, R.; Michel-Meyer, I.; Tsinober, A.; Shavit, U.

2017-12-01

The dissolution of supercritical CO2 in aquifer brine is one of the most important trapping mechanisms in CO2 geological storage. Diffusion-limited dissolution is a very slow process. However, since the CO2-rich water is slightly denser than the CO2-free water, when CO2-free water is overlaid by heavier CO2-rich water, convective instability results in fingers of dense CO2-rich water that propagate downwards, causing CO2-unsaturated water to move upwards. This convection process significantly accelerates the dissolution rate of CO2 into the aquifer water.Most previous works have neglected the effect of natural groundwater flow and assumed it has no effect on the dissolution dynamics. However, it was found that in some of the saline aquifers groundwater flow rate, although small, is not zero. In this research, we study the effect of groundwater flow on dissolution by performing laboratory experiments in a bead pack cell using a mixture of methanol and ethylene-glycol as a CO2 analog while varying the water horizontal flow rate. We find that water horizontal flow decreases the number of fingers, their wavelength and their propagation velocity. When testing high water flow rates, no fingers were developed and the dissolution process was entirely diffusive. The effect of water flow on the dissolution rate did not show a clear picture. When increasing the horizontal flow rate the convective dissolution flux slightly decreased and then increased again. It seems that the combination of density-driven flow, water horizontal flow, mechanical dispersion and molecular diffusion affect the dissolution rate in a complex and non-monotonic manner. These intriguing dynamics should be further studied to understand their effect on dissolution trapping.

Carbon Chemistry in Transitional Clouds from the GOT C+ Survey of CII 158 micron Emission in the Galactic Plane

NASA Astrophysics Data System (ADS)

Langer, W. D.; Velusamy, T.; Pineda, J.; Willacy, K.; Goldsmith, P. F.

2011-05-01

In understanding the lifecycle and chemistry of the interstellar gas, the transition from diffuse atomic to molecular gas clouds is a very important stage. The evolution of carbon from C+ to C0 and CO is a fundamental part of this transition, and C+ along with its carbon chemistry is a key diagnostic. Until now our knowledge of interstellar gas has been limited primarily to the diffuse atomic phase traced by HI and the dense molecular H2 phase traced by CO. However, we have generally been missing an important layer in diffuse and transition clouds, which is denoted by the warm "dark gas'', that is mostly H2 and little HI and CO, and is best traced with C+. Here, we discuss the chemistry in the transition from C+ to C0 and CO in these clouds as understood by a survey of the CII 1.9 THz (158 micron) line from a sparse survey of the inner galaxy over about 40 degrees in longitude as part of the Galactic Observations of Terahertz C+ (GOT C+) program, a Herschel Space Observatory Open Time Key Program to study interstellar clouds by sampling ionized carbon. Using the first results from GOT C+ along 11 LOSs, in a sample of 53 transition clouds, Velusamy, Langer et al. (A&A 521, L18, 2010) detected an excess of CII intensities indicative of a thick H2 layer (a significant warm H2, "dark gas'' component) around the 12CO core. Here we present a much larger, statistically significant sample of a few hundred diffuse and transition clouds traced by CII, along with auxiliary HI and CO data in the inner Galaxy between l=-30° and +30°. Our new and more extensive sample of transition clouds is used to elucidate the time dependent physical and carbon chemical evolution of diffuse to transition clouds, and transition layers. We consider the C+ to CO conversion pathways such as H++ O and C+ + H2 chemistry for CO production to constrain the physical parameters such as the FUV intensity and cosmic ray ionization rate that drive the CO chemistry in the diffuse transition clouds.

Bundle Sheath Diffusive Resistance to CO2 and Effectiveness of C4 Photosynthesis and Refixation of Photorespired CO2 in a C4 Cycle Mutant and Wild-Type Amaranthus edulis1

PubMed Central

Kiirats, Olavi; Lea, Peter J.; Franceschi, Vincent R.; Edwards, Gerald E.

2002-01-01

A mutant of the NAD-malic enzyme-type C4 plant, Amaranthus edulis, which lacks phosphoenolpyruvate carboxylase (PEPC) in the mesophyll cells was studied. Analysis of CO2 response curves of photosynthesis of the mutant, which has normal Kranz anatomy but lacks a functional C4 cycle, provided a direct means of determining the liquid phase-diffusive resistance of atmospheric CO2 to sites of ribulose 1,5-bisphosphate carboxylation inside bundle sheath (BS) chloroplasts (rbs) within intact plants. Comparisons were made with excised shoots of wild-type plants fed 3,3-dichloro-2-(dihydroxyphosphinoyl-methyl)-propenoate, an inhibitor of PEPC. Values of rbs in A. edulis were 70 to 180 m2 s−1 mol−1, increasing as the leaf matured. This is about 70-fold higher than the liquid phase resistance for diffusion of CO2 to Rubisco in mesophyll cells of C3 plants. The values of rbs in A. edulis are sufficient for C4 photosynthesis to elevate CO2 in BS cells and to minimize photorespiration. The calculated CO2 concentration in BS cells, which is dependent on input of rbs, was about 2,000 μbar under maximum rates of CO2 fixation, which is about six times the ambient level of CO2. High re-assimilation of photorespired CO2 was demonstrated in both mutant and wild-type plants at limiting CO2 concentrations, which can be explained by high rbs. Increasing O2 from near zero up to ambient levels under low CO2, resulted in an increase in the gross rate of O2 evolution measured by chlorophyll fluorescence analysis in the PEPC mutant; this increase was simulated from a Rubisco kinetic model, which indicates effective refixation of photorespired CO2 in BS cells. PMID:12376660

Atomically layer-by-layer diffusion of oxygen/hydrogen in highly epitaxial PrBaCo2O5.5+δ thin films

NASA Astrophysics Data System (ADS)

Bao, Shanyong; Xu, Xing; Enriquez, Erik; Mace, Brennan E.; Chen, Garry; Kelliher, Sean P.; Chen, Chonglin; Zhang, Yamei; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qinyu

2015-12-01

Single-crystalline epitaxial thin films of PrBaCo2O5.5+δ (PrBCO) were prepared, and their resistance R(t) under a switching flow of oxidizing and reducing gases were measured as a function of the gas flow time t in the temperature range of 200-800 °C. During the oxidation cycle under O2, the PrBCO films exhibit fast oscillations in their dR(t)/dt vs. t plots, which reflect the oxidation processes, Co2+/Co3+ → Co3+ and Co3+ → Co3+/Co4+, that the Co atoms of PrBCO undergo. Each oscillation consists of two peaks, with larger and smaller peaks representing the oxygen/hydrogen diffusion through the (BaO)(CoO2)(PrO)(CoO2) layers of PrBCO via the oxygen-vacancy-exchange mechanism. This finding paves a significant avenue for cathode materials operating in low-temperature solid-oxide-fuel-cell devices and for chemical sensors with wide range of operating temperature.

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

Cooke, Ilsa R.; Fayolle, Edith C.; Öberg, Karin I., E-mail: irc5zb@virginia.edu

CO{sub 2} ice is an important reservoir of carbon and oxygen in star- and planet-forming regions. Together with water and CO, CO{sub 2} sets the physical and chemical characteristics of interstellar icy grain mantles, including desorption and diffusion energies for other ice constituents. A detailed understanding of CO{sub 2} ice spectroscopy is a prerequisite to characterize CO{sub 2} interactions with other volatiles both in interstellar ices and in laboratory experiments of interstellar ice analogs. We report laboratory spectra of the CO{sub 2} longitudinal optical (LO) phonon mode in pure CO{sub 2} ice and in CO{sub 2} ice mixtures with H{submore » 2}O, CO, and O{sub 2} components. We show that the LO phonon mode position is sensitive to the mixing ratio of various ice components of astronomical interest. In the era of the James Webb Space Telescope , this characteristic could be used to constrain interstellar ice compositions and morphologies. More immediately, LO phonon mode spectroscopy provides a sensitive probe of ice mixing in the laboratory and should thus enable diffusion measurements with higher precision than has been previously possible.« less

Electrochemical Reduction of CO2 to Organic Acids by a Pd-MWNTs Gas-Diffusion Electrode in Aqueous Medium

PubMed Central

Lu, Guang; Bian, Zhaoyong; Liu, Xin

2013-01-01

Pd-multiwalled carbon nanotubes (Pd-MWNTs) catalysts for the conversion of CO2 to organic acids were prepared by the ethylene glycol reduction and fully characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) technologies. The amorphous Pd particles with an average size of 5.7 nm were highly dispersed on the surface of carbon nanotubes. Functional groups of the MWNTs played a key role in the palladium deposition. The results indicated that Pd-MWNTs could transform CO2 into organic acid with high catalytic activity and CO2 could take part in the reduction reaction directly. Additionally, the electrochemical reduction of CO2 was investigated by a diaphragm electrolysis device, using a Pd-MWNTs gas-diffusion electrode as a cathode and a Ti/RuO2 net as an anode. The main products in present system were formic acid and acetic acid identified by ion chromatograph. The selectivity of the products could be achieved by reaction conditions changing. The optimum faraday efficiencies of formic and acetic acids formed on the Pd-MWNTs gas-diffusion electrode at 4 V electrode voltages under 1 atm CO2 were 34.5% and 52.3%, respectively. PMID:24453849

Synthesis, characterization and field evaluation of a new calcium-based CO2 absorbent for radial diffusive sampler

NASA Astrophysics Data System (ADS)

Cucciniello, Raffaele; Proto, Antonio; Alfano, Davide; Motta, Oriana

2012-12-01

In this paper the use of passive sampling as a powerful approach to monitor atmospheric CO2 is assessed. Suitable substrate based on calcium-aluminium oxide was synthetized according to a process which permits to control the particle size of the CaO/Al based sorbent. The study shows that hydration of substrate is an essential part of the process of CO2 absorption and subsequent conversion to carbonate. X-ray diffraction, thermogravimetric analysis, environmental scanning electron microscopic analysis were used in order to characterize the substrate and to establish the best performances both in terms of particle size and CO2 absorption capacity. Passive samplers for CO2 monitoring were prepared and then tested at laboratory level and in the atmospheric environment. Validation was performed by comparison with an infrared continuous detector. Thermogravimetric analysis results, carried out to evaluate the absorbing capability of this new passive device, were in accordance with data collected at the same time by the active continuous analyser. The diffusive sampling rate and the diffusion coefficient of CO2 respect to this new passive device were also evaluated resulting equal to 47 ± 3 ml min-1 and 0.0509 ± 0.005 cm2 s-1, respectively.

Estimation of CO2 diffusion coefficient at 0-10 cm depth in undisturbed and tilled soils

USDA-ARS?s Scientific Manuscript database

Diffusion coefficients (D) of CO2 at 0 – 10 cm layers in undisturbed and tilled soil conditions were estimated using Penman, Millington-Quirk, Ridgwell et al. (1999), Troeh et al., and Moldrup et al. models. Soil bulk density and volumetric soil water content ('v) at 0 – 10 cm were measured on April...

The effect of aging and cardiorespiratory fitness on the lung diffusing capacity response to exercise in healthy humans.

PubMed

Coffman, Kirsten E; Carlson, Alex R; Miller, Andrew D; Johnson, Bruce D; Taylor, Bryan J

2017-06-01

Aging is associated with deterioration in the structure and function of the pulmonary circulation. We characterized the lung diffusing capacity for carbon monoxide (DL CO ), alveolar-capillary membrane conductance (Dm CO ), and pulmonary-capillary blood volume (Vc) response to discontinuous incremental exercise at 25, 50, 75, and 90% of peak work (W peak ) in four groups: 1 ) Young [27 ± 3 yr, maximal oxygen consumption (V̇o 2max ): 110 ± 18% age predicted]; 2) Young Highly Fit (27 ± 3 yr, V̇o 2max : 147 ± 8% age predicted); 3 ) Old (69 ± 5 yr, V̇o 2max : 116 ± 13% age predicted); and 4 ) Old Highly Fit (65 ± 5 yr, V̇o 2max : 162 ± 18% age predicted). At rest and at 90% W peak , DL CO , Dm CO , and Vc were decreased with age. At 90% W peak , DL CO , Dm CO , and Vc were greater in Old Highly Fit vs. Old adults. The slope of the DL CO -cardiac output (Q̇) relationship from rest to end exercise at 90% W peak was not different between Young, Young Highly Fit, Old, and Old Highly Fit (1.35 vs. 1.44 vs. 1.10 vs. 1.35 ml CO ·mmHg -1 ·liter blood -1 , P = 0.388), with no evidence of a plateau in this relationship during exercise; this was also true for Dm CO -Q̇ and Vc-Q̇. V̇o 2max was positively correlated with 1 ) DL CO , Dm CO , and Vc at rest; and 2 ) the rest to end exercise change in DL CO , Dm CO , and Vc. In conclusion, these data suggest that despite the age-associated deterioration in the structure and function of the pulmonary circulation, expansion of the pulmonary capillary network does not become limited during exercise in healthy individuals regardless of age or cardiorespiratory fitness level. NEW & NOTEWORTHY Healthy aging is a crucial area of research. This article details how differences in age and cardiorespiratory fitness level affect lung diffusing capacity, particularly during high-intensity exercise. We conclude that highly fit older adults do not experience a limit in lung diffusing capacity during high-intensity exercise. Interestingly, however, we found that highly fit older individuals demonstrate greater values of lung diffusing capacity during high-intensity exercise than their less fit age-matched counterparts. Copyright © 2017 the American Physiological Society.

Atomistic Molecular Dynamics Simulations of Carbon Dioxide Diffusivity in n-Hexane, n-Decane, n-Hexadecane, Cyclohexane, and Squalane.

PubMed

Moultos, Othonas A; Tsimpanogiannis, Ioannis N; Panagiotopoulos, Athanassios Z; Trusler, J P Martin; Economou, Ioannis G

2016-12-22

Atomistic molecular dynamics simulations were carried out to obtain the diffusion coefficients of CO 2 in n-hexane, n-decane, n-hexadecane, cyclohexane, and squalane at temperatures up to 423.15 K and pressures up to 65 MPa. Three popular models were used for the representation of hydrocarbons: the united atom TraPPE (TraPPE-UA), the all-atom OPLS, and an optimized version of OPLS, namely, L-OPLS. All models qualitatively reproduce the pressure dependence of the diffusion coefficient of CO 2 in hydrocarbons measured recently, and L-OPLS was found to be the most accurate. Specifically for n-alkanes, L-OPLS also reproduced the measured viscosities and densities much more accurately than the original OPLS and TraPPE-UA models, indicating that the optimization of the torsional potential is crucial for the accurate description of transport properties of long chain molecules. The three force fields predict different microscopic properties such as the mean square radius of gyration for the n-alkane molecules and pair correlation functions for the CO 2 -n-alkane interactions. CO 2 diffusion coefficients in all hydrocarbons studied are shown to deviate significantly from the Stokes-Einstein behavior.

Winter and early spring CO2 efflux from tundra communities of northern Alaska

NASA Astrophysics Data System (ADS)

Fahnestock, J. T.; Jones, M. H.; Brooks, P. D.; Walker, D. A.; Welker, J. M.

1998-11-01

Carbon dioxide concentrations through snow were measured in different arctic tundra communities on the North Slope of Alaska during winter and early spring of 1996. Subnivean CO2 concentrations were always higher than atmospheric CO2. A steady state diffusion model was used to generate conservative estimates of CO2 flux to the atmosphere. The magnitude of CO2 efflux differed with tundra community type, and rates of carbon release increased from March to May. Winter CO2 efflux was highest in riparian and snow bed communities and lowest in dry heath, upland tussock, and wet sedge communities. Snow generally accrues earlier in winter and is deeper in riparian and snow bed communities compared with other tundra communities, which are typically windswept and do not accumulate much snow during the winter. These results support the hypothesis that early and deep snow accumulation may insulate microbial populations from very cold temperatures, allowing sites with earlier snow cover to sustain higher levels of activity throughout winter compared to communities that have later developing snow cover. Extrapolating our estimates of CO2 efflux to the entire snow-covered season indicates that total carbon flux during winter in the Arctic is 13-109 kg CO2-C ha-1, depending on the vegetation community type. Wintertime CO2 flux is a potentially important, yet largely overlooked, part of the annual carbon cycle of tundra, and carbon release during winter should be accounted for in estimates of annual carbon balance in arctic ecosystems.

Fungal inoculation and elevated CO2 mediate growth of Lolium mutiforum and Phytolacca americana, metal uptake, and metal bioavailability in metal-contaminated soil: evidence from DGT measurement.

PubMed

Song, Ningning; Wang, Fangli; Zhang, Changbo; Tang, Shirong; Guo, Junkang; Ju, Xuehai; Smith, Donald L

2013-01-01

Fungal inoculation and elevated CO2 may mediate plant growth and uptake of heavy metals, but little evidence from Diffusive Gradients in Thin-films (DGT) measurement has been obtained to characterize the process. Lolium mutiforum and Phytolacca americana were grown at ambient and elevated CO2 on naturally Cd and Pb contaminated soils inoculated with and without Trichoderma asperellum strain C3 or Penicillium chrysogenum strain D4, to investigate plant growth, metal uptake, and metal bioavailability responses. Fungal inoculation increased plant biomass and shoot/root Cd and Pb concentrations. Elevated CO2 significantly increased plants biomass, but decreased Cd and Pb concentrations in shoot/root to various extents, leading to a metal dilution phenomenon. Total Cd and Pb uptake by plants, and DGT-measured Cd and Pb concentrations in rhizosphere soils, were higher in all fungal inoculation and elevated CO2 treatments than control treatments, with the combined treatments having more influence than either treatment alone. Metal dilution phenomenon occurred because the increase in DGT-measured bioavailable metal pools in plant rhizosphere due to elevated CO2 was unable to match the increase in requirement for plant uptake of metals due to plant biomass increase.

Diffuse CO2 degassing studies to reveal hidden geothermal resources in oceanic volcanic islands: The Canarian archipelago case study

NASA Astrophysics Data System (ADS)

Rodríguez, F.; Perez, N. M.; García-Merino, M.; Padron, E.; Melián, G.; Asensio-Ramos, M.; Hernandez Perez, P. A.; Padilla, G.; Barrancos, J.; Cótchico, M. A.

2016-12-01

The Canary Islands, owing to their recent volcanism, are the only Spanish territory with potential high enthalpy geothermal resources. The final goal of geothermal exploration in a specific area is to locate and define the size, shape, structure of hidden geothermal resources, and determine their characteristics (fluid type, temperature, chemical composition an ability to produce energy). At those areas where there is not any evidence of endogenous fluids manifestations at surface, that traditionally evidence the presence of an active geothermal system) the geochemical methods for geothermal exploration must include soil gas surveys. This is the case of five mining licenses for geothermal exploration in the Canay Islands, four in Tenerife and one in Gran Canaria Island. We report herein the results of diffuse CO2 emission studies in the five mining licenses during 2011-2014. The primary objective of the study was to sort the possible geothermal potential of these five mining licenses, thus reducing the uncertainty inherent to the selection of the areas with highest geothermal potential for future exploration works. The criterion used to sort the different areas was the contribution of volcano-hydrothermal CO2 in the degassing at each study area. Several hundreds of measurements of diffuse CO2 emission, soil CO2 concentration and isotopic composition were performed at each study area. Based in three different endmembers (biogenic, atmospheric and deep-seated CO2) with different CO2 concentrations (100, 0.04 and 100% respectively) and isotopic compositions (-20, -8 and -3 per mil vs. VPDB respectively) a mass balance to distinguish the different contribution of each endmember in the soil CO2 at each sampling site was made. The percentage of the volcano-hydrothermal contribution in the current diffuse CO2 degassing was in the range 2-19%.The Abeque mining license, that comprises part of the north-west volcanic rift of Tenerife, seemed to show the highest geothermal potential, with an average of 19% of CO2 being released from deep sources, followed by Atidama (south east of Gran Canaria) and Garehagua (southern volcanic rift of Tenerife), with 17% and 12% respectively.

Review of carbon dioxide research staffing and academic support

NASA Astrophysics Data System (ADS)

Clark, S. B.; Howard, L.; Stevenson, W.; Trice, J.

1985-04-01

More than 60 percent of the staff on Carbon Dioxide Research Division (CDRD) projects were university affiliated, and over one third of project scientists and engineers also had university teaching responsibilities. Almost 20 percent of project staff were students. CO2 research is unlikely to affect the general labor market for scientists and engineers because it uses such a small portion of the total pool. On the other hand, anticipated tight labor markets in some disciplines important to CO2 research may make it advantageous for CDRD to expand its support of university faculty, students, and staff to ensure that competent, knowledgeable researchers and managers are available for eventual policy decisions on CO2 issues. Options for academic support that lend themselves readily to the diffuse nature of CO2 research, while providing flexibility in the identification and accomplishment of specific programmatic objectives, include modifying procurement procedures for research contracts to enhance academic involvement, sponsoring summer institutes tailored to specific participants and focused on issues of interest to CDRD, and supporting traveling lecture programs designed to bring information of concern to CDRD to technical and nontechnical audiences.

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?

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

Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO 2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 10 3 s –1. Oxygen can survive longer inmore » deeper layers, but it does not promote CO 2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO 2 adsorption on copper.« less

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?

DOE PAGES

Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin

2018-01-17

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO 2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 10 3 s –1. Oxygen can survive longer inmore » deeper layers, but it does not promote CO 2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO 2 adsorption on copper.« less

Transport properties in mixtures involving carbon dioxide at low and moderate density: test of several intermolecular potential energies and comparison with experiment

NASA Astrophysics Data System (ADS)

Moghadasi, Jalil; Yousefi, Fakhri; Papari, Mohammad Mehdi; Faghihi, Mohammad Ali; Mohsenipour, Ali Asghar

2009-09-01

It is the purpose of this paper to extract unlike intermolecular potential energies of five carbon dioxide-based binary gas mixtures including CO2-He, CO2-Ne, CO2-Ar, CO2-Kr, and CO2-Xe from viscosity data and compare the calculated potentials with other models potential energy reported in literature. Then, dilute transport properties consisting of viscosity, diffusion coefficient, thermal diffusion factor, and thermal conductivity of aforementioned mixtures are calculated from the calculated potential energies and compared with literature data. Rather accurate correlations for the viscosity coefficient of afore-cited mixtures embracing the temperature range 200 K < T < 3273.15 K is reproduced from the present unlike intermolecular potentials energy. Our estimated accuracies for the viscosity are to within ±2%. In addition, the calculated potential energies are used to present smooth correlations for other transport properties. The accuracies of the binary diffusion coefficients are of the order of ±3%. Finally, the unlike interaction energy and the calculated low density viscosity have been employed to calculate high density viscosities using Vesovic-Wakeham method.

Secular Variations of Soil CO2 Efflux at Santa Ana-Izalco-Coatepeque Volcanic Complex, El Salvador, Central America

NASA Astrophysics Data System (ADS)

Olmos, R.; Barahona, F.; Cartagena, R.; Soriano, T.; Salazar, J.; Hernandez, P.; Perez, N.; Lopez, D.

2002-12-01

The Santa Ana-Izalco-Coatepeque volcanic complex (2,365 m elevation), located 40 Km west of San Salvador, consists of the Coatepeque collapse caldera (a 6.5 x 10.5 Km elliptical depression), the Santa Ana and Izalco stratovolcanoes, as well as numerous cinder cones and explosion craters. The summit of the Santa Ana volcano contains an acid lake where hot springs, gas bubbling and intense fumarolic emissions occur. A volcanic plume, usually driven by the NE trades, may be seen rising up to 500 m from the summit crater of the Santa Ana volcano. The goal of this study is to provide a multidisciplinary approach for the volcanic surveillance by means of performing geochemical continuous monitoring of diffuse CO2 emission rate in addition to seismic monitoring. Temporal variations of soil CO2 efflux measured at Cerro Pacho dome, Coatepeque caldera, by means of the accumulation chamber method and using a CO2 efflux continuous monitoring station developed by WEST Systems (Italy). From May 2001 till May 2002, CO2 efflux ranged from 4.3 to 327 gm-2d-1, with a median value of 98 and a quartile range of 26 gm-2d-1. Two distinct diffuse CO2 degassing periods have been observed: (1) an increasing trend from May to July 2001, and (2) a stationary period from November 2001 to May 2002. The increasing-trend period may be due to the anomalous plume degassing at the Santa Ana volcano during 2001 and soon after the January and February 2001 earthquakes. Temporal variations of CO2 efllux during the second period seem to be coupled with those of barometric pressure and wind speed at different time scales, though most of the variance is contained at diurnal and semi-diurnal frequencies. These observations can help to explain the existence of a persistent behavior (Hurst exponent, H=0.934 +/- 0.0039) within the diffuse CO2 degassing phenomena. However, further observations are in progress to understand the long-term memory of diffuse CO2 degassing at the Santa Ana volcanic complex.

Diffuse degassing at Longonot volcano, Kenya: Implications for CO2 flux in continental rifts

NASA Astrophysics Data System (ADS)

Robertson, Elspeth; Biggs, Juliet; Edmonds, Marie; Clor, Laura; Fischer, Tobias P.; Vye-Brown, Charlotte; Kianji, Gladys; Koros, Wesley; Kandie, Risper

2016-11-01

Magma movement, fault structures and hydrothermal systems influence volatile emissions at rift volcanoes. Longonot is a Quaternary caldera volcano located in the southern Kenyan Rift, where regional extension controls recent shallow magma ascent. Here we report the results of a soil carbon dioxide (CO2) survey in the vicinity of Longonot volcano, as well as fumarolic gas compositions and carbon isotope data. The total non-biogenic CO2 degassing is estimated at < 300 kg d- 1, and is largely controlled by crater faults and fractures close to the summit. Thus, recent volcanic structures, rather than regional tectonics, control fluid pathways and degassing. Fumarolic gases are characterised by a narrow range in carbon isotope ratios (δ13C), from - 4.7‰ to - 6.4‰ (vs. PDB) suggesting a magmatic origin with minor contributions from biogenic CO2. Comparison with other degassing measurements in the East African Rift shows that records of historical eruptions or unrest do not correspond directly to the magnitude of CO2 flux from volcanic centres, which may instead reflect the current size and characteristics of the subsurface magma reservoir. Interestingly, the integrated CO2 flux from faulted rift basins is reported to be an order of magnitude higher than that from any of the volcanic centres for which CO2 surveys have so far been reported.

ANALYTICAL SOLUTIONS OF THE ATMOSPHERIC DIFFUSION EQUATION WITH MULTIPLE SOURCES AND HEIGHT-DEPENDENT WIND SPEED AND EDDY DIFFUSIVITIES. (R825689C072)

EPA Science Inventory

Abstract

Three-dimensional analytical solutions of the atmospheric diffusion equation with multiple sources and height-dependent wind speed and eddy diffusivities are derived in a systematic fashion. For homogeneous Neumann (total reflection), Dirichlet (total adsorpti...

ANALYTICAL SOLUTIONS OF THE ATMOSPHERIC DIFFUSION EQUATION WITH MULTIPLE SOURCES AND HEIGHT-DEPENDENT WIND SPEED AND EDDY DIFFUSIVITIES. (R825689C048)

EPA Science Inventory

Abstract

Three-dimensional analytical solutions of the atmospheric diffusion equation with multiple sources and height-dependent wind speed and eddy diffusivities are derived in a systematic fashion. For homogeneous Neumann (total reflection), Dirichlet (total adsorpti...

Ion Diffusivity through the Solid Electrolyte Interphase in Lithium-Ion Batteries

DOE PAGES

Benitez, Laura; Seminario, Jorge M.

2017-05-17

Understanding the transport properties of the solid electrolyte interface (SEI) is a critical piece in the development of lithium ion batteries (LIB) with better performance. We studied the lithium ion diffusivity in the main components of the SEI found in LIB with silicon anodes and performed classical molecular dynamics (MD) simulations on lithium fluoride (LiF), lithium oxide (Li 2O) and lithium carbonate (Li 2CO 3) in order to provide insights and to calculate the diffusion coefficients of Li-ions at temperatures in the range of 250 K to 400 K, which is within the LIB operating temperature range. We find amore » slight increase in the diffusivity as the temperature increases and since diffusion is noticeable at high temperatures, Li-ion diffusion in the range of 130 to 1800 K was also studied and the diffusion mechanisms involved in each SEI compound were analyzed. We observed that the predominant mechanisms of Li-ion diffusion included vacancy assisted and knock-off diffusion in LiF, direct exchange in Li 2O, and vacancy and knock-off in Li 2CO 3. Moreover, we also evaluated the effect of applied electric fields in the diffusion of Li-ions at room temperature.« less

Ion Diffusivity through the Solid Electrolyte Interphase in Lithium-Ion Batteries

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

Benitez, Laura; Seminario, Jorge M.

Understanding the transport properties of the solid electrolyte interface (SEI) is a critical piece in the development of lithium ion batteries (LIB) with better performance. We studied the lithium ion diffusivity in the main components of the SEI found in LIB with silicon anodes and performed classical molecular dynamics (MD) simulations on lithium fluoride (LiF), lithium oxide (Li 2O) and lithium carbonate (Li 2CO 3) in order to provide insights and to calculate the diffusion coefficients of Li-ions at temperatures in the range of 250 K to 400 K, which is within the LIB operating temperature range. We find amore » slight increase in the diffusivity as the temperature increases and since diffusion is noticeable at high temperatures, Li-ion diffusion in the range of 130 to 1800 K was also studied and the diffusion mechanisms involved in each SEI compound were analyzed. We observed that the predominant mechanisms of Li-ion diffusion included vacancy assisted and knock-off diffusion in LiF, direct exchange in Li 2O, and vacancy and knock-off in Li 2CO 3. Moreover, we also evaluated the effect of applied electric fields in the diffusion of Li-ions at room temperature.« less

Characterization and quantification of geochemical reaction rates in mine waste piles using unsaturated zone gases

NASA Astrophysics Data System (ADS)

Birkham, T.; Hendry, J.; Kirkland, R.; Bradley, S.; Mendoza, C.; Wassenaar, L.

2003-04-01

From 1997 to the present, we have installed and monitored 240 gas probes (maximum depth of 43 m) in unsaturated waste rock, overburden and tailings piles at a uranium mine in northern Saskatchewan, Canada and an oil sands mine in northern Alberta, Canada. Depth profiles of O2, CO2, N2 and CH4 pore-gas concentrations, temperature, and moisture content were measured in the field and used to characterize and quantifyin situ geochemical reaction rates. An innovative field-portable GC system has been developed to monitor pore-gas concentrations. At most sites, gas migration has been attributed to diffusion. At sites where advective transport may be important, subsurface total pressure measurements have been used to assess the contribution of advection to gas migration. The stable isotopes of molecular O2 (16O2 and 18O16O) and C in CO2 (12CO2 and 13CO2) have also been measured and modeled. At the uranium mine, the modelling of the O2, CO2, δ18OO2, and δ13CCO2 depth profiles was used to identify an alternative mechanism of O2 consumption and CO2 production in mine waste-rock piles. At the oil sands mine, a complex and unique system involving O2, CO2, and CH4 fluxes in the unsaturated zone and across the capillary fringe has been identified and is currently being modeled.

Lessons Learned From Recent Research on Internal CO2 Transport in Trees. Part I, CO2 Efflux and Respiration

NASA Astrophysics Data System (ADS)

McGuire, M. A.; Bloemen, J.; Aubrey, D. P.; Steppe, K.; Teskey, R. O.

2016-12-01

Currently, the most pressing problem regarding respiration in trees is determining the rate of respiration in woody tissues. In stems and roots, barriers to diffusion promote the buildup of CO2 from respiration to high concentrations, often in the range of 3 to 10% and sometimes exceeding 20%, substantially higher than that of the atmosphere ( 0.04%). A substantial portion of this internal CO2 released from respiring cells in roots and stems can dissolve in xylem sap and move upward in the xylem stream, resulting in internal transport of respired CO2 that rivals the efflux of respired CO2from woody tissues. The importance of such internal CO2 transport for the assessment of above- and below-ground respiration has gained increasing interest and here we will synthesize the latest research. The most important recent finding has been that in tree roots, a large fraction of respired CO2 remains within the root system rather than diffusing into the soil. This CO2 is transported in xylem sap into the shoot, and because respiration is almost always measured as the flux of CO2 into the atmosphere from plant tissues, it represents an unaccounted- for component of tree root metabolism. In Populus deltoides trees, for which xylem CO2 transport and soil CO2 efflux near the tree was measured, twice the amount of CO2 derived from below-ground autotrophic respiration entered the xylem stream as diffused into the soil environment. For both Eucalyptus and Quercus, up to 24 and 19% of root-respired CO2 was transported via the transpiration stream, respectively, illustrating that a significant internal transport of root-respired CO2 is present across a wide range of plant families. These findings suggest that root and soil respiration can be substantially underestimated by "soil-centric" measurements. Moreover, internal transport of respired CO2, which has only recently been recognized and measured, has important implications for our understanding of carbon dynamics at both plant and ecosystem levels.

Diffusion coefficients of phenylbutazone in supercritical CO2 and in ethanol.

PubMed

Kong, Chang Yi; Watanabe, Kou; Funazukuri, Toshitaka

2013-03-01

The diffusion coefficients D(12) of phenylbutazone at infinite dilution in supercritical CO(2) were measured by the chromatographic impulse response (CIR) method. The measurements were carried out over the temperature range from 308.2 to 343.2 K at pressures up to 40.0 MPa. In addition, the D(12) data of phenylbutazone at infinite dilution in ethanol were also measured by the Taylor dispersion method at 298.2-333.2K and at atmospheric pressure. The D(12) value of phenylbutazone increased from 4.45×10(-10) m(2) s(-1) at 298.2 K and 0.1 MPa in ethanol to about 1.43×10(-8) m(2) s(-1) at 343.2 K and 14.0 MPa in supercritical CO(2). It was found that all diffusion data of phenylbutazone measured in this study in supercritical CO(2) and in ethanol can be satisfactorily represented by the hydrodynamic equation over a wide range of fluid viscosity from supercritical state to liquid state with average absolute relative deviation of 5.4% for 112 data points. Copyright © 2013 Elsevier B.V. All rights reserved.

Modeling CO2 Storage in Fractured Reservoirs: Fracture-Matrix Interactions of Free-Phase and Dissolved CO2

NASA Astrophysics Data System (ADS)

Oldenburg, C. M.; Zhou, Q.; Birkholzer, J. T.

2017-12-01

The injection of supercritical CO2 (scCO2) in fractured reservoirs has been conducted at several storage sites. However, no site-specific dual-continuum modeling for fractured reservoirs has been reported and modeling studies have generally underestimated the fracture-matrix interactions. We developed a conceptual model for enhanced CO2 storage to take into account global scCO2 migration in the fracture continuum, local storage of scCO2 and dissolved CO2 (dsCO2) in the matrix continuum, and driving forces for scCO2 invasion and dsCO2 diffusion from fractures. High-resolution discrete fracture-matrix models were developed for a column of idealized matrix blocks bounded by vertical and horizontal fractures and for a km-scale fractured reservoir. The column-scale simulation results show that equilibrium storage efficiency strongly depends on matrix entry capillary pressure and matrix-matrix connectivity while the time scale to reach equilibrium is sensitive to fracture spacing and matrix flow properties. The reservoir-scale modeling results shows that the preferential migration of scCO2 through fractures is coupled with bulk storage in the rock matrix that in turn retards the fracture scCO2 plume. We also developed unified-form diffusive flux equations to account for dsCO2 storage in brine-filled matrix blocks and found solubility trapping is significant in fractured reservoirs with low-permeability matrix.

Reaction diffusion in the NiCrAl and CoCrAl systems

NASA Technical Reports Server (NTRS)

Levine, S. R.

1978-01-01

The paper assesses the effect of overlay coating and substrate composition on the kinetics of coating depletion by interdiffusion. This is accomplished by examining the constitution, kinetics and activation energies for a series of diffusion couples primarily of the NiCrAl/Ni-10Cr or CoCrAl/Ni-10Cr type annealed at temperatures in the range 1000-1205 C for times up to 500 hr. A general procedure is developed for analyzing diffusion in multicomponent multiphase systems. It is shown that by introducing the concept of beta-source strength, which can be determined from appropriate phase diagrams, the Wagner solution for consumption of a second phase in a semiinfinite couple is successfully applied to the analysis of MCrAl couples. Thus, correlation of beta-recession rate constants with couple composition, total and diffusional activation energies, and interdiffusion coefficients are determined.

Fixing atmospheric CO2 by environment adaptive sorbent and renewable energy

NASA Astrophysics Data System (ADS)

Wang, T.; Liu, J.; Ge, K.; Fang, M.

2014-12-01

Fixing atmospheric CO2, followed by geologic storage in remote areas is considered an environmentally secure approach to climate mitigation. A moisture swing sorbent was investigated in the laboratory for CO2 capture at a remote area with humid and windy conditions. The energy requirement of moisture swing absorption could be greatly reduced compared to that of traditional high-temperature thermal swing, by assuming that the sorbent can be naturally dried and regenerated at ambient conditions. However, for currently developed moisture swing materials, the CO2 capacity would drop significantly at high relative humidity. The CO2 capture amount can be reduced by the poor thermodynamics and kinetics at high relative humidity or low temperature. Similar challenges also exist for thermal or vacuum swing sorbents. Developing sorbent materials which adapt to specific environments, such as high humidity or low temperature, can ensure sufficient capture capacity on the one hand, and realize better economics on the other hand (Figure 1) .An environment adaptive sorbent should have the abilities of tunable capacity and fast kinetics at extreme conditions, such as high humidity or low temperature. In this presentation, the possibility of tuning CO2 absorption capacity of a polymerized ionic liquid material is discussed. The energy requirement evaluation shows that tuning the CO2 binding energy of sorbent, rather than increasing the temperature or reducing the humidity of air, could be much more economic. By determining whether the absorption process is controlled by physical diffusion controlled or chemical reaction, an effective approach to fast kinetics at extreme conditions is proposed. A shrinking core model for mass transfer kinetics is modified to cope with the relatively poor kinetics of air capture. For the studied sample which has a heterogeneous structure, the kinetic analysis indicates a preference of sorbent particle size optimization, rather than support layer optimization. Chemical reaction kinetics could be enhanced by stronger binding energy or higher temperature. However, the total kinetics can only be significantly improved by chemical reaction enhancement if the physical diffusion is fast enough.

Diffusion of CO2 in Large Crystals of Cu-BTC MOF.

PubMed

Tovar, Trenton M; Zhao, Junjie; Nunn, William T; Barton, Heather F; Peterson, Gregory W; Parsons, Gregory N; LeVan, M Douglas

2016-09-14

Carbon dioxide adsorption in metal-organic frameworks has been widely studied for applications in carbon capture and sequestration. A critical component that has been largely overlooked is the measurement of diffusion rates. This paper describes a new reproducible procedure to synthesize millimeter-scale Cu-BTC single crystals using concentrated reactants and an acetic acid modulator. Microscopic images, X-ray diffraction patterns, Brunauer-Emmett-Teller surface areas, and thermogravimetric analysis results all confirm the high quality of these Cu-BTC single crystals. The large crystal size aids in the accurate measurement of micropore diffusion coefficients. Concentration-swing frequency response performed at varying gas-phase concentrations gives diffusion coefficients that show very little dependence on the loading up to pressures of 0.1 bar. The measured micropore diffusion coefficient for CO2 in Cu-BTC is 1.7 × 10(-9) m(2)/s.

Effects of Formation Heterogeneity in Semi-Confining Shale Layers in Enhancing Mixing and Storage of Dissolved CO2

NASA Astrophysics Data System (ADS)

Illangasekare, T. H.; Agartan Karacaer, E.; Vargas-Johnson, J.; Cihan, A.; Birkholzer, J. T.

2017-12-01

It is expected that heterogeneity of the deep geologic formation to play a key role in both trapping of supercritical CO2 and its mixing in the formation brine. In previously reported research by the authors, a set of laboratory experiments and field-scale simulations were used to show that convective mixing and diffusion controlled trapping are two important mechanisms that contribute to the dissolution trapping in multilayered systems with homogeneous low-permeability zones such as shale. However, these low-permeability layers (e.g. shale) are not always homogeneous due to their composition and texture variations in addition to the presence of faults, fractures and fissures. In this study, we investigated the potential outcomes of heterogeneity present within these semi-confining low-permeability layers in regards to mixing and storage of dissolved CO2. An intermediate-scale laboratory experiment was designed to investigate the contribution of convective mixing, diffusion controlled trapping and back diffusion to long-term storage of dissolved CO2 in multilayered formations with heterogeneous low-permeability layers. The experiment was performed using a surrogate fluid combination to represent dissolved CO2 and brine under ambient pressure and temperature conditions. After verifying the numerical model with the experimental results, different distributions of the same low-permeability materials having similar volume ratios with the experimentally studied scenario were tested numerically. The experiment and modeling results showed that connectivity of higher permeability material within the semi-confining low-permeability layers contributes to mixing through brine leakage between upper and lower aquifers, storage through diffusion, and in the long term, back diffusion of stored mass due to reversed concentration gradient.

Towards improved artificial lungs through biocatalysis.

PubMed

Kaar, Joel L; Oh, Heung-Il; Russell, Alan J; Federspiel, William J

2007-07-01

Inefficient CO(2) removal due to limited diffusion represents a significant barrier in the development of artificial lungs and respiratory assist devices, which use hollow fiber membranes (HFMs) as the blood-gas interface and can require large blood-contacting membrane area. To offset the underlying diffusional challenge, "bioactive" HFMs that facilitate CO(2) diffusion were prepared via covalent immobilization of carbonic anhydrase (CA), an enzyme which catalyzes the conversion of bicarbonate in blood to CO(2), onto the surface of plasma-modified conventional HFMs. This study examines the impact of enzyme attachment on the diffusional properties and the rate of CO(2) removal of the bioactive membranes. Plasma deposition of surface reactive hydroxyls, to which CA could be attached, did not change gas permeance of the HFMs or generate membrane defects, as determined by scanning electron microscopy, when low plasma discharge power and short exposure times were employed. Cyanogen bromide activation of the surface hydroxyls and subsequent modification with CA resulted in near monolayer enzyme coverage (88%) on the membrane. The effect of increased plasma discharge power and exposure time on enzyme loading was negligible while gas permeance studies showed enzyme attachment did not impede CO(2) or O(2) diffusion. Furthermore, when employed in a model respiratory assist device, the bioactive membranes improved CO(2) removal rates by as much as 75% from physiological bicarbonate solutions with no enzyme leaching. These results demonstrate the potential of bioactive HFMs with immobilized CA to enhance CO(2) exchange in respiratory devices.

A conversion of CO2-ECBM related lab observations to reservoir requirements

NASA Astrophysics Data System (ADS)

Gensterblum, Yves; Merkel, Alexej; Busch, Andreas; Krooß, Bernhard

2013-04-01

To predict a CBM production profile either during primary or secondary production, aspects like coal permeability and porosity, density, ash and moisture content, initial gas-in-place (GIP) (from canister desorption tests), gas sorption capacity from laboratory isotherms (to obtain gas saturations and desorption pressure), gas diffusivities, coal volumetrics (thickness and areal extent) need to be understood as a minimum requirement. When dealing with CO2-ECBM selective adsorption, counter diffusion in the coal matrix, or coal shrinkage and swelling (from CH4 desorption and CO2 adsorption, respectively) and the influence of moisture need to be investigated in addition to the parameters above. During CO2-ECBM processes, the areal distribution of the CO2 injected is accomplished by flow through the cleat network. When CO2 is entering the coal matrix by a combined sorption/diffusion process it will adsorb to the coal inner surface and at the same time replace part of the CH4. This replacement occurs either by a reduction in the CH4 partial pressure or by a higher selective sorption of CO2 over CH4. Because of a concentration gradient between CH4 in the matrix compared to the cleat system, CH4 diffuses from the coal matrix into the cleat system where, by pressure drawdown towards a production well, it can be produced. In this context this presentation summarizes gas (CO2, CH4) and water sorption on coal and specifically addresses the following topics: • CH4 and CO2 sorption capacity as a function depth and rank • CO2 and CH4 sorption on natural coals and its dependence on coal specific parameters like coal rank, maceral composition or ash content (Busch and Gensterblum, 2011). • Water sorption on coal, its dependence on coal properties such as rank and coal chemistry and gas sorption in the presence of water (Busch and Gensterblum, 2011). • Uncertainties in reservoir characterisation (Gensterblum et al., 2010; Gensterblum et al., 2009) • Sorption uptake kinetic as a function of surface coverage and the influence of moisture on the kinetic Busch, A. and Gensterblum, Y., 2011. CBM and CO2-ECBM related sorption processes in coal: A review. International Journal of Coal Geology, 87: 49-71. Gensterblum, Y. et al., 2010. European inter-laboratory comparison of high pressure CO2 sorption isotherms II: Natural coals. International Journal of Coal Geology, 84(2): 115-124. Gensterblum, Y. et al., 2009. European inter-laboratory comparison of high pressure CO2 sorption isotherms. I: Activated carbon. Carbon, 47(13): 2958-2969.

Cobalt Modification of Thin Rutile Films Magnetron-Sputtered in Vacuum

NASA Astrophysics Data System (ADS)

Afonin, N. N.; Logacheva, V. A.

2018-04-01

Using X-ray phase analysis, atomic force microscopy, and secondary ion mass-spectrometry, the phase formation and component distribution in a Co-TiO2 film system have been investigated during magnetron sputtering of the metal on the oxide and subsequent vacuum annealing. It has been found that cobalt diffuses deep into titanium oxide to form complex oxides CoTi2O5 and CoTiO3. A mechanism behind their formation at grain boundaries throughout the thickness of the TiO2 film is suggested. It assumes the reactive diffusion of cobalt along grain boundaries in the oxide. A quantitative model of reactive interdiffusion in a bilayer polycrystalline metal-oxide film system with limited solubility of components has been developed. The individual diffusion coefficients of cobalt and titanium have been determined in the temperature interval 923-1073 K.

Effects of process parameters on peanut skins extract and CO2 diffusivity by supercritical fluid extraction

NASA Astrophysics Data System (ADS)

Putra, N. R.; Yian, L. N.; Nasir, H. M.; Idham, Z. Binti; Yunus, M. A. C.

2018-03-01

Peanut skins (Arachis hypogea) are an agricultural waste product which has received much attention because they contain high nutritional values and can be potentially utilized in difference industries. At present, only a few studies have been conducted to study the effects of parameters on the peanut skins oil extraction. Therefore, this study aimed to determine the best extraction condition in order to obtain the highest extract yield using supercritical carbon dioxide (SC-CO2) with co-solvent Ethanol as compared to Soxhlet extraction method. Diffusivity of carbon dioxide in supercritical fluid extraction was determined using Crank model. The mean particle size used in this study was 425 µm. The supercritical carbon dioxide was performed at temperature (40 – 70 °C), flow rate of co-solvent ethanol (0 - 7.5% Vethanol/Vtotal), and extraction pressure (10 – 30 MPa) were used in this studies. The results showed that the percentage of oil yields and effective diffusivity increase as the pressure, rate of co-solvent, and temperature increased.

C+/CO Transitions in the Diffuse ISM: Transitional Cloud Sample from the GOT C+ Survey of [CII] in the inner Galaxy at l = -30deg to 30deg

NASA Astrophysics Data System (ADS)

Velusamy, T.; Pineda, J. L.; Langer, W. D.; Willacy, K.; Goldsmith, P. F.

2011-05-01

Our knowledge of interstellar gas has been limited primarily to the diffuse atomic phase traced by HI and the well-shielded molecular phase traced by CO. Recently, using the first results of the Herschel Key Project GOT C+, a HIFI C+ survey of the Galactic plane, Velusamy, Langer, Pineda et al. (A&A 521, L18, 2010) have shown that in the diffuse interstellar transition clouds a significant fraction of the carbon exists primarily as C^+ with little C^0 and CO in a warm 'dark gas' layer in which hydrogen is mostly H_2 with little atomic H, surrounding a modest 12CO-emitting core. The [CII] fine structure transition, at 1.9 THz (158 μm) is the best tracer of this component of the interstellar medium, which is critical to our understanding of the atomic to molecular cloud transitions. The Herschel Key Project GOT C+ is designed to study such clouds by observing with HIFI the [CII] line emission along 500 lines of sight (LOSs) throughout the Galactic disk. Here we present the identification and chemical status of a few hundred diffuse and transition clouds traced by [CII], along with auxiliary HI and CO data covering ~100 LOSs in the inner Galaxy between l= -30° and 30°. We identify transition clouds as [CII] components that are characterized by the presence of both HI and 12CO, but no 13CO emission. The intensities, I(CII) and I(HI), are used as measures of the visual extinction, AV, in the cloud up to the C^+/C^0/CO transition layer and a comparison with I(12CO) yields a more complete H_2 molecular inventory. Our results show that [CII] emission is an excellent tool to study transition clouds and their carbon chemistry in the ISM, in particular as a unique tracer of molecular H_2, which is not easily observed by other means. The large sample presented here will serve as a resource to study the chemical and physical status of diffuse transition clouds in a wide range of Galactic environments and constrain the physical parameters such as the FUV intensity and cosmic ray ionization rate that drive the CO chemistry in the diffuse ISM.

Blocking germanium diffusion inside silicon dioxide using a co-implanted silicon barrier

NASA Astrophysics Data System (ADS)

Barba, D.; Wang, C.; Nélis, A.; Terwagne, G.; Rosei, F.

2018-04-01

We investigate the effect of co-implanting a silicon sublayer on the thermal diffusion of germanium ions implanted into SiO2 and the growth of Ge nanocrystals (Ge-ncs). High-resolution imaging obtained by transmission electron microscopy and energy dispersive spectroscopy measurements supported by Monte-Carlo calculations shows that the Si-enriched region acts as a diffusion barrier for Ge atoms. This barrier prevents Ge outgassing during thermal annealing at 1100 °C. Both the localization and the reduced size of Ge-ncs formed within the sample region co-implanted with Si are observed, as well as the nucleation of mixed Ge/Si nanocrystals containing structural point defects and stacking faults. Although it was found that the Si co-implantation affects the crystallinity of the formed Ge-ncs, this technique can be implemented to produce size-selective and depth-ordered nanostructured systems by controlling the spatial distribution of diffusing Ge. We illustrate this feature for Ge-ncs embedded within a single SiO2 monolayer, whose diameters were gradually increased from 1 nm to 5 nm over a depth of 100 nm.

Characterization of thin film CO2 ice through the infrared ν1 + ν3 combination mode

NASA Astrophysics Data System (ADS)

He, Jiao; Vidali, Gianfranco

2018-01-01

Carbon dioxide is abundant in ice mantles of dust grains; some is found in the pure crystalline form as inferred from the double peak splitting of the bending profile at about 650 cm-1. To study how CO2 segregates into the pure form from water-rich mixtures of ice mantles and how it then crystallizes, we used Reflection Absorption InfraRed Spectroscopy to study the structural change of pure CO2 ice as a function of both ice thickness and temperature. We found that the ν1 + ν3 combination mode absorption profile at 3708 cm-1 provides an excellent probe to quantify the degree of crystallinity in CO2 ice. We also found that between 20 and 30 K, there is an ordering transition that we attribute to reorientation of CO2 molecules, while the diffusion of CO2 becomes significant at much higher temperatures. In the formation of pure crystalline CO2 in interstellar medium ices, the rate limiting process is the diffusion/segregation of CO2 molecules in the ice instead of the phase transition from amorphous to crystalline after clusters/islands of CO2 are formed.

Dynamics and mass transport of solutal convection in a closed porous media system

NASA Astrophysics Data System (ADS)

Wen, Baole; Akhbari, Daria; Hesse, Marc

2016-11-01

Most of the recent studies of CO2 sequestration are performed in open systems where the constant partial pressure of CO2 in the vapor phase results in a time-invariant saturated concentration of CO2 in the brine (Cs). However, in some closed natural CO2 reservoirs, e.g., Bravo Dome in New Mexico, the continuous dissolution of CO2 leads to a pressure drop in the gas that is accompanied by a reduction of Cs and thereby affects the dynamics and mass transport of convection in the brine. In this talk, I discuss the characteristics of convective CO2 dissolution in a closed system. The gas is assumed to be ideal and its solubility given by Henry's law. An analytical solution shows that the diffusive base state is no longer self-similar and that diffusive mass transfer declines rapidly. Scaling analysis reveals that the volume ratio of brine and gas η determines the behavior of the system. DNS show that no constant flux regime exists for η > 0 nevertheless, the quantity F /Cs2 remains constant, where F is the dissolution flux. The onset time is only affected by η when the Rayleigh number Ra is small. In this case, the drop in Cs during the initial diffusive regime significantly reduces the effective Ra and therefore delays the onset.

A Vertical Diffusion Scheme to estimate the atmospheric rectifier effect

NASA Astrophysics Data System (ADS)

Chen, Baozhang; Chen, Jing M.; Liu, Jane; Chan, Douglas; Higuchi, Kaz; Shashkov, Alexander

2004-02-01

The magnitude and spatial distribution of the carbon sink in the extratropical Northern Hemisphere remain uncertain in spite of much progress made in recent decades. Vertical CO2 diffusion in the planetary boundary layer (PBL) is an integral part of atmospheric CO2 transport and is important in understanding the global CO2 distribution pattern, in particular, the rectifier effect on the distribution [Keeling et al., 1989; Denning et al., 1995]. Attempts to constrain carbon fluxes using surface measurements and inversion models are limited by large uncertainties in this effect governed by different processes. In this study, we developed a Vertical Diffusion Scheme (VDS) to investigate the vertical CO2 transport in the PBL and to evaluate CO2 vertical rectification. The VDS was driven by the net ecosystem carbon flux and the surface sensible heat flux, simulated using the Boreal Ecosystem Productivity Simulator (BEPS) and a land surface scheme. The VDS model was validated against half-hourly CO2 concentration measurements at 20 m and 40 m heights above a boreal forest, at Fraserdale (49°52'29.9''N, 81°34'12.3''W), Ontario, Canada. The amplitude and phase of the diurnal/seasonal cycles of simulated CO2 concentration during the growing season agreed closely with the measurements (linear correlation coefficient (R) equals 0.81). Simulated vertical and temporal distribution patterns of CO2 concentration were comparable to those measured at the North Carolina tower. The rectifier effect, in terms of an annual-mean vertical gradient of CO2 concentration in the atmosphere that decreases from the surface to the top of PBL, was found at Fraserdale to be about 3.56 ppmv. Positive covariance between the seasonal cycles of plant growth and PBL vertical diffusion was responsible for about 75% of the effect, and the rest was caused by covariance between their diurnal cycles. The rectifier effect exhibited strong seasonal variations, and the contribution from the diurnal cycle was mostly confined to the surface layer (less than 300 m).

Assessment of mercury bioavailability to benthic macroinvertebrates using diffusive gradients in thin films (DGT).

PubMed

Amirbahman, Aria; Massey, Delia I; Lotufo, Guilherme; Steenhaut, Nicholas; Brown, Lauren E; Biedenbach, James M; Magar, Victor S

2013-10-01

Mercury-specific diffusive gradient in thin films (DGTs) were used in laboratory microcosms as a biomonitoring tool to assess the lability of mercury (Hg) total and monomethylmercury Hg (MeHg), and to develop a relationship between chemical lability and bioavailability in estuarine sediments. Time-series deployment of DGTs in sediments showed that sediment-bound MeHg is more labile than sediment-bound inorganic Hg. In subsequent experiments, DGTs were deployed simultaneously with three benthic macroinvertebrates (the estuarine amphipod, Leptocheirus plumulosus; the estuarine polychaete, Nereis virens; and the marine clam, Macoma nasuta) in sediments for up to 55 days. All organisms and their co-deployed DGTs exhibited an initial period of rapid Hg uptake followed by slower uptake reaching apparent steady state. Strong correlative relationships were generally observed between paddle-type DGTs and macroinvertebrate tissue data (r(2) between 0.57 and 0.97). Further, %MeHg:Total Hg ratios for M. nasuta and N. virens (38.5 ± 12.2 and 19.2 ± 5.2) were similar to their corresponding ratios for the DGTs (33.1 ± 13.3 and 24.4 ± 11.0), and they were significantly higher than the same ratios for sediment (2.9 ± 0.3) and pore water (8.5 ± 4.9). The %MeHg:Total Hg ratios for L. plumulosus (68.5 ± 6.2) were significantly higher than those for the DGTs. This may be because the tissue and DGT data for this organism were not truly co-located as L. plumulosus burrows close to the sediment surface, and the DGTs sampled the sediment surface. Overall, our results suggest that for benthic macroinvertebrates in estuarine sediments studied here, (a) sediment MeHg is more bioavailable than inorganic Hg, (b) sediment and pore-water concentration measurements are not good predictors for the extent of bioaccumulation of Hg species, and (c) DGTs are an effective biomonitoring tool for the assessment of bioavailability of Hg species.

Determination of Diffusion Parameters of CO2 Through Microporous PTFE Using a Potentiometric Method

NASA Astrophysics Data System (ADS)

Tarsiche, I.; Ciurchea, D.

Dk values at the diffusion of CO2 through microporous PTFE of 1 to 7 × 10- 7 cm2 s- 1 in the concentration range from 4 × 10- 4 to 0.22 g/l CO2 are determined using a simple, fast and reliable potentiometric method. The method is based on the least-squares fitting of the potential versus time response of a self made CO2 sensitive Severinghaus type sensor with PTFE as a gas-permeable membrane. The obtained results are in good agreement with other reported literature data, both experimental or calculated ones using molecular dynamics simulations. The proposed technique is very sensitive especially at low concentrations of gas and may be used for the study of other polymeric membranes too.

Evidence of a reduction reaction of oxidized iron/cobalt by boron atoms diffused toward naturally oxidized surface of CoFeB layer during annealing

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

Sato, Soshi, E-mail: sato.soshi@cies.tohoku.ac.jp; Honjo, Hiroaki; Niwa, Masaaki

2015-04-06

We have investigated the redox reaction on the surface of Ta/CoFeB/MgO/CoFeB magnetic tunnel junction stack samples after annealing at 300, 350, and 400 °C for 1 h using angle-resolved X-ray photoelectron spectroscopy for precise analysis of the chemical bonding states. At a capping tantalum layer thickness of 1 nm, both the capping tantalum layer and the surface of the underneath CoFeB layer in the as-deposited stack sample were naturally oxidized. By comparison of the Co 2p and Fe 2p spectra among the as-deposited and annealed samples, reduction of the naturally oxidized cobalt and iron atoms occurred on the surface of the CoFeB layer.more » The reduction reaction was more significant at higher annealing temperature. Oxidized cobalt and iron were reduced by boron atoms that diffused toward the surface of the top CoFeB layer. A single CoFeB layer was prepared on SiO{sub 2}, and a confirmatory evidence of the redox reaction with boron diffusion was obtained by angle-resolved X-ray photoelectron spectroscopy analysis of the naturally oxidized surface of the CoFeB single layer after annealing. The redox reaction is theoretically reasonable based on the Ellingham diagram.« less

Diffuse CO 2 soil degassing and CO 2 and H 2S concentrations in air and related hazards at Vulcano Island (Aeolian arc, Italy)

NASA Astrophysics Data System (ADS)

Carapezza, M. L.; Barberi, F.; Ranaldi, M.; Ricci, T.; Tarchini, L.; Barrancos, J.; Fischer, C.; Perez, N.; Weber, K.; Di Piazza, A.; Gattuso, A.

2011-10-01

La Fossa crater on Vulcano Island is quiescent since 1890. Periodically it undergoes "crises" characterized by marked increase of temperature (T), gas output and concentration of magmatic components in the crater fumaroles (T may exceed 600 °C). During these crises, which so far did not lead to any eruptive reactivation, the diffuse CO 2 soil degassing also increases and in December 2005 an anomalous CO 2 flux of 1350 tons/day was estimated by 1588 measurements over a surface of 1.66 km 2 extending from La Fossa crater to the inhabited zone of Vulcano Porto. The crater area and two other anomalously degassing sites (Levante Beach and Palizzi) have been periodically investigated from December 2004 to August 2010 for diffuse CO 2 soil flux. They show a marked variation with time of the degassing rate, with synchronous maxima in December 2005. Carbon dioxide soil flux and environmental parameters have been also continuously monitored for over one year by an automatic station at Vulcano Porto. In order to assess the hazard of the endogenous gas emissions, CO 2 and H 2S air concentrations have been measured by Tunable Diode Laser profiles near the fumaroles of the crater rim and of the Levante Beach area, where also the viscous gas flux has been estimated. In addition, CO 2 air concentration has been measured both indoor and outdoor in an inhabited sector of Vulcano Porto. Results show that in some sites usually frequented by tourists there is a dangerous H 2S air concentration and CO 2 exceeds the hazardous thresholds in some Vulcano houses. These zones should be immediately monitored for gas hazard should a new crisis arise.

Enhancement of crop photosynthesis by diffuse light: quantifying the contributing factors

PubMed Central

Li, T.; Heuvelink, E.; Dueck, T. A.; Janse, J.; Gort, G.; Marcelis, L. F. M.

2014-01-01

Background and Aims Plants use diffuse light more efficiently than direct light. However, experimental comparisons between diffuse and direct light have been obscured by co-occurring differences in environmental conditions (e.g. light intensity). This study aims to analyse the factors that contribute to an increase in crop photosynthesis in diffuse light and to quantify their relative contribution under different levels of diffuseness at similar light intensities. The hypothesis is that the enhancement of crop photosynthesis in diffuse light results not only from the direct effects of more uniform vertical and horizontal light distribution in the crop canopy, but also from crop physiological and morphological acclimation. Methods Tomato (Solanum lycopersicum) crops were grown in three greenhouse compartments that were covered by glass with different degrees of light diffuseness (0, 45 and 71 % of the direct light being converted into diffuse light) while maintaining similar light transmission. Measurements of horizontal and vertical photosynthetic photon flux density (PPFD) distribution in the crop, leaf photosynthesis light response curves and leaf area index (LAI) were used to quantify each factor's contribution to an increase in crop photosynthesis in diffuse light. In addition, leaf temperature, photoinhibition, and leaf biochemical and anatomical properties were studied. Key Results The highest degree of light diffuseness (71 %) increased the calculated crop photosynthesis by 7·2 %. This effect was mainly attributed to a more uniform horizontal (33 % of the total effect) and vertical PPFD distribution (21 %) in the crop. In addition, plants acclimated to the high level of diffuseness by gaining a higher photosynthetic capacity of leaves in the middle of the crop and a higher LAI, which contributed 23 and 13 %, respectively, to the total increase in crop photosynthesis in diffuse light. Moreover, diffuse light resulted in lower leaf temperatures and less photoinhibition at the top of the canopy when global irradiance was high. Conclusions Diffuse light enhanced crop photosynthesis. A more uniform horizontal PPFD distribution played the most important role in this enhancement, and a more uniform vertical PPFD distribution and higher leaf photosynthetic capacity contributed more to the enhancement of crop photosynthesis than did higher values of LAI. PMID:24782436

Molecular modeling of polymers 16. Gaseous diffusion in polymers: a quantitative structure-property relationship (QSPR) analysis.

PubMed

Patel, H C; Tokarski, J S; Hopfinger, A J

1997-10-01

The purpose of this study was to identify the key physicochemical molecular properties of polymeric materials responsible for gaseous diffusion in the polymers. Quantitative structure-property relationships, QSPRs were constructed using a genetic algorithm on a training set of 16 polymers for which CO2, N2, O2 diffusion constants were measured. Nine physicochemical properties of each of the polymers were used in the trial basis set for QSPR model construction. The linear cross-correlation matrices were constructed and investigated for colinearity among the members of the training sets. Common water diffusion measures for a limited training set of six polymers was used to construct a "semi-QSPR" model. The bulk modulus of the polymer was overwhelmingly found to be the dominant physicochemical polymer property that governs CO2, N2 and O2 diffusion. Some secondary physicochemical properties controlling diffusion, including conformational entropy, were also identified as correlation descriptors. Very significant QSPR diffusion models were constructed for all three gases. Cohesive energy was identified as the main correlation physicochemical property with aqueous diffusion measures. The dominant role of polymer bulk modulus on gaseous diffusion makes it difficult to develop criteria for selective transport of gases through polymers. Moreover, high bulk moduli are predicted to be necessary for effective gas barrier materials. This property requirement may limit the processing and packaging features of the material. Aqueous diffusion in polymers may occur by a different mechanism than gaseous diffusion since bulk modulus does not correlate with aqueous diffusion, but rather cohesive energy of the polymer.

Multi-Sensor Mapping of Diffuse Degassing of C-O-H Compounds in Terrestrial Hydrothermal Systems

NASA Astrophysics Data System (ADS)

Schwandner, F. M.; Shock, E. L.

2004-12-01

In-situ single-sensor detection and mapping of diffuse degassing phenomena in hydrothermal and volcanic areas can be used to elucidate subsurface tectonic structures, assess emission rates, and to monitor emission variability (Williams 1985; Chiodini et al. 1996, Werner et al., 2003). More than one technique has been deployed to measure several gas species simultaneously (e.g., Crenshaw et al. 1982), and correlations of one gas species (usually CO2) with physical parameters like heat flux (Brombach et al., 2001), or with one other gas species (Rn, He) have been demonstrated (Barberi & Carapezza 1994; Williams-Jones et al., 2000). Recently, correlations of multiple gas species with one another were reported (Schwandner et al., 2004), leading to the possibility of quantitative mapping of subsurface hydrothermal chemical processes by simultaneous measurement of reaction partners and products that continuously and diffusely degas. In the present study, we joined a fully-quantitative multi-sensor instrument (Draeger Multiwarn II) to a modified accumulation-chamber sensing method (Chiodini et al., 1996) and measured diffuse degassing of CH4, H2, CO2, CO, and H2S. In this approach, each batch of gas that is recirculated through the detector is simultaneously analyzed by all sensors. To test this approach we chose two magmatically influenced, hydrothermally active areas at Yellowstone National Park (USA): Sylvan Springs and the Greater Obsidian Pool Area. The area near Obsidian Pool was previously studied during a diffuse CO2 degassing campaign (Werner & Brantley, 2004). Preliminary results show that elevated reduced gas emissions appear to be most prominent near hydrothermal pools, whereas CO2-dominated degassing anomalies highlight subsurface tectonic structures. This multimodal distribution allows us to distinguish deep degassing sources (CO2 anomalies) from shallow localized hydrothermal processes (reduced gas anomalies). The results permit us to positively identify and partially map a previously-inferred active lineament in the Obsidian Pool area. In addition, reduced gas data are yielding areal ratio distributions of CO/CO2, H2/CH4, and CO/CH4, that may be indicative of reactions such as the catalytic hydrogenation of CO2 (Sabatier-Process) and of CO (Fischer-Tropsch-Process) within the shallow hydrothermal system. Barberi & Carapezza (1994). Bull. Volcanol. 56(5): 335-342. Brombach, et al. (2001). Geophys. Res. Lett. 28(1): 69-72. Crenshaw et al. (1982). Nature 300: 345-346. Chiodini et al. (1996). Bull. Volcanol. 58(1): 41-50. Schwandner et al. (2004). JGR D 109: D04301, doi:10.1029/2003JD003890. Werner & Brantley (2004) JGR B 105: 10,831-10,846. Werner et al. (2003). Earth Planet. Sci. Lett. 210: 561-577. Williams (1985). Science 229(4713): 551-553. Williams-Jones et al. (2000). Bull. Volcanol. 62: 130-142.

Diffusive leakage of brine from aquifers during CO2 geological storage

NASA Astrophysics Data System (ADS)

Dejam, Morteza; Hassanzadeh, Hassan

2018-01-01

The area of investigation in this study is designed around an improved understanding of fundamentals of the diffusive leakage of brine from a storage aquifer into overlying and underlying low permeability layers during geosequestration of carbon dioxide (CO2) through development of a theoretical model. Here, we consider a two-dimensional domain in cylindrical coordinates, comprised of an aquifer and an overburden, where the interaction between the two media is handled by imposing the continuities of pressures and fluid fluxes at the aquifer-overburden interface. This coupled problem is solved by successive implementation of the Laplace and finite Hankel transforms. The developed solutions can be used to analyze diffusive leakage of brine from the aquifer into overburden and generate type curves for average pressures in the aquifer and overburden during injection and post injection periods. The results show that the leakage rate at early times is scaled with t1/2 while it remains constant at late times. It is also shown that the average pressure in the aquifer is scaled with t for short and long times. Moreover, the average pressure in the overburden is scaled with t at late times while it is scaled with t3/2 at early times. In addition, the results reveal that factors affecting diffusive leakage rate through intact overburden during CO2 storage are, in decreasing order of significance, thickness of overburden, thickness of aquifer, aquifer to overburden permeability ratio, and aquifer to overburden porosity ratio. However, thickness of aquifer has minimal effect on diffusive leakage of brine within post injection period. To evaluate the theoretical model, case studies for two potential sites in United Kingdom, one in Lincolnshire and the other one in the Firth of Forth, are conducted. The field studies show that the diffusive leakage from the aquifer into the overburden diminishes ∼40 years after the injection has ceased for Lincolnshire while it stops after ∼12 years for Firth of Forth. The average amount of the brine leaked from the aquifers per standard cubic meter (Sm3) of the injected CO2 through diffusive leakage was found to be 6.28 × 10-4 m3 of brine (or 0.330 kg of brine/kg of CO2) over ∼70 years for Lincolnshire and 4.59 × 10-4 m3 of brine (or 0.242 kg of brine/kg of CO2) over ∼42 years for Firth of Forth.

Ab initio intermolecular potential energy surface for the CO2—N2 system and related thermophysical properties

NASA Astrophysics Data System (ADS)

Crusius, Johann-Philipp; Hellmann, Robert; Castro-Palacio, Juan Carlos; Vesovic, Velisa

2018-06-01

A four-dimensional potential energy surface (PES) for the interaction between a rigid carbon dioxide molecule and a rigid nitrogen molecule was constructed based on quantum-chemical ab initio calculations up to the coupled-cluster level with single, double, and perturbative triple excitations. Interaction energies for a total of 1893 points on the PES were calculated using the counterpoise-corrected supermolecular approach and basis sets of up to quintuple-zeta quality with bond functions. The interaction energies were extrapolated to the complete basis set limit, and an analytical site-site potential function with seven sites for carbon dioxide and five sites for nitrogen was fitted to the interaction energies. The CO2—N2 cross second virial coefficient as well as the dilute gas shear viscosity, thermal conductivity, and binary diffusion coefficient of CO2—N2 mixtures were calculated for temperatures up to 2000 K to validate the PES and to provide reliable reference values for these important properties. The calculated values are in very good agreement with the best experimental data.

Comparative study of the quality characteristics of defatted soy flour treated by supercritical carbon dioxide and organic solvent.

PubMed

Kang, Sung-Won; Rahman, M Shafiur; Kim, Ah-Na; Lee, Kyo-Yeon; Park, Chan-Yang; Kerr, William L; Choi, Sung-Gil

2017-07-01

Defatted soy flour is a potential source of food protein, amino acids, ash and isoflavones. The supercritical carbon dioxide (SC-CO 2 ) and a traditional organic solvent extraction methods were used to remove fat from soy flour, and the quality characteristics of a control soy flour (CSF), defatted soy flour by SC-CO 2 (DSFSC-CO 2 ) and defatted soy flour by an organic solvent (DSF-OS) were compared. The SC-CO 2 process was carried out at a constant temperature of 45 °C, and a pressure of 40 MPa for 3 h with a CO 2 flow rate of 30 g/min. The DSFSC-CO 2 had significantly higher protein, ash, and amino acids content than CSF and DSF-OS. The sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) analysis demonstrated that CSF and DSFSC-CO 2 had protein bands of similar intensity and area that indicated no denaturation of protein, whereas DSF-OS showed diffuse bands or no bands due to protein denaturation. In addition to higher nutritional value and protein contents, DSFSC-CO 2 showed superior functional properties in terms of total soluble solids content, water and oil absorption, emulsifying and foaming capacity. The SC-CO 2 method offers a nutritionally and environmentally friendly alternative extraction processing approach for the removal of oil from high-protein food sources. It has a great potential for producing high-protein fat-free, and low-calorie content diet than the traditional organic solvent extraction method.

Winter and early spring CO2 efflux from tundra communities of northern Alaska

USGS Publications Warehouse

Fahnestock, J.T.; Jones, M.H.; Brooks, P.D.; Walker, D.A.; Welker, J.M.

1998-01-01

Carbon dioxide concentrations through snow were measured in different arctic tundra communities on the North Slope of Alaska during winter and early spring of 1996. Subnivean CO2 concentrations were always higher than atmospheric CO2. A steady state diffusion model was used to generate conservative estimates of CO2 flux to the atmosphere. The magnitude of CO2 efflux differed with tundra community type, and rates of carbon release increased from March to May. Winter CO2 efflux was highest in riparian and snow bed communities and lowest in dry heath, upland tussock, and wet sedge communities. Snow generally accrues earlier in winter and is deeper in riparian and snow bed communities compared with other tundra communities, which are typically windswept and do not accumulate much snow during the winter. These results support the hypothesis that early and deep snow accumulation may insulate microbial populations from very cold temperatures, allowing sites with earlier snow cover to sustain higher levels of activity throughout winter compared to communities that have later developing snow cover. Extrapolating our estimates of CO2 efflux to the entire snow-covered season indicates that total carbon flux during winter in the Arctic is 13-109 kg CO2-C ha-1, depending on the vegetation community type. Wintertime CO2 flux is a potentially important, yet largely overlooked, part of the annual carbon cycle of tundra, and carbon release during winter should be accounted for in estimates of annual carbon balance in arctic ecosystems. Copyright 1998 by the American Geophysical Union.

Laser inscription of pseudorandom structures for microphotonic diffuser applications.

PubMed

Alqurashi, Tawfiq; Alhosani, Abdulla; Dauleh, Mahmoud; Yetisen, Ali K; Butt, Haider

2018-04-19

Optical diffusers provide a solution for a variety of applications requiring a Gaussian intensity distribution including imaging systems, biomedical optics, and aerospace. Advances in laser ablation processes have allowed the rapid production of efficient optical diffusers. Here, we demonstrate a novel technique to fabricate high-quality glass optical diffusers with cost-efficiency using a continuous CO2 laser. Surface relief pseudorandom microstructures were patterned on both sides of the glass substrates. A numerical simulation of the temperature distribution showed that the CO2 laser drills a 137 μm hole in the glass for every 2 ms of processing time. FFT simulation was utilized to design predictable optical diffusers. The pseudorandom microstructures were characterized by optical microscopy, Raman spectroscopy, and angle-resolved spectroscopy to assess their chemical properties, optical scattering, transmittance, and polarization response. Increasing laser exposure and the number of diffusing surfaces enhanced the diffusion and homogenized the incident light. The recorded speckle pattern showed high contrast with sharp bright spot free diffusion in the far field view range (250 mm). A model of glass surface peeling was also developed to prevent its occurrence during the fabrication process. The demonstrated method provides an economical approach in fabricating optical glass diffusers in a controlled and predictable manner. The produced optical diffusers have application in fibre optics, LED systems, and spotlights.

Ultraviolet Survey of CO and H2 in Diffuse Molecular Clouds: The Reflection of Two Photochemistry Regimes in Abundance Relationships

NASA Astrophysics Data System (ADS)

Sheffer, Y.; Rogers, M.; Federman, S. R.; Abel, N. P.; Gredel, R.; Lambert, D. L.; Shaw, G.

2008-11-01

We carried out a comprehensive far-UV survey of 12CO and H2 column densities along diffuse molecular Galactic sight lines. This sample includes new measurements of CO from HST spectra along 62 sight lines and new measurements of H2 from FUSE data along 58 sight lines. In addition, high-resolution optical data were obtained at the McDonald and European Southern Observatories, yielding new abundances for CH, CH+, and CN along 42 sight lines to aid in interpreting the CO results. These new sight lines were selected according to detectable amounts of CO in their spectra and provide information on both lower density (<=100 cm-3) and higher density diffuse clouds. A plot of log N(CO) versus log N(H2) shows that two power-law relationships are needed for a good fit of the entire sample, with a break located at log N(CO , cm -2) = 14.1 and log N(H2) = 20.4, corresponding to a change in production route for CO in higher density gas. Similar logarithmic plots among all five diatomic molecules reveal additional examples of dual slopes in the cases of CO versus CH (break at log N = 14.1, 13.0), CH+ versus H2 (13.1, 20.3), and CH+ versus CO (13.2, 14.1). We employ both analytical and numerical chemical schemes in order to derive details of the molecular environments. In the denser gas, where C2 and CN molecules also reside, reactions involving C+ and OH are the dominant factor leading to CO formation via equilibrium chemistry. In the low-density gas, where equilibrium chemistry studies have failed to reproduce the abundance of CH+, our numerical analysis shows that nonequilibrium chemistry must be employed for correctly predicting the abundances of both CH+ and CO.

Metalimnetic oxygen minima alter the vertical profiles of carbon dioxide and methane in a managed freshwater reservoir.

PubMed

McClure, Ryan P; Hamre, Kathleen D; Niederlehner, B R; Munger, Zackary W; Chen, Shengyang; Lofton, Mary E; Schreiber, Madeline E; Carey, Cayelan C

2018-04-30

Metalimnetic oxygen minimum zones (MOMs) commonly develop during the summer stratified period in freshwater reservoirs because of both natural processes and water quality management. While several previous studies have examined the causes of MOMs, much less is known about their effects, especially on reservoir biogeochemistry. MOMs create distinct redox gradients in the water column which may alter the magnitude and vertical distribution of dissolved methane (CH 4 ) and carbon dioxide (CO 2 ). The vertical distribution and diffusive efflux of CH 4 and CO 2 was monitored for two consecutive open-water seasons in a eutrophic reservoir that develops MOMs as a result of the operation of water quality engineering systems. During both summers, elevated concentrations of CH 4 accumulated within the anoxic MOM, reaching a maximum of 120 μM, and elevated concentrations of CO 2 accumulated in the oxic hypolimnion, reaching a maximum of 780 μM. Interestingly, the largest observed diffusive CH 4 effluxes occurred before fall turnover in both years, while peak diffusive CO 2 effluxes occurred both before and during turnover. Our data indicate that MOMs can substantially change the vertical distribution of CH 4 and CO 2 in the water column in reservoirs, resulting in the accumulation of CH 4 in the metalimnion (vs. at the sediments) and CO 2 in the hypolimnion. Copyright © 2018 Elsevier B.V. All rights reserved.

A rate-based transcutaneous CO2 sensor for noninvasive respiration monitoring.

PubMed

Chatterjee, M; Ge, X; Kostov, Y; Luu, P; Tolosa, L; Woo, H; Viscardi, R; Falk, S; Potts, R; Rao, G

2015-05-01

The pain and risk of infection associated with invasive blood sampling for blood gas measurements necessitate the search for reliable noninvasive techniques. In this work we developed a novel rate-based noninvasive method for a safe and fast assessment of respiratory status. A small sampler was built to collect the gases diffusing out of the skin. It was connected to a CO2 sensor through gas-impermeable tubing. During a measurement, the CO2 initially present in the sampler was first removed by purging it with nitrogen. The gases in the system were then recirculated between the sampler and the CO2 sensor, and the CO2 diffusion rate into the sampler was measured. Because the measurement is based on the initial transcutaneous diffusion rate, reaching mass transfer equilibrium and heating the skin is no longer required, thus, making it much faster and safer than traditional method. A series of designed experiments were performed to analyze the effect of the measurement parameters such as sampler size, measurement location, subject positions, and movement. After the factor analysis tests, the prototype was sent to a level IV NICU for clinical trial. The results show that the measured initial rate of increase in CO2 partial pressure is linearly correlated with the corresponding arterial blood gas measurements. The new approach can be used as a trending tool, making frequent blood sampling unnecessary for respiratory status monitoring.

Constraints on the magnitude and rate of CO 2 dissolution at Bravo Dome natural gas field

DOE PAGES

Sathaye, Kiran J.; Hesse, Marc A.; Cassidy, M.; ...

2014-10-13

The injection of carbon dioxide (CO 2) captured at large point sources into deep saline aquifers can significantly reduce anthropogenic CO 2 emissions from fossil fuels. Dissolution of the injected CO 2 into the formation brine is a trapping mechanism that helps to ensure the long-term security of geological CO 2 storage. We use thermochronology to estimate the timing of CO 2 emplacement at Bravo Dome, a large natural CO 2 field at a depth of 700 m in New Mexico. Together with estimates of the total mass loss from the field we present, to our knowledge, the first constraintsmore » on the magnitude, mechanisms, and rates of CO 2 dissolution on millennial timescales. Apatite (U-Th)/He thermochronology records heating of the Bravo Dome reservoir due to the emplacement of hot volcanic gases 1.2–1.5 Ma. The CO 2 accumulation is therefore significantly older than previous estimates of 10 ka, which demonstrates that safe long-term geological CO 2 storage is possible. Here, integrating geophysical and geochemical data, we estimate that 1.3 Gt CO 2 are currently stored at Bravo Dome, but that only 22% of the emplaced CO 2 has dissolved into the brine over 1.2 My. Roughly 40% of the dissolution occurred during the emplacement. The CO 2 dissolved after emplacement exceeds the amount expected from diffusion and provides field evidence for convective dissolution with a rate of 0.1 g/(m 2y). Finally, the similarity between Bravo Dome and major US saline aquifers suggests that significant amounts of CO 2 are likely to dissolve during injection at US storage sites, but that convective dissolution is unlikely to trap all injected CO 2 on the 10-ky timescale typically considered for storage projects.« less

The Optical-Mid-infrared Extinction Law of the l = 165° Sightline in the Galactic Plane: Diversity of the Extinction Law in the Diffuse Interstellar Medium

NASA Astrophysics Data System (ADS)

Wang, Shu; Jiang, B. W.; Zhao, He; Chen, Xiaodian; de Grijs, Richard

2017-10-01

Understanding the effects of dust extinction is important to properly interpret observations. The optical total-to-selective extinction ratio, {R}V={A}V/E(B-V), is widely used to describe extinction variations in ultraviolet and optical bands. Since the {R}V=3.1 extinction curve adequately represents the average extinction law of diffuse regions in the Milky Way, it is commonly used to correct observational measurements along sightlines toward diffuse regions in the interstellar medium. However, the {R}V value may vary even along different diffuse interstellar medium sightlines. In this paper, we investigate the optical-mid-infrared (mid-IR) extinction law toward a very diffuse region at l=165^\\circ in the Galactic plane, which was selected based on a CO emission map. Adopting red clump stars as extinction tracers, we determine the optical-mid-IR extinction law for our diffuse region in two APASS bands (B,V), three XSTPS-GAC bands (g,r,I), three 2MASS bands (J,H,{K}s), and two WISE bands (W1,W2). Specifically, 18 red clump stars were selected from the APOGEE-RC catalog based on spectroscopic data in order to explore the diversity of the extinction law. We find that the optical extinction curves exhibit appreciable diversity. The corresponding {R}V ranges from 1.7 to 3.8, while the mean {R}V value of 2.8 is consistent with the widely adopted average value of 3.1 for Galactic diffuse clouds. There is no apparent correlation between {R}V value and color excess E(B-V) in the range of interest, from 0.2 to 0.6 mag, or with specific visual extinction per kiloparsec, {A}V/d.

Control of Silver Diffusion in Low-Temperature Co-Fired Diopside Glass-Ceramic Microwave Dielectrics

PubMed Central

Chou, Chen-Chia; Chang, Chun-Yao; Chen, Guang-Yu; Feng, Kuei-Chih; Tsao, Chung-Ya

2017-01-01

Electrode material for low-temperature co-fired diopside glass-ceramic used for microwave dielectrics was investigated in the present work. Diffusion of silver from the electrode to diopside glass-ceramics degrades the performance of the microwave dielectrics. Two approaches were adopted to resolve the problem of silver diffusion. Firstly, silicon-oxide (SiO2) powder was employed and secondly crystalline phases were chosen to modify the sintering behavior and inhibit silver ions diffusion. Nanoscale amorphous SiO2 powder turns to the quartz phase uniformly in dielectric material during the sintering process, and prevents the silver from diffusion. The chosen crystalline phase mixing into the glass-ceramics enhances crystallinity of the material and inhibits silver diffusion as well. The result provides a method to decrease the diffusivity of silver ions by adding the appropriate amount of SiO2 and appropriate crystalline ceramics in diopside glass-ceramic dielectric materials. Finally, we used IEEE 802.11a 5.8 GHz as target specification to manufacture LTCC antenna and the results show that a good broadband antenna was made using CaMgSi2O6 with 4 wt % silicon oxide. PMID:29286330

Gas, dust, stars, star formation, and their evolution in M 33 at giant molecular cloud scales

NASA Astrophysics Data System (ADS)

Komugi, Shinya; Miura, Rie E.; Kuno, Nario; Tosaki, Tomoka

2018-06-01

We report on a multi-parameter analysis of giant molecular clouds (GMCs) in the nearby spiral galaxy M 33. A catalog of GMCs identifed in 12CO(J = 3-2) was used to compile associated 12CO(J = 1-0), dust, stellar mass, and star formation rate. Each of the 58 GMCs are categorized by their evolutionary stage. Applying the principal component analysis on these parameters, we construct two principal components, PC1 and PC2, which retain 75% of the information from the original data set. PC1 is interpreted as expressing the total interstellar matter content, and PC2 as the total activity of star formation. Young (< 10 Myr) GMCs occupy a distinct region in the PC1-PC2 plane, with lower interstellar medium (ISM) content and star formation activity compared to intermediate-age and older clouds. Comparison of average cloud properties in different evolutionary stages imply that GMCs may be heated or grow denser and more massive via aggregation of diffuse material in their first ˜ 10 Myr. The PCA also objectively identified a set of tight relations between ISM and star formation. The ratio of the two CO lines is nearly constant, but weakly modulated by massive star formation. Dust is more strongly correlated with the star formation rate than the CO lines, supporting recent findings that dust may trace molecular gas better than CO. Stellar mass contributes weakly to the star formation rate, reminiscent of an extended form of the Schmidt-Kennicutt relation with the molecular gas term substituted by dust.

Gas, dust, stars, star formation, and their evolution in M 33 at giant molecular cloud scales

NASA Astrophysics Data System (ADS)

Komugi, Shinya; Miura, Rie E.; Kuno, Nario; Tosaki, Tomoka

2018-04-01

We report on a multi-parameter analysis of giant molecular clouds (GMCs) in the nearby spiral galaxy M 33. A catalog of GMCs identifed in 12CO(J = 3-2) was used to compile associated 12CO(J = 1-0), dust, stellar mass, and star formation rate. Each of the 58 GMCs are categorized by their evolutionary stage. Applying the principal component analysis on these parameters, we construct two principal components, PC1 and PC2, which retain 75% of the information from the original data set. PC1 is interpreted as expressing the total interstellar matter content, and PC2 as the total activity of star formation. Young (< 10 Myr) GMCs occupy a distinct region in the PC1-PC2 plane, with lower interstellar medium (ISM) content and star formation activity compared to intermediate-age and older clouds. Comparison of average cloud properties in different evolutionary stages imply that GMCs may be heated or grow denser and more massive via aggregation of diffuse material in their first ˜ 10 Myr. The PCA also objectively identified a set of tight relations between ISM and star formation. The ratio of the two CO lines is nearly constant, but weakly modulated by massive star formation. Dust is more strongly correlated with the star formation rate than the CO lines, supporting recent findings that dust may trace molecular gas better than CO. Stellar mass contributes weakly to the star formation rate, reminiscent of an extended form of the Schmidt-Kennicutt relation with the molecular gas term substituted by dust.

A conversion of CO2-ECBM related lab observations to reservoir requirements

NASA Astrophysics Data System (ADS)

Gensterblum, Y.; Merkel, A.; Busch, A.; Krooss, B. M.

2012-04-01

To predict a CBM production profile either during primary or secondary production, aspects like coal permeability and porosity, density, ash and moisture content, initial gas-in-place (GIP) (from canister desorption tests), gas sorption capacity from laboratory isotherms (to obtain gas saturations and desorption pressure), gas diffusivities, coal volumetrics (thickness and areal extent) need to be understood as a minimum requirement. When dealing with CO2-ECBM selective adsorption, counter diffusion in the coal matrix, or coal shrinkage and swelling (from CH4 desorption and CO2 adsorption, respectively) and the influence of moisture need to be investigated in addition to the parameters above. During CO2-ECBM processes, the areal distribution of the CO2 injected is accomplished by flow through the cleat network. When CO2 is entering the coal matrix by a combined sorption/diffusion process it will adsorb to the coal inner surface and at the same time replace part of the CH4. This replacement occurs either by a reduction in the CH4 partial pressure or by a higher selective sorption of CO2 over CH4. Because of a concentration gradient between CH4 in the matrix compared to the cleat system, CH4 diffuses from the coal matrix into the cleat system where, by pressure drawdown towards a production well, it can be produced. In this context this presentation summarizes gas (CO2, CH4) and water sorption on coal and specifically addresses the following topics: • CH4 and CO2 sorption capacity as a function depth and rank • CO2 and CH4 sorption on natural coals and its dependence on coal specific parameters like coal rank, maceral composition or ash content (Busch and Gensterblum, 2011). • Water sorption on coal, its dependence on coal properties such as rank and coal chemistry and gas sorption in the presence of water (Busch and Gensterblum, 2011). • N2, CH4, CO2 displacement experiments and the volumetric response of the coal on the present gas type (sorbing or inert) in the pore system • Uncertainties in reservoir characterisation (Gensterblum et al., 2010; Gensterblum et al., 2009) • Sorption uptake kinetic as a function of surface coverage and the influence of moisture on the kinetic Busch, A. and Gensterblum, Y., 2011. CBM and CO2-ECBM related sorption processes in coal: A review. International Journal of Coal Geology, 87: 49-71. Gensterblum, Y. et al., 2010. European inter-laboratory comparison of high pressure CO2 sorption isotherms II: Natural coals. International Journal of Coal Geology, 84(2): 115-124. Gensterblum, Y. et al., 2009. European inter-laboratory comparison of high pressure CO2 sorption isotherms. I: Activated carbon. Carbon, 47(13): 2958-2969.

Encapsulation of Ionic Liquids with an Aprotic Heterocyclic Anion (AHA-IL) for CO2 Capture: Preserving the Favorable Thermodynamics and Enhancing the Kinetics of Absorption.

PubMed

Moya, Cristian; Alonso-Morales, Noelia; de Riva, Juan; Morales-Collazo, Oscar; Brennecke, Joan F; Palomar, Jose

2018-03-08

The performance of an ionic liquid with an aprotic heterocyclic anion (AHA-IL), trihexyl(tetradecyl)phosphonium 2-cyanopyrrolide ([P 66614 ][2-CNPyr]), for CO 2 capture has been evaluated considering both the thermodynamics and the kinetics of the phenomena. Absorption gravimetric measurements of the gas-liquid equilibrium isotherms of CO 2 -AHA-IL systems were carried out from 298 to 333 K and at pressures up to 15 bar, analyzing the role of both chemical and physical absorption phenomena in the overall CO 2 solubility in the AHA-IL, as has been done previously. In addition, the kinetics of the CO 2 chemical absorption process was evaluated by in situ Fourier transform infrared spectroscopy-attenuated total reflection, following the characteristic vibrational signals of the reactants and products over the reaction time. A chemical absorption model was used to describe the time-dependent concentration of species involved in the reactive absorption, obtaining kinetic parameters (such as chemical reaction kinetic constants and diffusion coefficients) as a function of temperatures and pressures. As expected, the results demonstrate that the CO 2 absorption rate is mass-transfer-controlled because of the relatively high viscosity of AHA-IL. The AHA-IL was encapsulated in a porous carbon sphere (Encapsulated Ionic Liquid, ENIL) to improve the kinetic performance of the AHA-IL for CO 2 capture. The newly synthesized AHA-ENIL material was evaluated as a CO 2 sorbent with gravimetric absorption measurements. AHA-ENIL systems preserve the good CO 2 absorption capacity of the AHA-IL but drastically enhance the CO 2 absorption rate because of the increased gas-liquid surface contact area achieved by solvent encapsulation.

The Effect of Thermal Convection on Earth-Atmosphere CO2 Gas Exchange in Aggregated Soil

NASA Astrophysics Data System (ADS)

Ganot, Y.; Weisbrod, N.; Dragila, M. I.

2011-12-01

Gas transport in soils and surface-atmosphere gas exchange are important processes that affect different aspects of soil science such as soil aeration, nutrient bio-availability, sorption kinetics, soil and groundwater pollution and soil remediation. Diffusion and convection are the two main mechanisms that affect gas transport, fate and emissions in the soils and in the upper vadose zone. In this work we studied CO2 soil-atmosphere gas exchange under both day-time and night-time conditions, focusing on the impact of thermal convection (TCV) during the night. Experiments were performed in a climate-controlled laboratory. One meter long columns were packed with matrix of different grain size (sand, gravel and soil aggregates). Air with 2000 ppm CO2 was injected into the bottom of the columns and CO2 concentration within the columns was continuously monitored by an Infra Red Gas Analyzer. Two scenarios were compared for each soil: (1) isothermal conditions, representing day time conditions; and (2) thermal gradient conditions, i.e., atmosphere colder than the soil, representing night time conditions. Our results show that under isothermal conditions, diffusion is the major mechanism for surface-atmosphere gas exchange for all grain sizes; while under night time conditions the prevailing mechanism is dependent on the air permeability of the matrix: for sand and gravel it is diffusion, and for soil aggregates it is TCV. Calculated CO2 flux for the soil aggregates column shows that the TCV flux was three orders of magnitude higher than the diffusive flux.

CO2 flux monitoring using Continuous Timeseries-Forced Diffusion (CT-FD): Development, Validation

NASA Astrophysics Data System (ADS)

McArthur, G. S.; Risk, D. A.; Nickerson, N. R.; Creelman, C. A.; Beltrami, H.

2009-12-01

Land-based CO2 flux measurements are a key indicator of the biological, chemical and physical processes occurring in the soil. While highly dense temporal flux measurements can be acquired using Eddy Covariance towers, or flux chambers, the challenge of gathering data that is rich both temporally and spatially persists. Over the past two years we have developed a new technique for measuring soil CO2 fluxes, called continuous timeseries-forced diffusion (CT-FD) attempts to satisfy the need for spatially and temporally rich data. The CT-FD probe consists of a Vaisala CO2 sensor, embodied in a PVC casing, with tear/UV resistant Tyvek membranes at both the inlet and outlet. The probe delivers continuous flux data and can be inexpensively replicated across the landscape.The CT-FD technique works by forcing a known diffusive regime between the soil and the atmosphere, allowing the calculation of fluxes across the soil/atmosphere boundary to be made from; the internal concentration of a CT-FD probe placed at the soil surface; and a common reference probe designed to capture the atmospheric CO2. For every concentration measurement, the difference between the probe and the reference concentration is indicative of a unique flux value. Here we examine properties of the instrument and method, as documented by a long series of developmental studies involving numerical gas transport modeling, laboratory and field experiments. A suite of 1D and 3D modeling experiments were needed to optimize embodiment and geometries of the probe. These show that the probe should have a relatively long collar, with relatively high diffusivity made possible by having large, highly diffusive membranes, both of which help to induce 1D movement of gases into the probe and reduce the lateral diffusion around the probe. Modeling also shows that correction for lateral diffusion is feasible. As for error, sensor error transfers linearly to errors in the flux, and that the sensor can be used in non free-atmospheric environments, for example when snow falls and persists. For calibration purposes we designed and built a flux generator, allowing us to test different mathematical approaches for reliability and calibrations which is done by plotting the known flux against the difference between probe and atmospheric CO2 measurements. Validation of the technique was also carried out in the lab using soil plots in which heating cables drove diurnal microbial CO2 production, and we found CT-FD to have an excellent correspondence with LI-8100, showing similar accuracy and precision. Using CT-FD we performed two extensive winter campaigns and one summer campaign in a salt marsh with both CO2-capable and CH4-capable (METS sensor-based) probes. Here we found the CT-FD capable of long, unattended deployments, continued effectiveness when buried under deep snowpack, exposed to long term freezing temperatures, and heavy rain events.

Y0.08Sr0.88TiO3-CeO2 composite as a diffusion barrier layer for stainless-steel supported solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Kim, Kun Joong; Kim, Sun Jae; Choi, Gyeong Man

2016-03-01

A new diffusion barrier layer (DBL) is proposed for solid oxide fuel cells (SOFCs) supported on stainless-steel where DBL prevents inter-diffusion of atoms between anode and stainless steel (STS) support during fabrication and operation of STS-supported SOFCs. Half cells consisting of dense yttria-stabilized zirconia (YSZ) electrolyte, porous Ni-YSZ anode layer, and ferritic STS support, with or without Y0.08Sr0.88TiO3-CeO2 (YST-CeO2) composite DBL, are prepared by tape casting and co-firing at 1250 and 1350 °C, respectively, in reducing (H2) atmosphere. The porous YST-CeO2 layer (t ∼ 60 μm) blocks inter-diffusion of Fe and Ni, and captures the evaporated Cr during cell fabrication (1350 °C). The cell with DBL and La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode achieved a maximum power density of ∼220 mW cm-2 which is stable at 700 °C. In order to further improve the power performance, Ni coarsening in anode during co-firing must be prevented or alternative anode which is resistive to coarsening is suggested. This study demonstrates that the new YST-CeO2 layer is a promising as a DBL for stainless-steel-supported SOFCs fabricated with co-firing process.

Microstructural response of variably hydrated Ca-rich montmorillonite to supercritical CO2.

PubMed

Lee, Mal-Soon; McGrail, B Peter; Glezakou, Vassiliki-Alexandra

2014-01-01

First-principles molecular dynamics simulations were carried out to explore the mechanistic and thermodynamic ramifications of the exposure of variably hydrated Ca-rich montmorillonites to supercritical CO2 and CO2-SO2 mixtures under geologic storage conditions. In sub- to single-hydrated systems (≤ 1W), CO2 intercalation causes interlamellar expansion of 8-12%, while systems transitioning to 2W may undergo contraction (∼ 7%) or remain almost unchanged. When compared to ∼2W hydration state, structural analysis of the ≤ 1W systems, reveals more Ca-CO2 contacts and partial transition to vertically confined CO2 molecules. Infrared spectra and projected vibrational frequency analysis imply that intercalated Ca-bound CO2 are vibrationally constrained and contribute to the higher frequencies of the asymmetric stretch band. Reduced diffusion coefficients of intercalated H2O and CO2 (10(-6)-10(-7) cm(2)/s) indicate that Ca-montmorillonites in ∼ 1W hydration states can be more efficient in capturing CO2. Simulations including SO2 imply that ∼ 0.66 mmol SO2/g clay can be intercalated without other significant structural changes. SO2 is likely to divert H2O away from the cations, promoting Ca-CO2 interactions and CO2 capture by further reducing CO2 diffusion (10(-8) cm(2)/s). Vibrational bands at ∼ 1267 or 1155 cm(-1) may be used to identify the chemical state (oxidation states +4 or +6, respectively) and the fate of sulfur contaminants.

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

Lee, Hak-Sung, E-mail: hslee@kims.re.kr; Park, Chanbum; Oh, Chang-Seok

Highlights: • We model the sample grain boundary of LiCoO2, one of important Li cathode materials. • Rigid body translation was found the asymmetric GB is more stable than symmetric GB. • The vacancy formation energy of Li and O was estimated with first principles calculations. • This model boundary can help to find a new dopant to improve Li diffusions. - Abstract: An atomic structure of LiCoO{sub 2} model grain boundary, Σ2 [1120](1102), is introduced and grain boundary energies with rigid body translations are investigated systematically to find the most stable interface structures. It is found that the coordinatedmore » structures of Co and O in the vicinity of grain boundary are strongly related to grain boundary energy. Examining nonstoichiometry at grain boundary, the defect energetics of Li and O site at grain boundary are estimated. In addition, the effect of grain boundary on Li diffusion is investigated to calculate Li diffusion across grain boundary.« less

System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO2, n-alkanes, and poly(ethylene glycol) dimethyl ethers

NASA Astrophysics Data System (ADS)

Moultos, Othonas A.; Zhang, Yong; Tsimpanogiannis, Ioannis N.; Economou, Ioannis G.; Maginn, Edward J.

2016-08-01

Molecular dynamics simulations were carried out to study the self-diffusion coefficients of CO2, methane, propane, n-hexane, n-hexadecane, and various poly(ethylene glycol) dimethyl ethers (glymes in short, CH3O-(CH2CH2O)n-CH3 with n = 1, 2, 3, and 4, labeled as G1, G2, G3, and G4, respectively) at different conditions. Various system sizes were examined. The widely used Yeh and Hummer [J. Phys. Chem. B 108, 15873 (2004)] correction for the prediction of diffusion coefficient at the thermodynamic limit was applied and shown to be accurate in all cases compared to extrapolated values at infinite system size. The magnitude of correction, in all cases examined, is significant, with the smallest systems examined giving for some cases a self-diffusion coefficient approximately 15% lower than the infinite system-size extrapolated value. The results suggest that finite size corrections to computed self-diffusivities must be used in order to obtain accurate results.

The influence of clouds and diffuse radiation on ecosystem-atmosphere CO2 and CO18O exhanges

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

Still, C.J.; Riley, W.J.; Biraud, S.C.

2009-05-01

This study evaluates the potential impact of clouds on ecosystem CO{sub 2} and CO{sub 2} isotope fluxes ('isofluxes') in two contrasting ecosystems (a broadleaf deciduous forest and a C{sub 4} grassland), in a region for which cloud cover, meteorological, and isotope data are available for driving the isotope-enabled land surface model, ISOLSM. Our model results indicate a large impact of clouds on ecosystem CO{sub 2} fluxes and isofluxes. Despite lower irradiance on partly cloudy and cloudy days, predicted forest canopy photosynthesis was substantially higher than on clear, sunny days, and the highest carbon uptake was achieved on the cloudiest day.more » This effect was driven by a large increase in light-limited shade leaf photosynthesis following an increase in the diffuse fraction of irradiance. Photosynthetic isofluxes, by contrast, were largest on partly cloudy days, as leaf water isotopic composition was only slightly depleted and photosynthesis was enhanced, as compared to adjacent clear sky days. On the cloudiest day, the forest exhibited intermediate isofluxes: although photosynthesis was highest on this day, leaf-to-atmosphere isofluxes were reduced from a feedback of transpiration on canopy relative humidity and leaf water. Photosynthesis and isofluxes were both reduced in the C{sub 4} grass canopy with increasing cloud cover and diffuse fraction as a result of near-constant light limitation of photosynthesis. These results suggest that some of the unexplained variation in global mean {delta}{sup 18}O of CO{sub 2} may be driven by large-scale changes in clouds and aerosols and their impacts on diffuse radiation, photosynthesis, and relative humidity.« less

Applying Alkyl-Chain Surface Functionalizations in Mesoporous Inorganic Structures: Their Impact on Gas Flow and Selectivity Depending on Temperature.

PubMed

Besser, Benjamin; Ahmed, Atiq; Baune, Michael; Kroll, Stephen; Thöming, Jorg; Rezwan, Kurosch

2016-10-12

Porous inorganic capillary membranes are prepared to serve as model structures for the experimental investigation of the gas transport in functionalized mesopores. The porous structures possess a mean pore diameter of 23 nm which is slightly reduced to 20 nm after immobilizing C 16 -alkyl chains on the surface. Gas permeation measurements are performed at temperatures ranging from 0 to 80 °C using Ar, N 2 , and CO 2 . Nonfunctionalized structures feature a gas transport according to Knudsen diffusion with regard to gas flow and selectivity. After C 16 -functionalization, the gas flow is reduced by a factor of 10, and the ideal selectivities deviate from the Knudsen theory. CO 2 adsorption measurements show a decrease in total amount of adsorbed gas and isosteric heat of adsorption. It is hypothesized that the immobilized C 16 -chains sterically influence the gas transport behavior without a contribution from adsorption effects. The reduced gas flow derives from an additional surface resistance caused by the C 16 -chains spacially limiting the adsorption and desorption directions for gas molecules propagating through the structure, resulting in longer diffusion paths. In agreement, the gas flow is found to correlate with the molecular diameter of the gas species (CO 2 < Ar < N 2 ) increasing the resistance for larger molecules. This affects the ideal selectivities with the relation [Formula: see text]. The influence on selectivity increases with increasing temperature which leads to the conclusion that the temperature induced movement of the C 16 -chains is responsible for the stronger interaction between gas molecules and surface functional groups.

Maximum leaf conductance driven by CO2 effects on stomatal size and density over geologic time.

PubMed

Franks, Peter J; Beerling, David J

2009-06-23

Stomatal pores are microscopic structures on the epidermis of leaves formed by 2 specialized guard cells that control the exchange of water vapor and CO(2) between plants and the atmosphere. Stomatal size (S) and density (D) determine maximum leaf diffusive (stomatal) conductance of CO(2) (g(c(max))) to sites of assimilation. Although large variations in D observed in the fossil record have been correlated with atmospheric CO(2), the crucial significance of similarly large variations in S has been overlooked. Here, we use physical diffusion theory to explain why large changes in S necessarily accompanied the changes in D and atmospheric CO(2) over the last 400 million years. In particular, we show that high densities of small stomata are the only way to attain the highest g(cmax) values required to counter CO(2)"starvation" at low atmospheric CO(2) concentrations. This explains cycles of increasing D and decreasing S evident in the fossil history of stomata under the CO(2) impoverished atmospheres of the Permo-Carboniferous and Cenozoic glaciations. The pattern was reversed under rising atmospheric CO(2) regimes. Selection for small S was crucial for attaining high g(cmax) under falling atmospheric CO(2) and, therefore, may represent a mechanism linking CO(2) and the increasing gas-exchange capacity of land plants over geologic time.

Maximum leaf conductance driven by CO2 effects on stomatal size and density over geologic time

PubMed Central

Franks, Peter J.; Beerling, David J.

2009-01-01

Stomatal pores are microscopic structures on the epidermis of leaves formed by 2 specialized guard cells that control the exchange of water vapor and CO2 between plants and the atmosphere. Stomatal size (S) and density (D) determine maximum leaf diffusive (stomatal) conductance of CO2 (gcmax) to sites of assimilation. Although large variations in D observed in the fossil record have been correlated with atmospheric CO2, the crucial significance of similarly large variations in S has been overlooked. Here, we use physical diffusion theory to explain why large changes in S necessarily accompanied the changes in D and atmospheric CO2 over the last 400 million years. In particular, we show that high densities of small stomata are the only way to attain the highest gcmax values required to counter CO2“starvation” at low atmospheric CO2 concentrations. This explains cycles of increasing D and decreasing S evident in the fossil history of stomata under the CO2 impoverished atmospheres of the Permo-Carboniferous and Cenozoic glaciations. The pattern was reversed under rising atmospheric CO2 regimes. Selection for small S was crucial for attaining high gcmax under falling atmospheric CO2 and, therefore, may represent a mechanism linking CO2 and the increasing gas-exchange capacity of land plants over geologic time. PMID:19506250

Availability of phosphate for phytoplankton and bacteria and of labile organic carbon for bacteria at different pCO2 levels in a mesocosm study

NASA Astrophysics Data System (ADS)

Tanaka, T.; Thingstad, T. F.; Løvdal, T.; Grossart, H.-P.; Larsen, A.; Schulz, K. G.; Riebesell, U.

2007-11-01

Availability of phosphate for phytoplankton and bacteria and of labile organic carbon for bacteria at different pCO2 levels were studied in a mesocosm experiment (PeECE III). Using nutrient-depleted SW Norwegian fjord waters, three different levels of pCO2 (350 μatm: 1×CO2; 750 μatm: 2×CO2; 1050 μatm: 3×CO2) were set up, and nitrate and phosphate were added at the start of the experiment in order to induce a phytoplankton bloom. Despite similar responses of total particulate P concentration and phosphate turnover time at the three different pCO2 levels, the size distribution of particulate P and 33PO4 uptake suggested that phosphate transferred to the >10 μm fraction was greater in the 3×CO2 mesocosm during the first 6-10 days when phosphate concentration was high. During the period of phosphate depletion (after Day 12), specific phosphate affinity and specific alkaline phosphatase activity (APA) suggested a P-deficiency (i.e. suboptimal phosphate supply) but not a P-limitation for the phytoplankton and bacterial community at the three different pCO2 levels. Although specific phosphate affinity and specific APA tended to be higher in 3×CO2 than in 2×CO2 and 1×CO2 mesocosms during the phosphate depletion period, no statistical differences were found. Responses of specific glucose affinity for bacteria were similar at the three different pCO2 levels. Measured specific glucose affinities were consistently much lower than the theoretical maximum predicted from the diffusion-limited model, suggesting that bacterial growth was not limited by the availability of labile dissolved organic carbon. These results suggest that availability of phosphate and glucose was similar at the three different pCO2 levels.

Magmatic carbon dioxide emissions at Mammoth Mountain, California

USGS Publications Warehouse

Farrar, Christopher D.; Neil, John M.; Howle, James F.

1999-01-01

Carbon dioxide (CO2) of magmatic origin is seeping out of the ground in unusual quantities at several locations around the flanks of Mammoth Mountain, a dormant volcano in Eastern California. The most recent volcanic activity on Mammoth Mountain was steam eruptions about 600 years ago, but seismic swarms and long-period earthquakes over the past decade are evidence of an active magmatic system at depth. The CO2 emission probably began in 1990 but was not recognized until 1994. Seismic swarms and minor ground deformation during 1989, believed to be results of a shallow intrusion of magma beneath Mammoth Mountain, probably triggered the release of CO2, which persists in 1998. The CO2 gas is at ambient temperatures and emanates diffusely from the soil surface rather than flowing from distinct vents. The CO2 has collected in the soil by displacing air in the pore spaces and reaches concentrations of greater than 95 percent by volume in places. The total area affected by high CO2 concentrations and high CO2 flux from the soil surface was estimated at 60 hectares in 1997. Coniferous forest covering about 40 hectares has been killed by high CO2 concentrations in the root zone. In more than 300 soil-gas samples collected from depths of 0.5 to 2 m in 1995, CO2 concentrations ranged from background levels (less than 1 percent) to greater than 95 percent by volume. At 250 locations, CO2 flux was measured using a closed chamber in 1996; values, in grams per square meter per day, ranged from background (less than 25) to more than 30,000. On the basis of these data, the total emission of magmatic CO2 in 1996 is estimated to be about 530 megagrams per day. Concentrations of CO2 exceeding Occupational Safety and Health Administration standards have been measured in pits dug in soil and snow, in poorly ventilated buildings, and in below-ground valve-boxes around Mammoth Mountain. CO2 concentrations greater than 10 percent in poorly ventilated spaces are not uncommon on some parts of Mammoth Mountain. Humans and other animals exposed to CO2 concentrations greater than 10 percent could lose consciousness and die rapidly. With knowledge of the problem and reasonable caution, however, the health hazard to humans can be avoided. As noted earlier, the CO2 emission is related to magmatic activity at depth, but at present (1998) it does not portend an imminent volcanic eruption.

Potential efficiencies of open- and closed-cycle CO, supersonic, electric-discharge lasers

NASA Technical Reports Server (NTRS)

Monson, D. J.

1976-01-01

Computed open- and closed-cycle system efficiencies (laser power output divided by electrical power input) are presented for a CW carbon monoxide, supersonic, electric-discharge laser. Closed-system results include the compressor power required to overcome stagnation pressure losses due to supersonic heat addition and a supersonic diffuser. The paper shows the effect on the system efficiencies of varying several important parameters. These parameters include: gas mixture, gas temperature, gas total temperature, gas density, total discharge energy loading, discharge efficiency, saturated gain coefficient, optical cavity size and location with respect to the discharge, and supersonic diffuser efficiency. Maximum open-cycle efficiency of 80-90% is predicted; the best closed-cycle result is 60-70%.

Magma Dynamics at Mid-Ocean Ridges by Noble Gas Kinetic Fractionation: Assessment of Magmatic Ascent Rates and Mantle Composition

NASA Astrophysics Data System (ADS)

Paonita, A.; Martelli, M.

2007-12-01

Topical scientific literature on magma degassing at mid-ocean ridges more and more focuses on exsolution processes occurring under conditions that are far from thermodynamic equilibrium between bubbles and silicate melt. Indeed, the dynamics of magma ascent and decompression can be faster than that of CO2 diffusion into bubbles, in which case the diffusivity ratios among volatiles are the main control of the composition of the exsolving gas phase. We have developed a model of bubble growth in silicate melts that calculates the extent of both CO2 supersaturation and kinetic fractionation among noble gases in vesicles in relation to the decompressive rate of basaltic melts. The model predicts that, due to comparable Ar and CO2 diffusivity, magma degassing at low pressure fractionates both He/Ar and He/CO2 ratios by a similar extent, while the slower CO2 diffusion at high pressure causes early kinetic effects on Ar/CO2 ratio and dramatically changes the degassing paths. By using this tool, we have reviewed the global He-Ar-CO2 dataset of fluid inclusions in mid-ocean-ridge glasses. We display that non-equilibrium fractionations among He, Ar and CO2, driven by their different diffusivities in silicate melts, are common in most of the natural conditions of magma decompression and their signature strongly depends on pressure of degassing. The different geochemical signatures among suites of data coming from different ridge segments mainly depend on the depth of the magma chamber where the melt was stored. Moreover, variations inside a single suite emerge due to the interplay between variable ascent speed of magma and cooling rate of the emplaced lava. As a result, two data groups coming from the Pito Seamount suite (Easter Microplate East ridge), showing different degree of CO2 supersaturation and He/Ar fractionation, provide ascent rates which differ by ten folds or even more. The large variations in both the He/CO2 and Ar/CO2 ratios at almost constant He/Ar, displayed in products coming from the Mid-Atlantic Ridge 24°N segment and the Rodriguez Triple Junction, require magma storage and degassing processes occurring at high-pressure conditions. In contrast, the simultaneous increase in both He/CO2 and He/Ar of the East Pacific Rise and South-East Indian Ridge data sets suggests the dominance of low-pressure fractionation, implying that the shallow magma chambers are at a lower depth than those of the Mid-Atlantic Ridge 24°N and Rodriguez Triple Junction. Our conclusions support the presence of a relationship between spreading rate and depth of high-temperature zones below ridges, and are consistent with the depth of magma chambers as suggested from seismic studies. Finally, the non-equilibrium degassing model provides striking constraints on the compositions of noble gases and carbon in mantle-derived magmas. Our results dispense in fact with the supposed need for He-Ar-CO2 heterogeneities in the upper mantle, because the degassing of a single, popping-rock-like primary magma is able to explain all the available data.

Diffusive emission of methane and carbon dioxide from two hydropower reservoirs in Brazil.

PubMed

Marcelino, A A; Santos, M A; Xavier, V L; Bezerra, C S; Silva, C R O; Amorim, M A; Rodrigues, R P; Rogerio, J P

2015-05-01

The role of greenhouse gas emissions from freshwater reservoirs and their contribution to increase greenhouse gas concentrations in the atmosphere is currently under discussion in many parts of the world. We studied CO2 and CH4 diffusive fluxes from two large neotropical hydropower reservoirs with different climate conditions. We used floating closed-chambers to estimate diffusive fluxes of these gaseous species. Sampling campaigns showed that the reservoirs studied were sources of greenhouse gases to the atmosphere. In the Serra da Mesa Reservoir, the CH4 emissions ranged from 0.530 to 396.96 mg.m(-2).d(-1) and CO2 emissions ranged from -1,738.33 to 11,166.61 mg.m(-2).d(-1) and in Três Marias Reservoir the CH4 fluxes ranged 0.720 to 2,578.03 mg.m(-2).d(-1) and CO2 emission ranged from -3,037.80 to 11,516.64 to mg.m(-2).d(-1). There were no statistically significant differences of CH4 fluxes between the reservoirs, but CO2 fluxes from the two reservoirs studied were significantly different. The CO2 emissions measured over the periods studied in Serra da Mesa showed some seasonality with distinctions between the wet and dry transition season. In Três Marias Reservoir the CO2 fluxes showed no seasonal variability. In both reservoirs, CH4 emissions showed a tendency to increase during the study periods but this was not statistically significant. These results contributed to increase knowledge about the magnitude of CO2 and CH4 emission in hydroelectric reservoirs, however due to natural variability of the data future sampling campaigns will be needed to better elucidate the seasonal influences on the fluxes of greenhouse gases.

Formaldehyde in the Diffuse Interstellar Cloud MBM40

NASA Astrophysics Data System (ADS)

Joy, Mackenzie; Magnani, Loris A.

2018-06-01

MBM40, a high-latitude molecular cloud, has been extensively studied using different molecular tracers. It appears that MBM40 is composed of a relatively dense, helical filament embedded in a more diffuse substrate of low density molecular gas. In order to study the transition between the two regimes, this project presents the first high-resolution mapping of MBM40 using the 110-111 hyperfine transition of formaldehyde (H2CO) at 4.83 GHz. We used H2CO spectra obtained with the Arecibo telescope more than a decade ago to construct this map. The results can be compared to previous maps made from the CO(1-0) transition to gain further understanding of the structure of the cloud. The intensity of the H2CO emission was compared to the CO emission. Although a correlation exists between the H2CO and CO emissivity, there seems to be a saturation of H2CO line strength for stronger CO emissivity. This is probably a radiative transfer effect of the CO emission. We have also found that the velocity dispersion of H2CO in the lower ridge of the cloud is significantly lower than in the rest of the cloud. This may indicate that this portion of the cloud is a coherent structure (analogous to an eddy) in a turbulent flow.

Synthesis and characterisation of Co-Co(OH)2 composite anode material on Cu current collector for energy storage devices

NASA Astrophysics Data System (ADS)

Yavuz, Abdulcabbar; Yakup Hacıibrahimoğlu, M.; Bedir, Metin

2017-04-01

A Co-Co(OH)2 modified electrode on inexpensive Cu substrate was synthesized at room temperature and demonstrated to be a promising anode material for energy storage devices. A modified Co film was obtained potentiostatically and was then potentiodynamically treated with KOH solution to form Co(OH)2. Co-Co(OH)2 coatings were obtained and were dominated by Co(OH)2 at the oxidized side, whereas Co dominant Co-Co(OH)2 occurred at the reduced side (-1.1 V). As OH- ions were able to diffuse into (out of) the film during oxidation (reduction) and did not react with the Cu current collector, the Co-Co(OH)2 electrode can be used as an anode material in energy storage devices. Although the specific capacitance of the electrodes varied depending on thickness, the redox reaction between the modified electrode and KOH electrolyte remained the same consisting of a surface-controlled and diffusion-controlled mechanism which had a desirable fast charge and discharge property. Capacity values remained constant after 250 cycles as the film evolved. Overall capacity retention was 84% for the film after 450 scans. A specific capacitance of 549 F g-1 was obtained for the Co-Co(OH)2 composite electrode in 6 M KOH at a scan rate of 5 mV s-1 and 73% of capacitance was retained when the scan rate was increased to 100 mV s-1.

CO2 Permeability of Biological Membranes and Role of CO2 Channels

PubMed Central

Endeward, Volker; Arias-Hidalgo, Mariela; Al-Samir, Samer; Gros, Gerolf

2017-01-01

We summarize here, mainly for mammalian systems, the present knowledge of (a) the membrane CO2 permeabilities in various tissues; (b) the physiological significance of the value of the CO2 permeability; (c) the mechanisms by which membrane CO2 permeability is modulated; (d) the role of the intracellular diffusivity of CO2 for the quantitative significance of cell membrane CO2 permeability; (e) the available evidence for the existence of CO2 channels in mammalian and artificial systems, with a brief view on CO2 channels in fishes and plants; and, (f) the possible significance of CO2 channels in mammalian systems. PMID:29064458

Volcanic soil gas 4He/CO2 ratio: a useful geochemical tool for eruption forecasting

NASA Astrophysics Data System (ADS)

Asensio-Ramos, M.; Perez, N. M.; Padron, E.; Melián, G.; Hernandez Perez, P. A.; Padilla, G.; Barrancos, J.; Rodríguez, F.; Sumino, H.; Calvo, D.

2016-12-01

Magmatic gases that percolate through volcano's porous flanks in a non-visible (diffuse) way disturb the chemical composition of soil gases at the surface environment of the volcano, generating enrichments of CO2, He and other gases. Two of the gases which have attracted attention in soil degassing studies are He and CO2 because both species have similar low solubility in silicate melts. However, once they are exsolved from the melts, their movement through the crust towards the surface is very different: CO2, which is a reactive gas, is affected by the occurrence of interfering processes, while interaction of He during its ascent is minimum. Their geochemical differences yield higher relative He/CO2 ratios in the fumarole gases than is actually present in the magma, but it decreases when the magma reservoir reaches enough pressure to generate incipient fracture systems approaching the eruption. In this work, we present quasi daily estimations of diffusive He through the whole surface of El Hierro, the youngest island of the Canarian archipelago, considering He emission data reported in the literature (Padrón et al., 2013. Geology, 41, 539-542), using the same procedure as for diffuse CO2 emission time series (Melián et al., 2014. J. Geophys. Res., 119, 6976-6991). After the occurrence of more than 11,000 seismic events, a shallow submarine eruption about 2 km off the south coast in the southernmost part of El Hierro, started in October 12, 2011 and lasted for 5 month. The herein presented methodology enables the calculation of the diffuse He/CO2 emission ratio of the entire island during the volcanic unrest. Two different emission peaks for both He and CO2, with approximately the same delay between them ( 23 days), were observed. The combination of both time series resulted in a drastic increase in the He/CO2 emission ratio of the island (up to 1.1×10-3) two weeks before the eruption onset. Additionally, a second significant He/CO2 emission peak (up to 5.5×10-4) was observed between 3 and 4 November, some days before the highest lava emission period. The detailed time series of He/CO2 emission ratio during El Hierro 2011-2012 submarine eruption presented here demonstrate the importance of its continuous monitoring in active volcanic regions, mainly in areas without visible manifestations of volcanic fluid discharges.

The diffusion of water in haploanesite

NASA Astrophysics Data System (ADS)

Ni, H.; Zhang, Y.

2008-12-01

Diffusive transport of water in silicate melts is a key process in magma dynamics and volcanic eruptions, including bubble growth. Previous studies demonstrate that in additional to temperature, water content and pressure, melt composition also plays an important role in determining water diffusivity. We carried out high temperature (1311-1512°C) diffusion-couple experiments and intermediate temperature (470- 600°C) dehydration experiments to investigate H2O diffusion in a melt of haploandesitic composition. The diffusion couple is composed of an anhydrous (with <0.1 wt.% H2O) and a hydrous (with 2 wt.% H2O) haploandesitic glass. A platinum capsule is used to contain the couple and then it is welded shut. Diffusion runs are carried out in a 12.7-mm piston-cylinder apparatus at 1 GPa and superliquidus temperatures of 1584-1785 K. Infrared microscopy is applied on quenched glass to measure the profile of total H2O concentration (H2Ot). The profile shape is best fit by an error function, indicating an H2O diffusivity virtually independent of H2O concentration, consistent with the results of Behrens et al. (2004) on an Fe-bearing andesite. Dehydration experiments are performed at 743-873 K in a rapid-quench cold-seal vessel, with a heated hydrous glass losing water to 0.1 GPa Ar atmosphere. Measured diffusion profiles, however, show that water diffusivity is dependent on water content. Experimental data can be explained by H2Om being the dominating diffusant or a total H2O diffusivity proportional to total H2O content. The distinction between the high-temperature experiments where H2Ot diffusivity is apparently independent of H2Ot content, and the intermediate-temperature experiments where H2Ot diffusivity depends on H2Ot can be rationalized if OH diffusion has a higher activation energy than molecular H2O diffusion, and their comparable diffusivities at high T gradually diverge as temperature is lowered. At below 1 wt.% H2O, water diffusivity increases from rhyolite to dacite to andesite at >1300°C, and this sequence is reversed at <600°C.

Interaction of CO2 concentrations and water stress in semiarid plants causes diverging response in instantaneous water use efficiency and carbon isotope composition

NASA Astrophysics Data System (ADS)

Zhao, Na; Meng, Ping; He, Yabing; Yu, Xinxiao

2017-07-01

In the context of global warming attributable to the increasing levels of CO2, severe drought may be more frequent in areas that already experience chronic water shortages (semiarid areas). This necessitates research on the interactions between increased levels of CO2 and drought and their effect on plant photosynthesis. It is commonly reported that 13C fractionation occurs as CO2 gas diffuses from the atmosphere to the substomatal cavity. Few researchers have investigated 13C fractionation at the site of carboxylation to cytoplasm before sugars are exported outward from the leaf. This process typically progresses in response to variations in environmental conditions (i.e., CO2 concentrations and water stress), including in their interaction. Therefore, saplings of two typical plant species (Platycladus orientalis and Quercus variabilis) from semiarid areas of northern China were selected and cultivated in growth chambers with orthogonal treatments (four CO2 concentration ([CO2]) × five soil volumetric water content (SWC)). The δ13C of water-soluble compounds extracted from leaves of saplings was determined for an assessment of instantaneous water use efficiency (WUEcp) after cultivation. Instantaneous water use efficiency derived from gas-exchange measurements (WUEge) was integrated to estimate differences in δ13C signal variation before leaf-level translocation of primary assimilates. The WUEge values in P. orientalis and Q. variabilis both decreased with increased soil moisture at 35-80 % of field capacity (FC) and increased with elevated [CO2] by increasing photosynthetic capacity and reducing transpiration. Instantaneous water use efficiency (iWUE) according to environmental changes differed between the two species. The WUEge in P. orientalis was significantly greater than that in Q. variabilis, while an opposite tendency was observed when comparing WUEcp between the two species. Total 13C fractionation at the site of carboxylation to cytoplasm before sugar export (total 13C fractionation) was species-specific, as demonstrated in the interaction of [CO2] and SWC. Rising [CO2] coupled with moistened soil generated increasing disparities in δ13C between water-soluble compounds (δ13CWSC) and estimates based on gas-exchange observations (δ13Cobs) in P. orientalis, ranging between 0.0328 and 0.0472 ‰. Differences between δ13CWSC and δ13Cobs in Q. variabilis increased as [CO2] and SWC increased (0.0384-0.0466 ‰). The 13C fractionation from mesophyll conductance (gm) and post-carboxylation both contributed to the total 13C fractionation that was determined by δ13C of water-soluble compounds and gas-exchange measurements. Total 13C fractionation was linearly dependent on stomatal conductance, indicating that post-carboxylation fractionation could be attributed to environmental variation. The magnitude and environmental dependence of apparent post-carboxylation fractionation is worth our attention when addressing photosynthetic fractionation.

Interfacial binding of divalent cations to calixarene-based Langmuir monolayers

DOE PAGES

Tulli, Ludovico G.; Wang, Wenjie; Lindemann, William R.; ...

2015-02-20

The interactions of Langmuir monolayers produced through the self-assembly of an amphiphilic p-carboxycalix[4]arene with a series of divalent, fourth-period transition metals, at the air-water interface, were investigated. Changes in the interfacial behavior of 1 in response to the presence of CuCl 2, CoCl 2, MnCl 2, and NiCl 2 were studied by means of Langmuir compression isotherms and Brewster angle microscopy (BAM). The measurements revealed that the self-assembly properties of 1 are significantly affected by Cu 2+ ions. The interactions of 1-based monolayers with Co 2+ and Cu 2+ ions were further investigated by means of synchrotron radiation-based X-ray reflectivitymore » (XRR), X-ray near-total-reflection fluorescence (XNTRF), and grazing incidence X-ray diffraction (GIXD). XNTRF and XRR analyses revealed that the monolayer of 1 binds more strongly to Cu 2+ than Co 2+ ions. In the presence of relatively high concentrations of Cu 2+ ions in the subphase (1.4 × 10 -3 M), XNTRF exhibited anomalous depth profile behavior and GIXD measurements showed considerably strong diffuse scattering. Furthermore, both measurements suggest the formation of Cu 2+ clusters contiguous to the monolayer of 1.« less

When phosphorylated at Thr148, the β2-subunit of AMP-activated kinase does not associate with glycogen in skeletal muscle.

PubMed

Xu, Hongyang; Frankenberg, Noni T; Lamb, Graham D; Gooley, Paul R; Stapleton, David I; Murphy, Robyn M

2016-07-01

The 5'-AMP-activated protein kinase (AMPK), a heterotrimeric complex that functions as an intracellular fuel sensor that affects metabolism, is activated in skeletal muscle in response to exercise and utilization of stored energy. The diffusibility properties of α- and β-AMPK were examined in isolated skeletal muscle fiber segments dissected from rat fast-twitch extensor digitorum longus and oxidative soleus muscles from which the surface membranes were removed by mechanical dissection. After the muscle segments were washed for 1 and 10 min, ∼60% and 75%, respectively, of the total AMPK pools were found in the diffusible fraction. After in vitro stimulation of the muscle, which resulted in an ∼80% decline in maximal force, 20% of the diffusible pool became bound in the fiber. This bound pool was not associated with glycogen, as determined by addition of a wash step containing amylase. Stimulation of extensor digitorum longus muscles resulted in 28% glycogen utilization and a 40% increase in phosphorylation of the downstream AMPK target acetyl carboxylase-CoA. This, however, had no effect on the proportion of total β2-AMPK that was phosphorylated in whole muscle homogenates measured by immunoprecipitation. These findings suggest that, in rat skeletal muscle, β2-AMPK is not associated with glycogen and that activation of AMPK by muscle contraction does not dephosphorylate β2-AMPK. These findings question the physiological relevance of the carbohydrate-binding function of β2-AMPK in skeletal muscle. Copyright © 2016 the American Physiological Society.

Observation of Li Diffusion in Cathode Sheets of Li-ion Battery by μ+SR

NASA Astrophysics Data System (ADS)

Umegaki, Izumi; Kawauchi, Shigehiro; Nozaki, Hiroshi; Sawada, Hiroshi; Nakano, Hiroyuki; Harada, Masashi; Cottrell, Stephen P.; Coomer, Fiona C.; Telling, Mark; Sugiyama, Jun

In order to know the change in Li diffusion during the operation of Li-ion batteries, we have initiated to measure Li diffusion not only in a powder sample but also in a cathode sheet with μ+SR. As the first step, we have measured μ+SR spectra on a cathode sheet, in which a mixture of a cathode material Li(Ni, Co)O2, a binder, and conducting additives is coated on an Al foil. The zero-field μ+SR spectrum exhibited a typical Kubo-Toyabe (KT) type relaxation at 100 K. By subtracting the contribution of the muons stopped in the Al foil, we found that Li+ ion starts to diffuse above 100 K in the Li(Ni, Co)O2. A self diffusion coefficient (DLi) at 300 K was estimated as 10-11 (cm2/s), which comparable with DLi (300 K) in the cathode materials previously reported. This leads to the future "in operando" measurements of DLi in Li-ion batteries.

Transparent, Ultrahigh-Gas-Barrier Films with a Brick-Mortar-Sand Structure.

PubMed

Dou, Yibo; Pan, Ting; Xu, Simin; Yan, Hong; Han, Jingbin; Wei, Min; Evans, David G; Duan, Xue

2015-08-10

Transparent and flexible gas-barrier materials have shown broad applications in electronics, food, and pharmaceutical preservation. Herein, we report ultrahigh-gas-barrier films with a brick-mortar-sand structure fabricated by layer-by-layer (LBL) assembly of XAl-layered double hydroxide (LDH, X=Mg, Ni, Zn, Co) nanoplatelets and polyacrylic acid (PAA) followed by CO2 infilling, denoted as (XAl-LDH/PAA)n-CO2. The near-perfectly parallel orientation of the LDH "brick" creates a long diffusion length to hinder the transmission of gas molecules in the PAA "mortar". Most significantly, both the experimental studies and theoretical simulations reveal that the chemically adsorbed CO2 acts like "sand" to fill the free volume at the organic-inorganic interface, which further depresses the diffusion of permeating gas. The strategy presented here provides a new insight into the perception of barrier mechanism, and the (XAl-LDH/PAA)n-CO2 film is among the best gas barrier films ever reported. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of C/O Ratio and Temperature on Sooting Limits of Spherical Diffusion Flames

NASA Technical Reports Server (NTRS)

Lecoustre, V. R.; Sunderland, P. B.; Chao, B. H.; Urban, D. L.; Stocker, D. P.; Axelbaum, R. L.

2008-01-01

Limiting conditions for soot particle inception in spherical diffusion flames were investigated numerically. The flames were modeled using a one-dimensional, time accurate diffusion flame code with detailed chemistry and transport and an optically thick radiation model. Seventeen normal and inverse flames were considered, covering a wide range of stoichiometric mixture fraction, adiabatic flame temperature, residence time and scalar dissipation rate. These flames were previously observed to reach their sooting limits after 2 s of microgravity. Sooting-limit diffusion flames with scalar dissipation rate lower than 2/s were found to have temperatures near 1400 K where C/O = 0.51, whereas flames with greater scalar dissipation rate required increased temperatures. This finding was valid across a broad range of fuel and oxidizer compositions and convection directions.

Effects of cation contaminants in conductive TiO2 ceramics

NASA Astrophysics Data System (ADS)

Yan, M. F.; Rhodes, W. W.

1982-12-01

Ten cation contaminants, namely Al, Ga, Co, Fe, Mg, Zn, Zr, Ca, Sr, and Ba were investigated for their effects on the electrical properties, microstructures, and discoloration of conductive TiO2 ceramics. It was found that Al, Ga, Co, Fe, and Mg cause discoloration and increase the electrical resistivity by a factor of 104 to 106 in Nb-doped TiO2 ceramics. The other dopants do not introduce such changes in TiO2. The electrical properties, microstructures, and discoloration were measured in specimens of AlxNb0.007Ti0.993-xO2 with 0≤x≤0.01. When the Al content exceeds a critical value, ranging from 0.48% at 1400 °C to 0.25% at 1200 °C, the electrical resistivities and grain size increase rapidly, and the specimen is discolored from the original black to an ivory white color. Color boundary migration induced by Al diffusion in Nb-doped TiO2 was quantitatively measured. From the kinetics of the boundary migration, the Al diffusivity (D) was calculated to be D=2.67 exp(-53.3 kcal/mole/RT) cm2/s in the temperature range of 1200 to 1400 °C. The rapid diffusion of the small cations, namely Al, Ga, Co, Fe, and Mg, results from an interstitial diffusion mechanism. However, other cations, having a radius larger than the interstitial channel (˜0.77 Å radius), cannot diffuse by this mechanism. Defect reactions are proposed to explain the increase in the electrical resistivity and microstructural changes due to Al diffusion. These defect reactions also show that the problem of acceptor contamination cannot be avoided by adding an excess quantity of donor dopant if the solubility of the donor is much less than that of the acceptor contaminant.

Simultaneous measurement of pulmonary diffusing capacity for carbon monoxide and nitric oxide.

PubMed

Yamaguchi, Kazuhiro; Tsuji, Takao; Aoshiba, Kazutetsu; Nakamura, Hiroyuki

2018-03-01

In Europe and America, the newly-developed, simultaneous measurement of diffusing capacity for CO (D LCO ) and NO (D LNO ) has replaced the classic D LCO measurement for detecting the pathophysiological abnormalities in the acinar regions. However, simultaneous measurement of D LCO and D LNO is currently not used by Japanese physicians. To encourage the use of D LNO in Japan, the authors reviewed aspects of simultaneously-estimated D LCO and D LNO from previously published manuscripts. The simultaneous D LCO -D LNO technique identifies the alveolocapillary membrane-related diffusing capacity (membrane component, D M ) and the blood volume in pulmonary microcirculation (V C ); V C is the principal factor constituting the blood component of diffusing capacity (D B ,D B =θ·V C where θ is the specific gas conductance for CO or NO in the blood). As the association velocity of NO with hemoglobin (Hb) is fast and the affinity of NO with Hb is high in comparison with those of CO, θ NO can be taken as an invariable simply determined by diffusion limitation inside the erythrocyte. This means that θ NO is independent of the partial pressure of oxygen (PO 2 ). However, θ CO involves the limitations by diffusion and chemical reaction elicited by the erythrocyte, resulting in θ CO to be a PO 2 -dependent variable. Furthermore, D LCO is determined primarily by D B (∼77%), while D LNO is determined equally by D M (∼55%) and D B (∼45%). This suggests that D LCO is more sensitive for detecting microvascular diseases, while D LNO can equally identify alveolocapillary membrane and microcirculatory abnormalities. Copyright © 2017 The Japanese Respiratory Society. Published by Elsevier B.V. All rights reserved.

Predictive modeling of CO2 sequestration in deep saline sandstone reservoirs: Impacts of geochemical kinetics

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

Balashov, Victor N.; Guthrie, George D.; Hakala, J. Alexandra

2013-03-01

One idea for mitigating the increase in fossil-fuel generated CO{sub 2} in the atmosphere is to inject CO{sub 2} into subsurface saline sandstone reservoirs. To decide whether to try such sequestration at a globally significant scale will require the ability to predict the fate of injected CO{sub 2}. Thus, models are needed to predict the rates and extents of subsurface rock-water-gas interactions. Several reactive transport models for CO{sub 2} sequestration created in the last decade predicted sequestration in sandstone reservoirs of ~17 to ~90 kg CO{sub 2} m{sup -3|. To build confidence in such models, a baseline problem including rockmore » + water chemistry is proposed as the basis for future modeling so that both the models and the parameterizations can be compared systematically. In addition, a reactive diffusion model is used to investigate the fate of injected supercritical CO{sub 2} fluid in the proposed baseline reservoir + brine system. In the baseline problem, injected CO{sub 2} is redistributed from the supercritical (SC) free phase by dissolution into pore brine and by formation of carbonates in the sandstone. The numerical transport model incorporates a full kinetic description of mineral-water reactions under the assumption that transport is by diffusion only. Sensitivity tests were also run to understand which mineral kinetics reactions are important for CO{sub 2} trapping. The diffusion transport model shows that for the first ~20 years after CO{sub 2} diffusion initiates, CO{sub 2} is mostly consumed by dissolution into the brine to form CO{sub 2,aq} (solubility trapping). From 20-200 years, both solubility and mineral trapping are important as calcite precipitation is driven by dissolution of oligoclase. From 200 to 1000 years, mineral trapping is the most important sequestration mechanism, as smectite dissolves and calcite precipitates. Beyond 2000 years, most trapping is due to formation of aqueous HCO{sub 3}{sup -}. Ninety-seven percent of the maximum CO{sub 2} sequestration, 34.5 kg CO{sub 2} per m{sup 3} of sandstone, is attained by 4000 years even though the system does not achieve chemical equilibrium until ~25,000 years. This maximum represents about 20% CO{sub 2} dissolved as CO{sub 2},aq, 50% dissolved as HCO{sub 3}{sup -}{sub ,aq}, and 30% precipitated as calcite. The extent of sequestration as HCO{sub 3}{sup -} at equilibrium can be calculated from equilibrium thermodynamics and is roughly equivalent to the amount of Na+ in the initial sandstone in a soluble mineral (here, oligoclase). Similarly, the extent of trapping in calcite is determined by the amount of Ca2+ in the initial oligoclase and smectite. Sensitivity analyses show that the rate of CO{sub 2} sequestration is sensitive to the mineral-water reaction kinetic constants between approximately 10 and 4000 years. The sensitivity of CO{sub 2} sequestration to the rate constants decreases in magnitude respectively from oligoclase to albite to smectite.« less

Spatial and temporal variations of diffuse CO_{2} degassing at the Tenerife North-South Rift Zone (NSRZ) volcano (Canary Islands) during the period 2002-2016

NASA Astrophysics Data System (ADS)

Rodríguez, Fátima; McCollum, John J. K.; Orland, Elijah D. M.; Barrancos, José; Padilla, Germán D.; Calvo, David; Amonte, Cecilia; Pérez, Nemesio M.

2017-04-01

Subaerial volcanic activity on Tenerife (2034 km2), the largest island of the Canary archipelago, started 14 My ago and 4 volcanic eruptions have occurred in historical times during the last 300 years. The main volcano-structural and geomorphological features of Tenerife are (i) the central volcanic complex, nowadays formed by Las Cañadas caldera, a volcanic depression measuring 16×9 km that resulted from multiple vertical collapses and partially filled by post-caldera volcanic products and (ii) the triple junction-shaped rift system, formed by numerous aligned monogenetic cones. Up to 297 mafic monogenetic cones have been recognized on Tenerife, and they represent the most common eruptive activity occurring on the island during the last 1 My (Dóniz et al., 2008). The North-South Rift Zone (NSRZ) of Tenerife comprises at least 139 cones. The main structural characteristic of the NSRZ of the island is an apparent absence of a distinct ridge, and a fan shaped distribution of monogenetic cones. Since there are currently no visible gas emissions at the NSRZ, diffuse degassing surveys have become an important geochemical tool for the surveillance of this volcanic system. Five diffuse CO2 degassing surveys have been carried out at NSRZ of Tenerife since 2002, the last one in the summer period of 2016, to evaluate the spatio-temporal variations of CO2 degassing as a volcanic surveillance tool for the NSRZ of Tenerife. At each survey, around 600 sampling sites were selected to cover homogenously the study area (325 km2) using the accumulation chamber method. The diffuse CO2 output ranged from 78 to 707 t/d in the study period, with the highest emission rate measured in 2015. The backgroung emission rate was estimated in 300 t/d. The last results the soil CO2 efflux values ranged from non-detectable up to 24.7 g m-2 d-1. The spatial distribution map, constructed following the sequential Gaussian simulation (sGs) procedure, showed the highest CO2 values as multiple isolated anomalies and did not show a clear relation with the main volcano-structural features of the area. The CO2 output released to the atmosphere in a diffuse way has been estimated at 524 t d-1, which represents a value lower than the previous one (707 t d-1 at summer of 2015) but higher than the background emission rate. These changes in the temporal series confirm the need of periodic diffuse emission surveys in the area as a powerful volcanic surveillance tool in volcanic systems where visible gas emanations are absent. References: Dóniz et al., 2008. J. Volcanol. Geotherm. Res. 173, 185.

Molecular Dynamic Simulation of Diffusion Coefficients for Alkanols in Supercritical CO2 1

NASA Astrophysics Data System (ADS)

Li, Zhiwei; Lai, Shuhui; Gao, Wei; Chen, Liuping

2018-07-01

The infinite dilution diffusion coefficients ( D 12) of methanol, ethanol, 1-propanol, 1-butanol and 1-pentanol in supercritical CO2 (scCO2) at 313.2 K and 10-16 MPa were simulated by molecular dynamics (MD) simulation. The microscopic structure was also analyzed by calculation of the radial distribution function, coordination number (CN) between the center mass of solute and solvent molecules, and the average number of hydrogen bonding of this system. In infinite dilute solution, the probability of forming hydrogen bond between alkanol molecules is greatly reduced relative to pure alkanol fluid, and the weak hydrogen bonds formed between alkanol and CO2 molecules. In general, this work provides a reliable simulation method for transfer properties of solutes in scCO2. The prediction data were provides for the design and development of chemical processing. The results are helpful for one to deeper understand the relationship between microscopic structures of fluid and its transfer properties.

Rate of disappearance of labeled carbon dioxide from the lungs of humans during breath holding: a method for studying the dynamics of pulmonary CO2 exchange

PubMed Central

Hyde, Richard W.; Puy, Ricardo J. M.; Raub, William F.; Forster, Robert E.

1968-01-01

The dynamics of CO2 exchange in the lungs of man was studied by observing the rate of disappearance of a stable isotope of CO2 (13CO2) from the alveolar gas during breath holding. Over 50% of the inspired isotope disappeared within the first 3 sec followed by a moderately rapid logarithmic decline in which one-half of the remaining 13CO2 disappeared every 10 sec. The large initial disappearance of 13CO2 indicated that alveolar 13CO2 equilibrated in less than 3 sec with the CO2 stored in the pulmonary tissues and capillary blood. The volume of CO2 in the pulmonary tissues calculated from this initial disappearance was 200 ml or 0.33 ml of CO2 per milliliter of pulmonary tissue volume. The alveolar to end-capillary gradient for 13CO2 was calculated by comparing the simultaneous disappearance rates of 13CO2 and acetylene. At rest and during exercise this gradient for 13CO2 was either very small or not discernible, and diffusing capacity for CO2 (DLCO2) exceeded 200 ml/(min × mm Hg). After the administration of a carbonic anhydrase inhibitor the rate of disappearance of 13CO2 decreased markedly. DLCO2 fell to 42 ml/(min × mm Hg) and at least 70% of the exchange of 13CO2 with the CO2 stores in the pulmonary tissues and blood was blocked by the inhibitor. These changes were attributed to impairment of exchange of 13CO2 with the bicarbonate in the pulmonary tissues and blood. The pH of the pulmonary tissues (Vtis) was determined by a method based on the premise that the CO2 space in the pulmonary tissues blocked by the inhibitor represented total bicarbonate content. At an alveolar PCO2 of 40 mm Hg pH of Vtis equalled 6.97 ± 0.09. PMID:5658586

Emphysema on Thoracic CT and Exercise Ventilatory Inefficiency in Mild-to-Moderate COPD.

PubMed

Jones, Joshua H; Zelt, Joel T; Hirai, Daniel M; Diniz, Camilla V; Zaza, Aida; O'Donnell, Denis E; Neder, J Alberto

2017-04-01

There is growing evidence that emphysema on thoracic computed tomography (CT) is associated with poor exercise tolerance in COPD patients with only mild-to-moderate airflow obstruction. We hypothesized that an excessive ventilatory response to exercise (ventilatory inefficiency) would underlie these abnormalities. In a prospective study, 19 patients (FEV 1 = 82 ± 13%, 12 Global Initiative for Chronic Obstructive Lung Disease (GOLD) stage 1) and 26 controls underwent an incremental exercise test. Ventilatory inefficiency was assessed by the ventilation ([Formula: see text]E)/CO 2 output ([Formula: see text]CO 2 ) nadir. Pulmonary blood flow (PBF) in a submaximal test was calculated by inert gas rebreathing. Emphysema was quantified as % of attenuation areas below 950 HU. Patients typically presented with centrilobular emphysema (76.8 ± 10.1% of total emphysema) in the upper lobes (upper/total lung ratio = 0.82 ± 0.04). They had lower peak oxygen uptake ([Formula: see text]O 2 ), higher [Formula: see text]E/[Formula: see text]CO 2 nadir, and greater dyspnea scores than controls (p < 0.05). Lower peak [Formula: see text]O 2 and worse dyspnea were found in patients with higher [Formula: see text]E/[Formula: see text]CO 2 nadirs (≥30). Patients had blunted increases in PBF from rest to iso-[Formula: see text]O 2 exercise (p < 0.05). Higher [Formula: see text]E/[Formula: see text]CO 2 nadir in COPD was associated with emphysema severity (r = 0.63) which, in turn, was related to reduced lung diffusing capacity (r = -0.72) and blunted changes in PBF from rest to exercise (r = -0.69) (p < 0.01). Ventilation "wasted" in emphysematous areas is associated with impaired exercise ventilatory efficiency in mild-to-moderate COPD. Exercise ventilatory inefficiency links structure (emphysema) and function (D L CO) to a key clinical outcome (poor exercise tolerance) in COPD patients with only modest spirometric abnormalities.

Experimental studies and model analysis of noble gas fractionation in low-permeability porous media

NASA Astrophysics Data System (ADS)

Ding, Xin; Mack Kennedy, B.; Molins, Sergi; Kneafsey, Timothy; Evans, William C.

2017-05-01

Gas flow through the vadose zone from sources at depth involves fractionation effects that can obscure the nature of transport and even the identity of the source. Transport processes are particularly complex in low permeability media but as shown in this study, can be elucidated by measuring the atmospheric noble gases. A series of laboratory column experiments was conducted to evaluate the movement of noble gas from the atmosphere into soil in the presence of a net efflux of CO2, a process that leads to fractionation of the noble gases from their atmospheric abundance ratios. The column packings were designed to simulate natural sedimentary deposition by interlayering low permeability ceramic plates and high permeability beach sand. Gas samples were collected at different depths at CO2 fluxes high enough to cause extreme fractionation of the noble gases (4He/36Ar > 20 times the air ratio). The experimental noble gas fractionation-depth profiles were in good agreement with those predicted by the dusty gas (DG) model, demonstrating the applicability of the DG model across a broad spectrum of environmental conditions. A governing equation based on the dusty gas model was developed to specifically describe noble gas fractionation at each depth that is controlled by the binary diffusion coefficient, Knudsen diffusion coefficient and the ratio of total advection flux to total flux. Finally, the governing equation was used to derive the noble gas fractionation pattern and illustrate how it is influenced by soil CO2 flux, sedimentary sequence, thickness of each sedimentary layer and each layer's physical parameters. Three potential applications of noble gas fractionation are provided: evaluating soil attributes in the path of gas flow from a source at depth to the atmosphere, testing leakage through low permeability barriers used to isolate buried waste, and tracking biological methanogenesis and methane oxidation associated with hydrocarbon degradation.

Diffuse degassing He/CO2 ratio before and during the 2011-12 El Hierro submarine eruption, Canary Islands

NASA Astrophysics Data System (ADS)

Padrón, Eleazar; Hernández, Pedro A.; Melián, Gladys V.; Barrancos, José; Padilla, Germán; Pérez, Nemesio M.; Dionis, Samara; Rodríguez, Fátima; Asensio-Ramos, María; Calvo, David

2015-04-01

El Hierro Island (278 km2) is the youngest and the SW-most of the Canary Islands. On July 16, 2011, a seismic-volcanic crisis started with the occurrence of more than 11,900 seismic events and significant deformation along the island, culminating with the eruption onset in October 12. Since at El Hierro Islands there are not any surface geothermal manifestation (fumaroles, etc), we have focused our studies on soil degassing surveys. Between July 2011 to March 2012, seventeen diffuse CO2 and He emissions soil gas surveys were undertaken at El Hierro volcanic system (600 observation sites) with the aim to investigate the relationship between their temporal variations and the volcanic activity (Padrón et al., 2013; Melián et al., 2014). Based on the diffuse He/CO2 emission ratio, a sharp increase before the eruption onset was observed, reaching the maximum value on September 26 (6.8×10-5), sixteen days before the occurrence of the eruption. This increase coincided with an increase in seismic energy release during the volcanic unrest and occurred together with an increase on the 3He/4He isotopic ratio in groundwaters from a well in El Hierro Island (Padrón et al., 2013; from 2-3 RA to 7.2 RA where RA = 3He/4He ratio in air), one month prior to the eruption onset. Early degassing of new gas-rich magma batch at depth could explain the observed increase on the He/CO2 ratio, causing a preferential partitioning of CO2 in the gas phase with respect to the He, due to the lower solubility of CO2 than that of He in basaltic magmas. During the eruptive period (October 2011-March 2012) the prevalence of a magmatic CO2-dominated component is evident, as indicated by the generally lower He/CO2 ratios and high 3He/4He values (Padrón et al., 2013). The onset of the submarine eruption might have produced a sudden release of volcanic gases, and consequently, a decrease in the volcanic gas pressure of the magma bodies moving beneath the island, reflected by a drastic decrease in the diffuse helium emissions measured after the eruption onset. Therefore, this study shows that higher diffuse He/CO2 emission ratios preceded the 2011-2012 El Hierro submarine eruption, clearly show the critical role that both gas species can play in the prediction of major volcanic events and demonstrates the importance of performing soil He and CO2 surveys as a useful geochemical monitoring tool in active volcanic regions. Padrón et al. (2013) Geology 41(5), 539-542; Melián et al. (2014) JGR, 119: 6976-6991, doi:10.1002/2014JB011013

Field ion microscopic studies of the CO oxidation on platinum: Bistability and oscillations

NASA Astrophysics Data System (ADS)

Gorodetskii, V.; Drachsel, W.; Ehsasi, M.; Block, J. H.

1994-05-01

The oscillating CO oxidation is investigated on a Pt-field emitter tip by using the field ion mode of surface imaging of Oad sites with O2 as imaging gas. Based on data of the titration reactions [V. Gorodetskii, W. Drachsel, and J. H. Block, J. Chem. Phys. 100, C. E. UPDATE (1994)], external control parameters for the regions of bistability and of self-sustained isothermal oscillations could be found. On a field emitter tip, oscillations can be generated in a rather large parameter space. The anticlockwise hysteresis of O+2 ion currents in temperature cycles occurs in agreement with results on single crystal planes. Unexpected regular oscillation sequences could occasionally be obtained on the small surface areas of a field emitter tip and measured as function of the CO partial pressure and of the temperature. Different stages within oscillating cycles were documented by field ion images. Oscillations of total ion currents are correlated with variations in the spatial brightness of field ion images. In the manifold of single crystal planes of a field emitter {331} planes around the {011} regions are starting points for oscillations which mainly proceed along [100] vicinals. This excludes the {111} regions from autonomous oscillations. With slightly increased CO partial pressures fast local oscillations at a few hundred surface sites of the Pt(001) plane display short-living CO islands of 40 to 50 Å diameter. Temporal oscillations of the total O+2 ion current are mainly caused by surface plane specific spatial oscillations. The synchronization is achieved by diffusion reaction fronts rather than by gas phase synchronization.

Increased wintertime CO2 loss as a result of sustained tundra warming

NASA Astrophysics Data System (ADS)

Webb, Elizabeth E.; Schuur, Edward A. G.; Natali, Susan M.; Oken, Kiva L.; Bracho, Rosvel; Krapek, John P.; Risk, David; Nickerson, Nick R.

2016-02-01

Permafrost soils currently store approximately 1672 Pg of carbon (C), but as high latitudes warm, this temperature-protected C reservoir will become vulnerable to higher rates of decomposition. In recent decades, air temperatures in the high latitudes have warmed more than any other region globally, particularly during the winter. Over the coming century, the arctic winter is also expected to experience the most warming of any region or season, yet it is notably understudied. Here we present nonsummer season (NSS) CO2 flux data from the Carbon in Permafrost Experimental Heating Research project, an ecosystem warming experiment of moist acidic tussock tundra in interior Alaska. Our goals were to quantify the relationship between environmental variables and winter CO2 production, account for subnivean photosynthesis and late fall plant C uptake in our estimate of NSS CO2 exchange, constrain NSS CO2 loss estimates using multiple methods of measuring winter CO2 flux, and quantify the effect of winter soil warming on total NSS CO2 balance. We measured CO2 flux using four methods: two chamber techniques (the snow pit method and one where a chamber is left under the snow for the entire season), eddy covariance, and soda lime adsorption, and found that NSS CO2 loss varied up to fourfold, depending on the method used. CO2 production was dependent on soil temperature and day of season but atmospheric pressure and air temperature were also important in explaining CO2 diffusion out of the soil. Warming stimulated both ecosystem respiration and productivity during the NSS and increased overall CO2 loss during this period by 14% (this effect varied by year, ranging from 7 to 24%). When combined with the summertime CO2 fluxes from the same site, our results suggest that this subarctic tundra ecosystem is shifting away from its historical function as a C sink to a C source.

Strategies of dissolved inorganic carbon use in macroalgae across a gradient of terrestrial influence: implications for the Great Barrier Reef in the context of ocean acidification

NASA Astrophysics Data System (ADS)

Diaz-Pulido, Guillermo; Cornwall, Christopher; Gartrell, Patrick; Hurd, Catriona; Tran, Dien V.

2016-12-01

Macroalgae are generally used as indicators of coral reef status; thus, understanding the drivers and mechanisms leading to increased macroalgal abundance are of critical importance. Ocean acidification (OA) due to elevated carbon dioxide (CO2) concentrations has been suggested to stimulate macroalgal growth and abundance on reefs. However, little is known about the physiological mechanisms by which reef macroalgae use CO2 from the bulk seawater for photosynthesis [i.e., (1) direct uptake of bicarbonate (HCO3 -) and/or CO2 by means of carbon concentrating mechanisms (CCM) and (2) the diffusive uptake of CO2], which species could benefit from increased CO2 or which habitats may be more susceptible to acidification-induced algal proliferations. Here, we provide the first quantitative examination of CO2-use strategies in coral reef macroalgae and provide information on how the proportion of species and the proportional abundance of species utilising each of the carbon acquisition strategies varies across a gradient of terrestrial influence (from inshore to offshore reefs) in the Great Barrier Reef (GBR). Four macroalgal groups were identified based on their carbon uptake strategies: (1) CCM-only (HCO3 - only users); (2) CCM-HCO3 -/CO2 (active uptake HCO3 - and/or CO2 use); (3) Non-CCM species (those relying on diffusive CO2 uptake); and (4) Calcifiers. δ13C values of macroalgae, confirmed by pH drift assays, show that diffusive CO2 use is more prevalent in deeper waters, possibly due to low light availability that limits activity of CCMs. Inshore shallow reefs had a higher proportion of CCM-only species, while reefs further away from terrestrial influence and exposed to better water quality had a higher number of non-CCM species than inshore and mid-shelf reefs. As non-CCM macroalgae are more responsive to increased seawater CO2 and OA, reef slopes of the outer reefs are probably the habitats most vulnerable to the impacts of OA. Our results suggest a potentially important role of carbon physiology in structuring macroalgal communities in the GBR.

Tetraspanin Tspan9 regulates platelet collagen receptor GPVI lateral diffusion and activation

PubMed Central

Haining, Elizabeth J.; Matthews, Alexandra L.; Noy, Peter J.; Romanska, Hanna M.; Harris, Helen J.; Pike, Jeremy; Morowski, Martina; Gavin, Rebecca L.; Yang, Jing; Milhiet, Pierre-Emmanuel; Berditchevski, Fedor; Nieswandt, Bernhard; Poulter, Natalie S.; Watson, Steve P.; Tomlinson, Michael G.

2017-01-01

Abstract The tetraspanins are a superfamily of four-transmembrane proteins, which regulate the trafficking, lateral diffusion and clustering of the transmembrane proteins with which they interact. We have previously shown that tetraspanin Tspan9 is expressed on platelets. Here we have characterised gene-trap mice lacking Tspan9. The mice were viable with normal platelet numbers and size. Tspan9-deficient platelets were specifically defective in aggregation and secretion induced by the platelet collagen receptor GPVI, despite normal surface GPVI expression levels. A GPVI activation defect was suggested by partially impaired GPVI-induced protein tyrosine phosphorylation. In mechanistic experiments, Tspan9 and GPVI co-immunoprecipitated and co-localised, but super-resolution imaging revealed no defects in collagen-induced GPVI clustering on Tspan9-deficient platelets. However, single particle tracking using total internal reflection fluorescence microscopy showed that GPVI lateral diffusion was reduced by approximately 50% in the absence of Tspan9. Therefore, Tspan9 plays a fine-tuning role in platelet activation by regulating GPVI membrane dynamics. PMID:28032533

Effects of High Carbon Dioxide Soil-Gas Concentrations and Emission Rates From Mammoth Mountain, California, USA

NASA Astrophysics Data System (ADS)

Farrar, C. D.; Evans, W. C.

2006-12-01

High concentrations (90 vol %) of carbon dioxide (CO2) are present in shallow soils, and CO2 is emitted to the atmosphere at high rates (1,000 g/d/m2), in several locations around Mammoth Mountain. The CO2 emissions have been diffuse and at ambient temperature. CO2 in the soil has killed most of the coniferous forest in five areas totaling 35 ha around the north, west, and south sides of the mountain at altitudes between 2,600 and 3,000 m. Part of the CO2 has dissolved in ground water, causing acidic conditions and severely corroding steel casings in several wells. The high CO2 emission rates are implicated in the deaths of four people in the past eight years. During winter, a large quantity of CO2 is sequestered in the snow pack on parts of the mountain, posing potential dangers for winter recreation. One U.S. Forest Service campground has been closed and safety plans have been implemented by the local ski resort. Mammoth Mountain is a dormant Quaternary volcanic center, but overlies an area that has been affected by periods of magmatic unrest during the past two decades. Hypocenters of long-period earthquakes indicate that basaltic intrusions reach depths as shallow as 20 to 15 km, from which CO2 has exsolved during decompression and (or) crystallization of these intrusions. CO2 moves to the land surface along fracture zones associated with faults and possibly geologic contacts. The magmatic source of CO2 is confirmed by ¦Ä13C = -3 to -5 PDB, a lack of 14C, and 3He/4He = 4 to 5 R/RA. The present-day high CO2 soil-gas concentrations and emission rates were first documented in 1994; however, anecdotal information and low 14C in post-1989 tree rings suggest that an abrupt increase in both concentrations and emission rates probably began in 1990, following a 6-month period of seismic swarm activity beneath the mountain. Emissions in an area on the south flank of the mountain have been the focus of CO2 monitoring and have shown no indications of abatement between 1994 and 2005, during which estimates of the total CO2 efflux ranged from 90 to 150 MT/d. The variations can be partly attributed to the precision of the techniques and to minor differences in measurement protocols between researchers; variations in soil- moisture and atmospheric conditions alone can cause fluctuations in efflux of ± 10% over periods of hours to days.

Mapping the Spatial Distribution of CO2 release from Kīlauea Volcano, Hawaii, USA

NASA Astrophysics Data System (ADS)

Elias, T.; Werner, C. A.; Kern, C.; Sutton, A. J.; Hauri, E. H.; Kelly, P. J.

2014-12-01

Kīlauea Volcano is a large emitter of volcanic CO2 with emission rates ranging from 7500-30,000 t/d. However, Kīlauea presents a challenging situation for CO2 emission rate measurement in that the main source of SO2 is the active vent in Halema'uma'u Crater, whereas CO2 emits mainly from a large (> 1km2) diffuse region east of the vent. Previous researchers recognized this issue and advocated for the use of a plume-integrated concentration ratio paired with the SO2 emission to determine CO2 emission rates; however, this worked best prior to the opening of the summit vent in 2008, or when SO2emission was still diffuse as opposed to focused degassing from the vent. We used two techniques to study the spatial distribution and temporal variability of CO2 release from the summit caldera in July, 2014. Eddy covariance measurements made at 14 locations in the area of diffuse emission resulted in elevated fluxes that generally ranged from 500 to > 5000 g/m2d, or typical of other volcanic and hydrothermal areas worldwide. MultiGas measurements of the CO2 and SO2 concentration in air at 1-m above the ground identified approximately seven areas of elevated area of CO2 degassing in the caldera. The CO2 concentrations in air were spatially well correlated to approximately 100 m and displayed anisotropy that was consistent with the measured wind direction. Areas of highest CO2 concentration correlated with the areas of highest flux using the eddy covariance method and were found near the middle of the caldera approximately 1 km NE of the active vent. This area overlies the inferred location of the shallow summit reservoir, and is characterized by linear fractures with adhered sublimate deposits at the surface. A few of the fractures are visibly fuming, but much of the degassing in the area is not apparent. Future work includes monitoring the fluxes in this area over time, and attempting to quantify emission rates from the areas of measured flux.

Electrochemical Study of Cobalt in Urea and Choline Chloride

NASA Astrophysics Data System (ADS)

Li, Min; Shi, Zhongning; Wang, Zhaowen; Reddy, Ramana G.

The nucleation mechanism of Co(II) in urea-choline chloride-CoCl2 melt at 373 K was studied using chronoamperometry. Chronoamperometry experiments confirm that the electrodeposition of cobalt on tungsten electrode is governed by three-dimensional (3D) progressive nucleation and diffusion-controlled growth mechanisms. The average diffusion coefficient of Co(II) in the melt at 373 K is 1.1 × 10-6 cm2 s-1, which is in good agreement with the estimated value obtained from cyclic voltammetry data. Characterization of the Co electrodeposit using scanning electron microscope (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD) techniques indicate that the electrodeposit obtained at -0.75 V and 373 K contain dense and compact surface formed from pure cobalt metal.

Soil CO2 efflux measurement network by means of closed static chambers to monitor volcanic activity at Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Amonte, Cecilia; García-Merino, Marta; Asensio-Ramos, María; Melián, Gladys; García-Hernández, Rubén; Pérez, Aaron; Hernández, Pedro A.; Pérez, Nemesio M.

2017-04-01

Tenerife (2304 km2) is the largest of the Canary Islands and has developed a central volcanic complex (Cañadas edifice), that started to grow about 3.5 My ago. Coeval with the construction of the Cañadas edifice, shield basaltic volcanism continued until the present along three rift zones oriented NW-SE, NE-SW and NS (hereinafter referred as NW, NE and NS respectively). Main volcanic historical activity has occurred along de NW and NE rift-zones, although summit cone of Teide volcano, in central volcanic complex, is the only area of the island where surface geothermal manifestations are visible. Uprising of deep-seated gases occurs along the aforementioned volcanic structures causing diffuse emissions at the surface environment of the rift-zones. In the last 20 years, there has been considerable interest in the study of diffuse degassing as a powerful tool in volcano monitoring programs. Diffuse degassing studies are even more important volcanic surveillance tool at those volcanic areas where visible manifestations of volcanic gases are absent. Historically, soil gas and diffuse degassing surveys in volcanic environments have focused mainly on CO2 because it is, after water vapor, the most abundant gas dissolved in magma. One of the most popular methods used to determine CO2 fluxes in soil sciences is based on the absorption of CO2 through an alkaline medium, in its solid or liquid form, followed by gravimetric, conductivity, or titration analyses. In the summer of 2016, a network of 31 closed static chambers was installed, covering the three main structural zones of Tenerife (NE, NW and NS) as well as Cañadas Caldera with volcanic surveillance porpoises. 50 cc of 0.1N KOH solution is placed inside the chamber to absorb the CO2 released from the soil. The solution is replaced weekly and the trapped CO2 is then analyzed at the laboratory by titration. The are expressed as weekly integrated CO2 efflux values. The CO2 efflux values ranged from 3.2 to 12.9 gṡm-2ṡd-1, with average values of 7.0 gṡm-2ṡd-1 for the NE rift-zone and 6.4 gṡm-2ṡd-1 for NW and NS rift-zones. The most significant CO2 efflux values were observed in the NE rift-zone, with maximum values of 12.5 gṡm-2ṡd-1. To investigate the origin of the soil CO2 at the three volcanic rifts, soil gas samples were weekly taken on the head space of the closed chambers to study the chemical composition and the isotopic composition of the CO2. Collected gas samples can be considered as CO2-enriched air, showing concentrations of CO2 in the range 370-22,448 ppmV, with average values of 2,859 ppmV, 1,396 ppmV and 1,216 ppmV for the NE, NW and NS rift-zones, respectively. The CO2isotopic composition, expressed as dxzC-CO2, indicates that most of the sampling sites exhibited CO2 composed by different mixing degrees between atmospheric and biogenic CO2 with slight inputs of deep-seated CO2, with mean values of -17.5‰ -13.6‰ and -16.4‰ for the NE, NW and NS rift-zones, respectively. The methodology presented here represents an inexpensive method that might help to detect early warning signals of future unrest episodes in Tenerife.

Influence of crystal structure on the Co{sup II} diffusion behavior in the Zn{sub 1-x}Co{sub x}O system

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

Peiteado, M.; Makovec, D.; Villegas, M.

2008-09-15

The solid state interaction of the Zn{sub 1-x}Co{sub x}O nominal system is investigated by means of diffusion couples and analysis of co-precipitated samples. The formation of a homogeneous Co:ZnO solid solution is found to be determined by the crystal structure from which Co{sup II} ions diffuse into the wurtzite lattice. No diffusion is observed whenever the CoO rock-salt structure is formed from the Co{sup II} precursor. On the contrary, the diffusion from the Co{sub 3}O{sub 4} spinel phase is feasible but has a limited temperature range defined by the reduction at a high temperature of Co{sup III}-Co{sup II}, since thismore » process again leads to the formation of the rock-salt structure. However, when using a highly reactive and homogeneous co-precipitated starting powder, neither the spinel phase nor the rock-salt structure is formed, and a Co{sup II}:ZnO solid solution is obtained, which remains stable up to high temperatures. - Graphical abstract: Maximum diffusion distance for the ZnO-CoO{sub x} couple as a function of temperature. Dashed gray lines represent the temperature values at which the transformations between CoO and Co{sub 3}O{sub 4} compounds take place.« less

The Martian diffuse aurora: Monte Carlo simulations and comparison with IUVS-MAVEN observations

NASA Astrophysics Data System (ADS)

Gerard, J. C. M. C.; Soret, L.; Schneider, N. M.; Shematovich, V.; Bisikalo, D.; Bougher, S. W.; Jain, S.; Lillis, R. J.; Mitchell, D. L.; Jakosky, B. M.; Deighan, J.; Larson, D. E.

2016-12-01

A new type of Martian aurora, characterized by an extended spatial distribution, an altitude lower than the discrete aurora and electron precipitation up to 200 keV has been observed following solar activity on several occasions with the IUVS on board the MAVEN spacecraft. We describe the results of Monte Carlo simulations of the production of several ultraviolet and visible auroral emissions for initial electron energies from 0.1 to 200 keV. These include the CO2+ ultraviolet doublet (UVD) at 288.3 and 289.6 nm and the Fox-Duffendack-Barker (FDB) bands, CO Cameron and Fourth Positive bands, OI 130.4 and 297.2 nm and CI 156.1 nm and 165.7 nm multiplets. We calculate the nadir and limb intensities of several of these emissions for a unit precipitated energy flux. Our results indicate that electrons in the range 100-200 keV produce maximum CO2+ UVD emission near 75 km. We combine SWEA and SEP electron energy spectra measured during diffuse aurora to calculate the volume emission rates and compare with IUVS observations of the emission limb profiles. The strongest predicted emissions are the CO2+ FDB, UVD and the CO Cameron bands. The metastable a 3Π state which radiates the Cameron bands is deactivated by collisions below 110 km. As a consequence, we show that the CO2+ UVD to the Cameron bands ratio increases at low altitude in the energetic diffuse aurora.

Geochemistry and fluxes of volatiles in the Magadi and Natron thermal springs, East African Rift

NASA Astrophysics Data System (ADS)

Lee, H.; Fischer, T. P.; Muirhead, J.; Ebinger, C. J.; Kattenhorn, S. A.; Sharp, Z. D.; Sano, Y.; Takahata, N.

2016-12-01

The Magadi and Natron basin (MNB) is in the earliest stages of continental rifting (<10 Ma) in the East African Rift, and is bounded by numerous normal faults releasing a significant amount of CO2 (4.05 Mt/yr). Although many thermal springs have been observed along fault zones, sources and fluxes of volatiles from these fluids are poorly known. This study reports geochemistry and fluxes of dissolved gases in thermal springs of the MNB (T = 36.8 - 83.5°C and pH = 8.5 - 10.3), including major gas chemistry, d13C-CO2, d15N-N2, and 3He/4He ratios. N2 (< 94.7 vol%) is the most abundant gas, with minor air contamination (mean value of O2 = 1.79 vol%). The majority of CO2 (mean = 11.8 vol%) is dissolved in alkaline waters. Abundant CH4 concentrations (19.3 and 25.1 vol%) are observed only in high temperature (82.3 - 83.5°C) samples. Mean values of Ar and He are 1.75 and 0.59 vol%, respectively. d13C-CO2 (-5.68 to 1.62‰) and CO2/3He (7.24 x 108 - 1.81 x 1011) values show that CO2 originates from both mantle and limestone. d15N-N2 (-1.46 to 0.35‰) and N2/3He (3.92 x 106 - 1.33 x 109) values indicate that the major source of N2 is atmospheric, with a minor input of mantle N2 (fmantle < 22%), except for an anomalous biogenic sample (d15N-N2 = 5.93‰). 3He/4He ratios (0.64 - 4.00 Ra) suggest contributions of radiogenic 4He derived from a crustal source. 4He flux rates (3.64 x 1011 - 3.34 x 1014 atoms/m2 sec) calculated using spring flow rates are much greater than reported mean of continental flux values (4.18x1010 atoms/m2 sec), implying that magma intrusions or widespread normal faulting may help to mobilize crustal 4He in the study area. Total flux values (mol/yr) of CO2, N2, 3He, and 4He are 7.91 x 106, 1.77 x 107, 8.18, and 9.33 x 104, respectively. In particular, the total CO2 flux of springs is 0.01% of the total diffuse CO2 flux reported in the region. Our results reveal an interaction between mantle-derived volatiles and continental crust during early stage continental rifting in the MNB, with their upward rise facilitated by dilatational fault systems.

A Novel Method for Determining the Gas Transfer Velocity of Carbon Dioxide in Streams

NASA Astrophysics Data System (ADS)

McDowell, M. J.; Johnson, M. S.

2016-12-01

Characterization of the global carbon cycle relies on the accurate quantification of carbon fluxes into and out of natural and human-dominated ecosystems. Among these fluxes, carbon dioxide (CO2) evasion from surface water has received increasing attention in recent years. However, limitations of current methods, including determination of the gas transfer velocity (k), compromise our ability to evaluate the significance of CO2 fluxes between freshwater systems and the atmosphere. We developed an automated method to determine gas transfer velocities of CO2 (kCO2), and tested it under a range of flow conditions for a first-order stream of a headwater catchment in southwestern British Columbia, Canada. Our method uses continuous in situ measurements of CO2 concentrations using two non-dispersive infrared (NDIR) sensors enclosed in water impermeable, gas permeable membranes (Johnson et al., 2010) downstream from a gas diffuser. CO2 was injected into the stream at regular intervals via a compressed gas tank connected to the diffuser. CO2 injections were controlled by a datalogger at fixed time intervals and in response to storm-induced changes in streamflow. Following the injection, differences in CO2 concentrations at known distances downstream from the diffuser relative to pre-injection baseline levels allowed us to calculate kCO2. Here we present relationships between kCO2 and hydro-geomorphologic (flow velocity, streambed slope, stream width, stream depth), atmospheric (wind speed and direction), and water quality (stream temperature, pH, electrical conductivity) variables. This method has advantages of being automatable and field-deployable, and it does not require supplemental gas chromatography, as is the case for propane injections typically used to determine k. The dataset presented suggests the potential role of this method to further elucidate the role that CO2 fluxes from headwater streams play in the global carbon cycle. Johnson, M. S., Billett, M. F., Dinsmore, K. J., Wallin, M., Dyson, K. E., & Jassal, R. S. (2010). Direct and continuous measurement of dissolved carbon dioxide in freshwater aquatic systems—method and applications. Ecohydrology, 3(1), 68-78. http://doi.org/10.1002/eco.95

System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO{sub 2}, n-alkanes, and poly(ethylene glycol) dimethyl ethers

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

Moultos, Othonas A.; Economou, Ioannis G.; Zhang, Yong

Molecular dynamics simulations were carried out to study the self-diffusion coefficients of CO{sub 2}, methane, propane, n-hexane, n-hexadecane, and various poly(ethylene glycol) dimethyl ethers (glymes in short, CH{sub 3}O–(CH{sub 2}CH{sub 2}O){sub n}–CH{sub 3} with n = 1, 2, 3, and 4, labeled as G1, G2, G3, and G4, respectively) at different conditions. Various system sizes were examined. The widely used Yeh and Hummer [J. Phys. Chem. B 108, 15873 (2004)] correction for the prediction of diffusion coefficient at the thermodynamic limit was applied and shown to be accurate in all cases compared to extrapolated values at infinite system size. Themore » magnitude of correction, in all cases examined, is significant, with the smallest systems examined giving for some cases a self-diffusion coefficient approximately 15% lower than the infinite system-size extrapolated value. The results suggest that finite size corrections to computed self-diffusivities must be used in order to obtain accurate results.« less

Gas emission into the atmosphere from controlled landfills: an example from Legoli landfill (Tuscany, Italy).

PubMed

Raco, Brunella; Battaglini, Raffaele; Lelli, Matteo

2010-07-01

Landfill gas (LFG) tends to escape from the landfill surface even when LFG collecting systems are installed. Since LFG leaks are generally a noticeable percentage of the total production of LFG, the optimisation of the collection system is a fundamental step for both energy recovery and environmental impact mitigation. In this work, we suggest to take into account the results of direct measurements of gas fluxes at the air-cover interface to achieve this goal. During the last 5 years (2004-2009), 11 soil gas emission surveys have been carried out at the Municipal Solid Waste landfill of Legoli (Peccioli municipality, Pisa Province, Italy) by means of the accumulation chamber method. Direct and simultaneous measurements of CH(4) and CO(2) fluxes from the landfill cover (about 140,000 m(2)) have been performed to estimate the total output of both gases discharged into the atmosphere. Three different data processing have been applied and compared: Arithmetic mean of raw data (AMRD), sequential Gaussian conditional simulations (SGCS) and turning bands conditional simulations (TBCS). The total amount of LFG (captured and not captured) obtained from processing of direct measurements has been compared with the corresponding outcomes of three different numerical models (LandGEM, IPCC waste model and GasSim). Measured fluxes vary from undetectable values (<0.05 mol m(-2) day(-1) for CH(4) and <0.02 mol m(-2) day(-1) for CO(2)) to 246 mol m(-2) day(-1) for CH(4) and 275 mol m(-2) day(-1) for CO(2). The specific CH(4) and CO(2) fluxes (flux per surface unit) vary from 1.8 to 7.9 mol m(-2) day(-1) and from 2.4 to 7.8 mol m(-2) day(-1), respectively. The three different estimation methodologies (AMRD, SGCS and TBCS) used to evaluate the total output of diffused CO(2) and CH(4) fluxes from soil provide similar estimations, whereas there are some mismatches between these results and those of numerical LFG production models. Isoflux maps show a non-uniform spatial distribution, with high-flux zones not always corresponding with high-temperature areas shown by thermographic images. The average value estimated over the 5-year period for the Legoli landfill is 245 mol min(-1) for CH(4) and 379 mol min(-1) for CO(2), whereas the volume percentage of CH(4) in the total gas discharged into the atmosphere varies from 29% to 51%, with a mean value of 39%. The estimated yearly emissions from the landfill cover is about 1.29 x 10(8) mol annum(-1) (2,100 t year(-1)) of CH(4) and 1.99 x 10(8) mol annum(-1) (8,800 t year(-1)) of CO(2). Considering that the CH(4) global warming potential is 63 times greater than that of CO(2) (20 a time horizon, Lashof and Ahuja 1990), the emission of methane corresponds to 130,000 t annum(-1) of CO(2). The importance of these studies is to provide data for the worldwide inventory of CH(4) and CO(2) emissions from landfills, with the ultimate aim of determining the contribution of waste disposal to global warming. This kind of studies could be extended to other gas species, like the volatile organic compounds.

A missing element of the deep carbon cycle: CO2 degassing estimates from rift length analysis during Pangea fragmentation

NASA Astrophysics Data System (ADS)

Brune, S.; Williams, S.; Müller, D.

2016-12-01

The deep carbon cycle connects CO2 within the atmosphere and oceans to the vast CO2 reservoir in Earth's mantle: subducted lithosphere carries CO2 into the mantle, while extensional plate boundaries and arc volcanoes release it back to Earth's surface. The length of plate boundaries thereby exerts first-order control on global CO2 fluxes on geological time scales. Here we provide a worldwide census of extensional plate boundary length from the Triassic to present day, in one million year time intervals, using a novel analysis technique (Brune et al. 2016, Nature, doi:10.1038/nature18319). The most extensive rift phase during the fragmentation of Pangea occurred in the Cretaceous with extension along the South Atlantic (9700 km) and North Atlantic rifts (9100 km), within East Gondwana (8500 km), and the failed African rift systems (4900 km). The combined extent of these and several smaller rifts amounts to more than 30.000 km of simultaneously active continental rifting. It is well-accepted that volcanoes at plate boundaries release large amounts of CO2 from the Earth's interior. Recent work, however, revealed the importance of deep-cutting faults and diffuse degassing on CO2 emissions in the East African rift (Lee et al. 2016, Nature Geoscience, doi: 10.1038/ngeo2622). Upscaling these measured CO2 fluxes to all concurrently active global rift zones, we compute first-order estimates of total rift-related CO2 degassing rates for the last 240 Myr. Our results show that rift-related CO2 release rates may have reached 600 Mt/yr in the Early Cretaceous, while Cenozoic rates rarely exceeded 200 Mt/yr. By comparison, present-day estimates of CO2 release at mid-ocean ridges range between 53 and 97 Mt/yr. We suggest that rift-related degassing during supercontinental breakup played a major role in maintaining high atmospheric CO2 concentrations through Mesozoic times, which exceeded Quaternary values by 400%.

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.

Discrimination in the dark. Resolving the interplay between metabolic and physical constraints to phosphoenolpyruvate carboxylase activity during the crassulacean acid metabolism cycle.

PubMed

Griffiths, Howard; Cousins, Asaph B; Badger, Murray R; von Caemmerer, Susanne

2007-02-01

A model defining carbon isotope discrimination (delta13C) for crassulacean acid metabolism (CAM) plants was experimentally validated using Kalanchoe daigremontiana. Simultaneous measurements of gas exchange and instantaneous CO2 discrimination (for 13C and 18O) were made from late photoperiod (phase IV of CAM), throughout the dark period (phase I), and into the light (phase II). Measurements of CO2 response curves throughout the dark period revealed changing phosphoenolpyruvate carboxylase (PEPC) capacity. These systematic changes in PEPC capacity were tracked by net CO2 uptake, stomatal conductance, and online delta13C signal; all declined at the start of the dark period, then increased to a maximum 2 h before dawn. Measurements of delta13C were higher than predicted from the ratio of intercellular to external CO2 (p(i)/p(a)) and fractionation associated with CO2 hydration and PEPC carboxylations alone, such that the dark period mesophyll conductance, g(i), was 0.044 mol m(-2) s(-1) bar(-1). A higher estimate of g(i) (0.085 mol m(-2) s(-1) bar(-1)) was needed to account for the modeled and measured delta18O discrimination throughout the dark period. The differences in estimates of g(i) from the two isotope measurements, and an offset of -5.5 per thousand between the 18O content of source and transpired water, suggest spatial variations in either CO2 diffusion path length and/or carbonic anhydrase activity, either within individual cells or across a succulent leaf. Our measurements support the model predictions to show that internal CO2 diffusion limitations within CAM leaves increase delta13C discrimination during nighttime CO2 fixation while reducing delta13C during phase IV. When evaluating the phylogenetic distribution of CAM, carbon isotope composition will reflect these diffusive limitations as well as relative contributions from C3 and C4 biochemistry.

Quantification of the CO2 emitted from volcanic lakes in Pico Island (Azores)

NASA Astrophysics Data System (ADS)

Andrade, César; Cruz, José; Viveiros, Fátima; Branco, Rafael

2017-04-01

This study shows the results of the diffuse CO2 degassing surveys performed in lakes from Pico volcanic Island (Azores archipelago, Portugal). Detailed flux measurements using the accumulation chamber method were made at six lakes (Capitão, Caiado, Paul, Rosada, Peixinho and Negra) during two field campaigns, respectively, in winter (February 2016) and late summer (September 2016). Pico is the second largest island of the Azores archipelago with an area of 444.8 km2; the oldest volcanic unit is dated from about 300,000 years ago. The edification of Pico was mainly due to Hawaiian and Strombolian type volcanic activity, resulting in pahoehoe and aa lava flows of basaltic nature, as well as scoria and spatter cones. Three main volcanic complexes are identified in the island, namely (1) the so-called Montanha Volcanic Complex, corresponding to a central volcano located in the western side of the island that reaches a maximum altitude of 2351 m, (2) the São Roque-Piedade Volcanic Complex, and (3) the Topo-Lajes Volcanic Complex, this last one corresponding to the remnants of a shield volcano located in the south coast. The studied lakes are spread along the São Roque-Piedade Volcanic Complex at altitudes between 785 m and 898 m. Three are associated with depressions of undifferentiated origin (Caiado, Peixinho, Negra), two with depressions of tectonic origin (Capitão, Paul), while Rosada lake is located inside a scoria cone crater. The lakes surface areas vary between 1.25x10-2 and 5.38x10-2 km2, and the water column maximum depth is 7.9 m (3.5-7.9 m). The water storage ranges between 3.6x104 to 9.1x104 m3, and the estimated residence time does not exceed 1.8x10-1 years. A total of 1579 CO2 flux measurements were made during both surveys (868 in summer and 711 in the winter campaign), namely 518 in Caiado lake (293; 225), 358 in Paul (195; 163), 279 in Capitão (150, 129), 200 in Rosada (106, 94), 171 in Peixinho (71, 100) and 53 measurements in Negra lake. Negra Lake was only sampled in the summer season. The CO2 flux values range between 0.68 g m-2 d-1 (Paul lake) and 20.47 g m-2 d-1 (Negra). The total CO2 emission varies between 0.03 t d-1 (Negra and Peixinho lakes) and 0.30 t d-1 (Caiado lake) for the summer surveys, and between 0.04 t d-1 (Rosada lake) and 0.26 t d-1 (Caiado lake) for the winter data. The higher CO2 emission is observed for Rosada lake (8.89 t km-2 d-1) during summer and the lower corresponds to the Negra lake (1.67 t km-2 d-1) during summer. Considering the set of the studied volcanic lakes, the CO2 emission sums up to 64 t d-1 (winter campaign) and 72 t d-1 (summer). These emissions are probably mainly associated to a biogenic source, but the characterization of the CO2 emission in these volcanic lakes during periods of quiescence is relevant for any seismo-volcanic monitoring programme. Key words: volcanic lakes, CO2 flux, diffuse degassing, Pico Island, Azores

Wollastonite Carbonation in Water-Bearing Supercritical CO2: Effects of Particle Size.

PubMed

Min, Yujia; Li, Qingyun; Voltolini, Marco; Kneafsey, Timothy; Jun, Young-Shin

2017-11-07

The performance of geologic CO 2 sequestration (GCS) can be affected by CO 2 mineralization and changes in the permeability of geologic formations resulting from interactions between water-bearing supercritical CO 2 (scCO 2 ) and silicates in reservoir rocks. However, without an understanding of the size effects, the findings in previous studies using nanometer- or micrometer-size particles cannot be applied to the bulk rock in field sites. In this study, we report the effects of particle sizes on the carbonation of wollastonite (CaSiO 3 ) at 60 °C and 100 bar in water-bearing scCO 2 . After normalization by the surface area, the thickness of the reacted wollastonite layer on the surfaces was independent of particle sizes. After 20 h, the reaction was not controlled by the kinetics of surface reactions but by the diffusion of water-bearing scCO 2 across the product layer on wollastonite surfaces. Among the products of reaction, amorphous silica, rather than calcite, covered the wollastonite surface and acted as a diffusion barrier to water-bearing scCO 2 . The product layer was not highly porous, with a specific surface area 10 times smaller than that of the altered amorphous silica formed at the wollastonite surface in aqueous solution. These findings can help us evaluate the impacts of mineral carbonation in water-bearing scCO 2 .

Enhancement of crop photosynthesis by diffuse light: quantifying the contributing factors.

PubMed

Li, T; Heuvelink, E; Dueck, T A; Janse, J; Gort, G; Marcelis, L F M

2014-07-01

Plants use diffuse light more efficiently than direct light. However, experimental comparisons between diffuse and direct light have been obscured by co-occurring differences in environmental conditions (e.g. light intensity). This study aims to analyse the factors that contribute to an increase in crop photosynthesis in diffuse light and to quantify their relative contribution under different levels of diffuseness at similar light intensities. The hypothesis is that the enhancement of crop photosynthesis in diffuse light results not only from the direct effects of more uniform vertical and horizontal light distribution in the crop canopy, but also from crop physiological and morphological acclimation. Tomato (Solanum lycopersicum) crops were grown in three greenhouse compartments that were covered by glass with different degrees of light diffuseness (0, 45 and 71 % of the direct light being converted into diffuse light) while maintaining similar light transmission. Measurements of horizontal and vertical photosynthetic photon flux density (PPFD) distribution in the crop, leaf photosynthesis light response curves and leaf area index (LAI) were used to quantify each factor's contribution to an increase in crop photosynthesis in diffuse light. In addition, leaf temperature, photoinhibition, and leaf biochemical and anatomical properties were studied. The highest degree of light diffuseness (71 %) increased the calculated crop photosynthesis by 7·2 %. This effect was mainly attributed to a more uniform horizontal (33 % of the total effect) and vertical PPFD distribution (21 %) in the crop. In addition, plants acclimated to the high level of diffuseness by gaining a higher photosynthetic capacity of leaves in the middle of the crop and a higher LAI, which contributed 23 and 13 %, respectively, to the total increase in crop photosynthesis in diffuse light. Moreover, diffuse light resulted in lower leaf temperatures and less photoinhibition at the top of the canopy when global irradiance was high. Diffuse light enhanced crop photosynthesis. A more uniform horizontal PPFD distribution played the most important role in this enhancement, and a more uniform vertical PPFD distribution and higher leaf photosynthetic capacity contributed more to the enhancement of crop photosynthesis than did higher values of LAI. © The Author 2014. Published by Oxford University Press on behalf of the Annals of Botany Company. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Geophysical image of the hydrothermal system of Merapi volcano

NASA Astrophysics Data System (ADS)

Byrdina, S.; Friedel, S.; Vandemeulebrouck, J.; Budi-Santoso, A.; Suhari; Suryanto, W.; Rizal, M. H.; Winata, E.; Kusdaryanto

2017-01-01

We present an image of the hydrothermal system of Merapi volcano based on results from electrical resistivity tomography (ERT), self-potential, and CO2 flux mappings. The ERT models identify two distinct low-resistivity bodies interpreted as two parts of a probably interconnected hydrothermal system: at the base of the south flank and in the summit area. In the summit area, a sharp resistivity contrast at ancient crater rim Pasar-Bubar separates a conductive hydrothermal system (20-50 Ω m) from the resistive andesite lava flows and pyroclastic deposits (2000-50,000 Ω m). The existence of preferential fluid circulation along this ancient crater rim is also evidenced by self-potential data. The significative diffuse CO2 degassing (with a median value of 400 g m-2 d-1) is observed in a narrow vicinity of the active crater rim and close to the ancient rim of Pasar-Bubar. The total CO2 degassing across the accessible summital area with a surface of 1.4 ṡ 105 m2 is around 20 t d-1. Before the 2010 eruption, Toutain et al. (2009) estimated a higher value of the total diffuse degassing from the summit area (about 200-230 t d-1). This drop in the diffuse degassing from the summit area can be related to the decrease in the magmatic activity, to the change of the summit morphology, to the approximations used by Toutain et al. (2009), or, more likely, to a combination of these factors. On the south flank of Merapi, the resistivity model shows spectacular stratification. While surficial recent andesite lava flows are characterized by resistivity exceeding 100,000 Ω m, resistivity as low as 10 Ω m has been encountered at a depth of 200 m at the base of the south flank and was interpreted as a presence of the hydrothermal system. No evidence of the hydrothermal system is found on the basis of the north flank at the same depth. This asymmetry might be caused by the asymmetry of the heat supply source of Merapi whose activity is moving south or/and to the asymmetry in topography caused by the presence of Merbabu volcano in the north. On the basis of our results we suggest that stratified pyroclastic deposits on the south flank of Merapi screen and separate the flow of hydrothermal fluids with the gaseous part rising through the crater rims, while the liquid part is flowing downwards to the base of the edifice.

Spatially Variable CO2 Degassing in the Main Ethiopian Rift: Implications for Magma Storage, Volatile Transport, and Rift-Related Emissions

NASA Astrophysics Data System (ADS)

Hunt, Jonathan A.; Zafu, Amdemichael; Mather, Tamsin A.; Pyle, David M.; Barry, Peter H.

2017-10-01

Deep carbon emissions from historically inactive volcanoes, hydrothermal, and tectonic structures are among the greatest unknowns in the long-term (˜Myr) carbon cycle. Recent estimates of diffuse CO2 flux from the Eastern Rift of the East African Rift System (EARS) suggest this could equal emissions from the entire mid-ocean ridge system. We report new CO2 surveys from the Main Ethiopian Rift (MER, northernmost EARS), and reassess the rift-related CO2 flux. Since degassing in the MER is concentrated in discrete areas of volcanic and off-edifice activity, characterization of such areas is important for extrapolation to a rift-scale budget. Locations of hot springs and fumaroles along the rift show numerous geothermal areas away from volcanic edifices. With these new data, we estimate total CO2 emissions from the central and northern MER as 0.52-4.36 Mt yr-1. Our extrapolated flux from the Eastern Rift is 3.9-32.7 Mt yr-1 CO2, overlapping with lower end of the range presented in recent estimates. By scaling, we suggest that 6-18 Mt yr-1 CO2 flux can be accounted for by magmatic extension, which implies an important role for volatile-enriched lithosphere, crustal assimilation, and/or additional magmatic intrusion to account for the upper range of flux estimates. Our results also have implications for the nature of volcanism in the MER. Many geothermal areas are found >10 km from the nearest volcanic center, suggesting ongoing hazards associated with regional volcanism.

Resistivity structure of the Furnas hydrothermal system (Azores archipelago, Portugal) from AMT and ERT imaging.

NASA Astrophysics Data System (ADS)

Byrdina, Svetlana; Vandemeulebrouck, Jean; Rath, Volker; Silva, Catarina; Hogg, Colin; Kiyan, Duygu; Viveiros, Fatima; Eleuterio, Joana; Gresse, Marceau

2016-04-01

The Furnas volcanic complex is located in the eastern part of the São Miguel Island and comprises a 5 km × 8 km summit depression filled by two nested calderas with several craters and a lake. Present-day volcanic activity of Furnas volcano is mostly located in the northern part of the caldera, within the Furnas village and north to Furnas Lake, where hydrothermal manifestations are mainly fumarolic fields, steam vents, thermal springs, and intense soil diffuse degassing. Considering the Furnas volcano as a whole, the total integrated CO2 efflux is extremely high, with a total amount of CO2 close to 1000 ton per day (Viveiros et al., 2009). We present the first results of an electrical resistivity tomography (ERT), combined with audio-magneto-telluric (AMT) measurements aligned along two profiles inside the caldera. The purpose of this survey is to delimit the extent, the geometry, and the depth of the hydrothermal system and to correlate the deep resistivity structure with high resolution cartography of diffuse CO2 flux (Viveiros et al, 2015). The ERT and AMT methods are complementary in terms of resolution and penetration depth: ERT can image the structural details of shallow hydrothermal system (down to 100 m in our study) while AMT can image at lower resolution deeper structures at the roots of a volcano (down to 4 km in our study). Our first independent 2D inversions of the ERT-AMT data show a good agreement between the surficial and deeper features. Below the main fumarole area we observe a low resistivity body (less than 1 Ohmm) which corresponds well to the high CO2 flux at the surface and is associated with an extended conductive body at larger depth. These results strongly suggest the presence of hydrothermal waters at depth or/and the presence of altered clay-rich material. On a larger scale however, the geometry of the conducting zones differs slightly from what was expected from earlier surface studies, and may not be directly related to fault zones mapped at the surface. These slight, but measurable discrepancies might have different origins but they stress the necessity of 3D modelling and the importance of the joint inversion of the data which we consider as a next step in our work.

Beyond the Methanogenic Black-Box: Greenhouse Gas Fluxes (CO2, CH4, N2O) as Evidence for Wetlands as Dynamic Redox Systems

NASA Astrophysics Data System (ADS)

Mcnicol, G.; Knox, S. H.; Sturtevant, C. S.; Baldocchi, D. D.; Silver, W. L.

2015-12-01

Seminal wetland research in the 1990s demonstrated that annual methane (CH4) fluxes scaled positively with ecosystem production across distinctive wetlands globally. This relationship implies a model of flooded wetland ecosystems as 'methanogenic black-boxes'; poised at a low redox state, and tending to release a fixed fraction of incoming annual productivity as CH4. In contrast, recent studies have reported high ratios of carbon dioxide (CO2) to CH4 emissions, and are adding to a body of evidence suggesting wetlands can vary more widely in their redox state. To explore this apparent incongruence we used principles of redox thermodynamics and laboratory experiments to develop predictions of wetland greenhouse gas (GHG) fluxes under different redox regimes. We then used a field study to test the hypothesis that ecosystem seasonality in gross primary productivity (GPP) and temperature would drive changes in GHG emissions, mediated by a dynamic - as opposed to static - redox regime. We estimated wetland GHG emissions from an emergent marsh in the Sacramento Delta, CA from March 2014-2015. We measured CO2, CH4 and N2O emissions via diffusion and ebullition with manual sampling, and whole-ecosystem fluxes of CO2 and CH4 using eddy-covariance. Ebullition and diffusive CH4 fluxes were strongly seasonal, with minimum rates (0.86 and 0.35 mg C-CH­­4 m-2 yr-1, respectively) during winter, and maximum rates (1.3 and 1.8 g C-CH­­4 m-2 yr-1, respectively) during the summer growing season. In contrast, winter diffusive CO2 fluxes (494 g C-CO2 m-2 yr-1) and fall bubble CO2 concentrations (1.49%) were highest, despite being seasons of lower GPP, temperature, and CH4 flux. Further, diffusive and ebullition fluxes of N2O showed zero net flux only during spring and summer months, whereas the wetland was a significant source of N2O during winter (81.2 ± 24.4 mg N-N2O m-2 yr-1). These seasonal flux dynamics contradict a 'methanogenic black box' model of wetland redox, which predicts carbon limitation of, and concurrent maxima in, heterotrophic CO2 and CH4 emissions, and no significant N2O emissions. Rather these results suggest that wetlands can function as dynamic redox environments where GHG emission rate and composition varies predictably in time with seasonal changes in GPP and temperature.

Reversible Redox Effect on Gas Permeation of Cobalt Doped Ethoxy Polysiloxane (ES40) Membranes

PubMed Central

Miller, Christopher R.; Wang, David K.; Smart, Simon; Diniz da Costa, João C.

2013-01-01

This work reports the remarkable effect of reversible gas molecular sieving for high temperature gas separation from cobalt doped ethoxy polysiloxane (CoES40) membranes. This effect stemmed from alternating the reducing and oxidising (redox) state of the cobalt particles embedded in the ES40 matrix. The reduced membranes gave the best H2 permeances of 1 × 10−6 mol m−2 s−1 Pa−1 and H2/N2 permselectivities of 65. The reduction process tailored a molecular gap attributed to changes in the specific volume between the reduced cobalt (Co(OH)2 and CoO) particles in the ES40 structure, thus allowing for the increased diffusion of gases. Upon re-oxidation, the tailored molecular gap became constricted as the particles reversed to Co3O4 resulting a lower gas diffusion, particularly for the larger gases ie. CO2 and N2. The ES40 matrix proved to be structurally rigid enough to withstand the reversible redox effect of cobalt particles across multiple cycles. PMID:23571730

Comparison of slime-producing coagulase-negative Staphylococcus colonization rates on vinyl and ceramic tile flooring materials.

PubMed

Yazgi, H; Uyanik, M H; Ayyildiz, A

2009-01-01

This study investigated the colonization of slime-producing coagulase-negative Staphylococcus (CoNS) in 80 patient wards in Turkey (40 vinyl and 40 ceramic tile floors). A total of 480 samples that included 557 CoNS isolates were obtained. Slime production was investigated with the Christensen method and methicillin-susceptibility was tested by the disk-diffusion method. There was a significant difference in the percentage of slime-producing CoNS isolates on vinyl (12.4%) versus ceramic tile flooring (4.4%). From vinyl flooring, the percentage of slime producing methicillin-resistant CoNS (MRCoNS) (8.9%) was significantly higher than for methicillin-sensitive CoNS (MSCoNS) (3.6%), whereas there was no difference from ceramic tile flooring (2.5% MRCoNS versus 1.8% MSCoNS). The most commonly isolated slime-producing CoNS species was S. epidermidis on both types of flooring. It is concluded that vinyl flooring seems to be a more suitable colonization surface for slime-producing CoNS than ceramic tile floors. Further studies are needed to investigate bacterial strains colonized on flooring materials, which are potential pathogens for nosocomial infections.

Hazardous indoor CO2 concentrations in volcanic environments.

PubMed

Viveiros, Fátima; Gaspar, João L; Ferreira, Teresa; Silva, Catarina

2016-07-01

Carbon dioxide is one of the main soil gases released silently and permanently in diffuse degassing areas, both in volcanic and non-volcanic zones. In the volcanic islands of the Azores (Portugal) several villages are located over diffuse degassing areas. Lethal indoor CO2 concentrations (higher than 10 vol %) were measured in a shelter located at Furnas village, inside the caldera of the quiescent Furnas Volcano (S. Miguel Island). Hazardous CO2 concentrations were detected not only underground, but also at the ground floor level. Multivariate regression analysis was applied to the CO2 and environmental time series recorded between April 2008 and March 2010 at Furnas village. The results show that about 30% of the indoor CO2 variation is explained by environmental variables, namely barometric pressure, soil water content and wind speed. The highest indoor CO2 concentrations were recorded during bad weather conditions, characterized by low barometric pressure together with rainfall periods and high wind speed. In addition to the spike-like changes observed on the CO2 time series, long-term oscillations were also identified and appeared to represent seasonal variations. In fact, indoor CO2 concentrations were higher during winter period when compared to the dry summer months. Considering the permanent emission of CO2 in various volcanic regions of the world, CO2 hazard maps are crucial and need to be accounted by the land-use planners and authorities. Copyright © 2016 Elsevier Ltd. All rights reserved.

Diffusion-cooled high-power single-mode waveguide CO2 laser for transmyocardial revascularization

NASA Astrophysics Data System (ADS)

Berishvili, I. I.; Bockeria, L. A.; Egorov, E. N.; Golubev, Vladimir S.; Galushkin, Michail G.; Kheliminsky, A. A.; Panchenko, Vladislav Y.; Roshin, A. P.; Sigaev, I. Y.; Vachromeeva, M. N.; Vasiltsov, Victor V.; Yoshina, V. I.; Zabelin, Alexandre M.; Zelenov, Evgenii V.

1999-01-01

The paper presents the results on investigations and development of multichannel waveguide CO2 laser with diffusion cooling of active medium excited by discharge of audio-frequency alternating current. The description of high-power single-mode CO2 laser with average beam power up to 1 kW is presented. The result of measurement of the laser basic parameters are offered, as well as the outcomes of performances of the laser head with long active zone, operating in waveguide mode. As an example of application of these laser, various capabilities a description of the developed medical system 'Genom' used in the transmyocardial laser revascularization (TMLR) procedure and clinical results of the possibilities of the TMLR in the surgical treatment are presented.

Enhanced Oxygen Diffusion Within the Internal Oxidation Zone of Alloy 617 in Controlled Impurity Helium Environments from 1023 K to 1123 K (750 °C to 850 °C)

NASA Astrophysics Data System (ADS)

Gulsoy, Gokce; Was, Gary S.

2015-04-01

Alloy 617 was exposed to He-CO-CO2 environments with of either 9 or 1320 at temperatures from 1023 K to 1123 K (750 °C to 850 °C) to determine the oxygen diffusion coefficients within the internal oxidation zone of the alloy. The oxygen diffusion coefficients determined based on both intergranular and transgranular oxidation rates were several orders of magnitude greater than those reported in pure nickel and in nickel-based binary alloys, indicating that the rapid internal aluminum oxidation of Alloy 617 was primarily due to enhanced oxygen diffusion along the incoherent Al2O3-alloy interfaces. The range of activation energy values determined for oxygen diffusion associated with the intergranular aluminum oxidation was from 149.6 to 154.7 kJ/mol, and that associated with the transgranular aluminum oxidation was from 244.7 to 283.5 kJ/mol.

Excess diffuse light absorption in upper mesophyll limits CO2 drawdown and depresses photosynthesis

USDA-ARS?s Scientific Manuscript database

Sun-grown and shade-grown leaves of some species absorb direct and diffuse light differently. Sun-grown leaves can photosynthesize ~10-15% less under diffuse compared to direct irradiance, while shade-grown leaves do not exhibit this sensitivity. In this study, we investigate if the spatial differen...

Copper Gas Diffusers For Purging Line-Focus Laser Welds

NASA Technical Reports Server (NTRS)

Fonteyne, Steve L.; Hosking, Timothy J.; Shelley, D. Mark

1996-01-01

Modified flow diffusers built for inert-gas purging of welds made with 5-kW CO(2) lasers operating with line-focus optics in conduction mode instead of with point-focus optics in customary keyhole mode. Diffusers made of copper components brazed together, robust enough to withstand strong reflections of line-focused laser energy.

Toxicological Assessment of CoO and La2O3 Metal Oxide Nanoparticles in Human Small Airway Epithelial Cells

PubMed Central

Pirela, Sandra V.; Shaffer, Justine; Mihalchik, Amy L.; Chisholm, William P.; Andrew, Michael E.; Schwegler-Berry, Diane; Castranova, Vincent; Demokritou, Philip; Qian, Yong

2016-01-01

Cobalt monoxide (CoO) and lanthanum oxide (La2O3) nanoparticles are 2 metal oxide nanoparticles with different redox potentials according to their semiconductor properties. By utilizing these two nanoparticles, this study sought to determine how metal oxide nanoparticle’s mode of toxicological action is related to their physio-chemical properties in human small airway epithelial cells (SAEC). We investigated cellular toxicity, production of superoxide radicals and alterations in gene expression related to oxidative stress, and cellular death at 6 and 24 h following exposure to CoO and La2O3 (administered doses: 0, 5, 25, and 50 µg/ml) nanoparticles. CoO nanoparticles induced gene expression related to oxidative stress at 6 h. After characterizing the nanoparticles, transmission electron microscope analysis showed SAEC engulfed CoO and La2O3 nanoparticles. CoO nanoparticles were toxic after 6 and 24 h of exposure to 25.0 and 50.0 µg/ml administered doses, whereas, La2O3 nanoparticles were toxic only after 24 h using the same administered doses. Based upon the Volumetric Centrifugation Method in vivo Sedimentation, Diffusion, and Dosimetry, the dose of CoO and La2O3 nanoparticles delivered at 6 and 24 h were determined to be: CoO: 1.25, 6.25, and 12.5 µg/ml; La2O3: 5, 25, and 50 µg/ml and CoO: 4, 20, and 40 µg/ml; and La2O3: 5, 25, 50 µg/ml, respectively. CoO nanoparticles produced more superoxide radicals and caused greater stimulation of total tyrosine and threonine phosphorylation at both 6 and 24 h when compared with La2O3 nanoparticles. Taken together, these data provide evidence that different toxicological modes of action were involved in CoO and La2O3 metal oxide nanoparticle-induced cellular toxicity. PMID:26769336

Soil matrix tracer contamination and canopy recycling did not impair ¹³CO₂ plant-soil pulse labelling experiments.

PubMed

Barthel, Matthias; Sturm, Patrick; Knohl, Alexander

2011-09-01

When conducting (13)CO(2) plant-soil pulse labelling experiments, tracer material might cause unwanted side effects which potentially affect δ(13)C measurements of soil respiration (δ(13)C(SR)) and the subsequent data interpretation. First, when the soil matrix is not isolated from the atmosphere, contamination of the soil matrix with tracer material occurs leading to a physical back-diffusion from soil pores. Second, when using canopy chambers continuously, (13)CO(2) is permanently re-introduced into the atmosphere due to leaf respiration which then aids re-assimilation of tracer material by the canopy. Accordingly, two climate chamber experiments on European beech saplings (Fagus sylvatica L.) were conducted to evaluate the influence of soil matrix (13)CO(2) contamination and canopy recycling on soil (13)CO(2) efflux during (13)CO(2) plant-soil pulse labelling experiments. For this purpose, a combined soil/canopy chamber system was developed which separates soil and canopy compartments in order to (a) prevent diffusion of (13)C tracer into the soil chamber during a (13)CO(2) canopy pulse labelling and (b) study stable isotope processes in soil and canopy individually and independently. In combination with laser spectrometry measuring CO(2) isotopologue mixing ratios at a rate of 1 Hz, we were able to measure δ(13)C in canopy and soil at very high temporal resolution. For the soil matrix contamination experiment, (13)CO(2) was applied to bare soil, canopy only or, simultaneously, to soil and canopy of the beech trees. The obtained δ(13)C(SR) fluxes from the different treatments were then compared with respect to label re-appearance, first peak time and magnitude. By determining the δ(13)C(SR) decay of physical (13)CO(2) back-diffusion from bare soils (contamination), it was possible to separate biological and physical components in δ(13)C(SR) of a combined flux of both. A second pulse labelling experiment, with chambers permanently enclosing the canopy, revealed that (13)CO(2) recycling at canopy level had no effect on δ(13)C(SR) dynamics.

Role of Water Activity on Intergranular Transport at High Pressure

NASA Astrophysics Data System (ADS)

Gasc, J.; Brunet, F.; Brantut, N.; Corvisier, J.; Findling, N.; Verlaguet, A.; Lathe, C.

2016-12-01

The kinetics of the reaction Ca(OH)2 + MgCO3 = CaCO3 + Mg(OH)2 were investigated at a pressure of 1.8 GPa and temperatures of 120-550°C, using synchrotron X-ray diffraction and analysis of reaction rims on recovered samples. Comparable reaction kinetics were obtained under water saturated ( 10 wt.%), intermediate (0.1-1 wt.%) and dry conditions at 150, 400 and 550°C, respectively, where, in the latter case, water activity was buffered below one (no free water). At a given temperature, these gaps imply differences of several orders of magnitude in terms of reaction kinetics. Microscopy analysis shows that intergranular transport of Ca controls the reaction progress. Grain boundary diffusivities were retrieved from measurements of reaction rim widths on recovered samples. In addition, an innovative reaction rim growth model was developed to simulate and fit kinetic data. The diffusion values thus obtained show that both dry and intermediate datasets are in fact consistent with a water saturated intergranular medium with different levels of connectivity. Diffusivity of Ca in the CaCO3 + Mg(OH)2 rims is found to be much larger than that of Mg in enstatite rims, which emphasizes the prominent role of interactions between diffusing species and mineral surfaces on diffusion. We suggest that diffusivity of major species (Mg, Ca) in low-porosity metamorphic rocks is not only water-content dependent but also strongly depends on the interaction between diffusing species and mineral surfaces. This parameter, which will vary from one rock-type to the other, needs to be considered when extrapolating (P,T,t, xH2O) laboratory diffusion data to metamorphic processes. The present study, along with previous data from the literature, will help quantify the tremendous effect of small water content variations, i.e., within the 0-1 wt. % range, on intergranular transport and reaction kinetics (Gasc et al., J. Pet., In press).

[In situ diffuse reflectance FTIR spectroscopy study of CO adsorption on Ni2P/mesoporous molecule sieve catalysts].

PubMed

Liu, Qian-qian; Ji, Sheng-fu; Wu, Ping-yi; Hu, Lin-hua; Huang, Xiao-fan; Zhu, Ji-qin; Li, Cheng-yue

2009-05-01

Abstract The supported nickel phosphate precursors were prepared by incipient wetness impregnation using nickel nitrate as nickel source, diammonium hydrogen phosphate as phosphorus source, and MCM-41, MCM-48, SBA-15 and SBA-16 as supports, respectively. Then, the supported Ni2 P catalysts were prepared by temperature-programmed reduction in flowing Hz from their nickel phosphate precursors. The in situ diffuse reflectance FTIR spectroscopy (DRIFTS) analysis with the probe molecule CO was carried out to characterize the surface properties. The results indicated that there were significant differences in the spectral features of the samples. The upsilon(CO) absorbances observed for adsorbed CO on mesoporous molecule sieve was attributed to weak physical adsorption. There are four different kinds of upsilon(CO) absorbances observed for adsorbed CO on Ni2 P/MCM-41 catalyst with the following assignments: (1) the formation of Ni(CO)4 at 2055 cm(-1). (2) CO terminally bonded to cus Ni(delta+) (0

The Chemical Route to a Carbon Dioxide Neutral World.

PubMed

Martens, Johan A; Bogaerts, Annemie; De Kimpe, Norbert; Jacobs, Pierre A; Marin, Guy B; Rabaey, Korneel; Saeys, Mark; Verhelst, Sebastian

2017-03-22

Excessive CO 2 emissions in the atmosphere from anthropogenic activity can be divided into point sources and diffuse sources. The capture of CO 2 from flue gases of large industrial installations and its conversion into fuels and chemicals with fast catalytic processes seems technically possible. Some emerging technologies are already being demonstrated on an industrial scale. Others are still being tested on a laboratory or pilot scale. These emerging chemical technologies can be implemented in a time window ranging from 5 to 20 years. The massive amounts of energy needed for capturing processes and the conversion of CO 2 should come from low-carbon energy sources, such as tidal, geothermal, and nuclear energy, but also, mainly, from the sun. Synthetic methane gas that can be formed from CO 2 and hydrogen gas is an attractive renewable energy carrier with an existing distribution system. Methanol offers advantages as a liquid fuel and is also a building block for the chemical industry. CO 2 emissions from diffuse sources is a difficult problem to solve, particularly for CO 2 emissions from road, water, and air transport, but steady progress in the development of technology for capturing CO 2 from air is being made. It is impossible to ban carbon from the entire energy supply of mankind with the current technological knowledge, but a transition to a mixed carbon-hydrogen economy can reduce net CO 2 emissions and ultimately lead to a CO 2 -neutral world. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of modeling factors on the dissolution-diffusion-convection process during CO2 geological storage in deep saline formations

NASA Astrophysics Data System (ADS)

Zhang, Wei

2013-06-01

It is well known that during CO2 geological storage, density-driven convective activity can significantly accelerate the dissolution of injected CO2 into water. This action could limit the escape of supercritical CO2 from the storage formation through vertical pathways such as fractures, faults and abandoned wells, consequently increasing permanence and security of storage. First, we investigated the effect of numerical perturbation caused by time and grid resolution and the convergence criteria on the dissolution-diffusion-convection (DDC) process. Then, using the model with appropriate spatial and temporal resolution, some uncertainty parameters investigated in our previous paper such as initial gas saturation and model boundaries, and other factors such as relative liquid permeability and porosity modification were used to examine their effects on the DDC process. Finally, we compared the effect of 2D and 3D models on the simulation of the DDC process. The above modeling results should contribute to clear understanding and accurate simulation of the DDC process, especially the onset of convective activity, and the CO2 dissolution rate during the convection-dominated stage.

Monitoring CO2 emissions in tree kill areas near the resurgent dome at Long Valley Caldera, California

USGS Publications Warehouse

Bergfeld, D.; Evans, William C.

2011-01-01

We report results of yearly measurements of the diffuse CO2 flux and shallow soil temperatures collected since 2006 across two sets of tree-kill areas at Long Valley Caldera, California. These data provide background information about CO2 discharge during a period with moderate seismicity, but little to no deformation. The tree kills are located at long-recognized areas of weak thermal fluid upflow, but have expanded in recent years, possibly in response to geothermal fluid production at Casa Diablo. The amount of CO2 discharged from the older kill area at Basalt Canyon is fairly constant and is around 3-5 tonnes of CO2 per day from an area of about 15,000 m2. The presence of isobutane in gas samples from sites in and around Basalt Canyon suggests that geothermal fluid production directly effects fluid upflow in the region close to the power plant. The average fluxes at Shady Rest are lower than average fluxes at Basalt Canyon, but the area affected by fluid upflow is larger. Total CO2 discharged from the central portion of the kill area at Shady Rest has been variable, ranging from 6 to11 tonnes per day across 61,000 m2. Gas collected at Shady Rest contains no detectable isobutane to link emissions chemically to geothermal fluid production, but two samples from 2009-10 have detectable H2S and suggest an increasing geothermal character of emitted gas. The appearance of this gas at the surface may signal increased drawdown of water levels near the geothermal productions wells.

Determination of diffusion coefficients of carbon dioxide in water between 268 and 473 K in a high-pressure capillary optical cell with in situ Raman spectroscopic measurements

USGS Publications Warehouse

Lu, Wanjun; Guo, Huirong; Chou, I.-Ming; Burruss, R.C.; Li, Lanlan

2013-01-01

Accurate values of diffusion coefficients for carbon dioxide in water and brine at reservoir conditions are essential to our understanding of transport behavior of carbon dioxide in subsurface pore space. However, the experimental data are limited to conditions at low temperatures and pressures. In this study, diffusive transfer of carbon dioxide in water at pressures up to 45 MPa and temperatures from 268 to 473 K was observed within an optical capillary cell via time-dependent Raman spectroscopy. Diffusion coefficients were estimated by the least-squares method for the measured variations in carbon dioxide concentration in the cell at various sample positions and time. At the constant pressure of 20 MPa, the measured diffusion coefficients of carbon dioxide in water increase with increasing temperature from 268 to 473 K. The relationship between diffusion coefficient of carbon dioxide in water [D(CO2) in m2/s] and temperature (T in K) was derived with Speedy–Angell power-law approach as: D(CO2)=D0[T/Ts-1]m where D0 = 13.942 × 10−9 m2/s, Ts = 227.0 K, and m = 1.7094. At constant temperature, diffusion coefficients of carbon dioxide in water decrease with pressure increase. However, this pressure effect is rather small (within a few percent).

Slow acidification of the winter mixed layer in the subarctic western North Pacific

NASA Astrophysics Data System (ADS)

Wakita, Masahide; Nagano, Akira; Fujiki, Tetsuichi; Watanabe, Shuichi

2017-08-01

We used carbon dioxide (CO2) system data collected during 1999-2015 to investigate ocean acidification at time series sites in the western subarctic region of the North Pacific Ocean. The annual mean pH at station K2 decreased at a rate of 0.0025 ± 0.0010 year-1 mostly in response to oceanic uptake of anthropogenic CO2. The Revelle factor increased rapidly (0.046 ± 0.022 year-1), an indication that the buffering capacity of this region of the ocean has declined faster than at other time series sites. In the western subarctic region, the pH during the winter decline at a slower rate of 0.0008 ± 0.0004 year-1. This was attributed to a reduced rate of increase of dissolved inorganic carbon (DIC) and an increase of total alkalinity (TA). The reduction of DIC increase was caused by the decline of surface water density associated with the pycnocline depression and the reduction of vertical diffusion flux from the upper pycnocline. These physical changes were probably caused by northward shrinkage of the western subarctic gyre and global warming. Meanwhile, the contribution of the density decline to the TA increase is canceled out by that of the reduced vertical diffusive flux. We speculated that the winter TA increase is caused mainly by the accumulation of TA due to the weakened calcification by organisms during the winter.

Atmospheric carbon mineralization in an industrial-scale chrysotile mining waste pile.

PubMed

Nowamooz, Ali; Dupuis, J Christian; Beaudoin, Georges; Molson, John; Lemieux, Jean-Michel; Horswill, Micha; Fortier, Richard; Larachi, Faïçal; Maldague, Xavier; Constantin, Marc; Duchesne, Josee; Therrien, René

2018-06-12

Magnesium rich minerals that are abundant in ultramafic mining waste have the potential to be used as a safe and permanent sequestration solution for carbon dioxide (CO2). Our understanding of thermo-hydro-chemical regimes that govern this reaction at an industrial scale, however, has remained an important challenge to its widespread implementation. Through a year-long monitoring experiment performed at a 110Mt chrysotile waste pile, we have documented the existence of two distinct thermo-hydro-chemical regimes that control the ingress of CO2 and the subsequent mineral carbonation of the waste. The experimental results are supported by coupled free-air/porous media numerical flow and transport model that provides insights into optimization strategies to increase the efficiency of mineral sequestration at an industrial-scale. Although functioning passively under less than optimal conditions compared to lab-scale experiments, the 110Mt Thetford Mines pile is nevertheless estimated to be sequestering up to 100 tonnes of CO2 per year, with a potential total carbon capture capacity under optimal conditions of 3 Mt. Yearly, over 100 Mt of ultramafic mine waste suitable for mineral carbonation are generated by the global mining industry. Our results show that this waste material could become a safe and permanent carbon sink for diffuse sources of CO2.

Carbon dioxide diffusion across stomata and mesophyll and photo-biochemical processes as affected by growth CO2 and phosphorus nutrition in cotton

USDA-ARS?s Scientific Manuscript database

Nutrients such as phosphorus availability may exert a major control over plant response to rising atmospheric carbon dioxide concentration (CO2), which is projected to double by the end of 21st century. Elevated CO2 may overcome the diffusional limitation to photosynthesis posed by stomata and mesop...

Constraining the subsoil carbon source to cave-air CO2 and speleothem calcite in central Texas

NASA Astrophysics Data System (ADS)

Bergel, Shelly J.; Carlson, Peter E.; Larson, Toti E.; Wood, Chris T.; Johnson, Kathleen R.; Banner, Jay L.; Breecker, Daniel O.

2017-11-01

Canonical models for speleothem formation and the subsurface carbon cycle invoke soil respiration as the dominant carbon source. However, evidence from some karst regions suggests that belowground CO2 originates from a deeper, older source. We therefore investigated the carbon sources to central Texas caves. Drip-water chemistry of two caves in central Texas implies equilibration with calcite at CO2 concentrations (PCO2_sat) higher than the maximum CO2 concentrations observed in overlying soils. This observation suggests that CO2 is added to waters after they percolate through the soils, which requires a subsoil carbon source. We directly evaluate the carbon isotope composition of the subsoil carbon source using δ13C measurements on cave-air CO2, which we independently demonstrate has little to no contribution from host rock carbon. We do so using the oxidative ratio, OR, defined as the number of moles of O2 consumed per mole of CO2 produced during respiration. However, additional belowground processes that affect O2 and CO2 concentrations, such as gas-water exchange and/or diffusion, may also influence the measured oxidative ratio, yielding an apparent OR (ORapparent). Cave air in Natural Bridge South Cavern has ORapparent values (1.09 ± 0.06) indistinguishable from those expected for respiration alone (1.08 ± 0.06). Pore space gases from soils above the cave have lower values (ORapparent = 0.67 ± 0.05) consistent with respiration and gas transport by diffusion. The simplest explanation for these observations is that cave air in NB South is influenced by respiration in open-system bedrock fractures such that neither diffusion nor exchange with water influence the composition of the cave air. The radiocarbon activities of NB South cave-air CO2 suggest the subsoil carbon source is hundreds of years old. The calculated δ13C values of the subsoil carbon source are consistent with tree-sourced carbon (perhaps decomposing root matter), the δ13C values of which have shifted during industrialization due to changes in the δ13C values and concentrations of atmospheric CO2. Seasonal variations in PCO2_sat in most of the drip waters suggest that these waters exchange with ventilated bedrock fractures in the epikarst, implying that the subsoil CO2 source contributes carbon to speleothems.

Combined effects of inspired oxygen, carbon dioxide, and carbon monoxide on oxygen transport and aerobic capacity.

PubMed

Crocker, George H; Toth, Balazs; Jones, James H

2013-09-01

We hypothesized that breathing hypoxic, hypercapnic, and CO-containing gases together reduces maximal aerobic capacity (Vo2max) as the sum of each gas' individual effect on Vo2max. To test this hypothesis, goats breathed combinations of inspired O2 fraction (FiO2) of 0.06-0.21 and inspired CO2 fraction of 0.00 or 0.05, with and without inspired CO that elevated carboxyhemoglobin fraction (FHbCO) to 0.02-0.45, while running on a treadmill at speeds eliciting Vo2max. Individually, hypoxia and elevated FHbCO decreased fractional Vo2max (FVo2max, fraction of a goat's Vo2max breathing air) in linear, dose-dependent manners; hypercapnia did not change Vo2max. Concomitant hypoxia and elevated FHbCO decreased Vo2max less than the individual gas effects summed, indicating their combined effects on Vo2max are attenuated, fitting the following regression: FVo2max = 4.24 FiO2 + 0.519 FHbCO - 8.22 (FiO2 × FHbCO) + 0.117, (R(2) = 0.965, P < 0.001). The FVo2max correlated highly with total cardiopulmonary O2 delivery, not peripheral diffusing capacity, and with arterial O2 concentration (CaO2), not cardiac output. Hypoxia and elevated FHbCO decreased CaO2 by different mechanisms: hypoxia decreased arterial O2 saturation (SaO2), whereas elevated FHbCO decreased O2 capacitance {concentration of hemoglobin (Hb) available to bind O2 ([Hbavail])}. When breathing hypoxic gas (FiO2 0.12), CaO2 did not change with increasing FHbCO up to 0.30 because higher SaO2 of Hbavail offset decreased [Hbavail] due to the following: 1) hyperventilation with hypoxia and/or elevated FHbCO; 2) increased Hb affinity for O2 due to both Bohr and direct carboxyhemoglobin effects; and 3) the sigmoid relationship between O2 saturation and partial pressure elevating SaO2 more with hypoxia than normoxia.

Origin and distribution of carbon dioxide in the unsaturated zone of the southern High Plains of Texas

USGS Publications Warehouse

Wood, Warren W.; Petraitis, Michael J.

1984-01-01

Partial pressures of CO2, O2, N2, and Ar were monitored at two locations in the Ogallala aquifer system on the Southern High Plains of Texas. Samples were collected monthly during parts of 1980–1981 from nine depths ranging from 0.6 to 36 meters below land surface. PCO2 was observed to be greater at depth than in the active soil zone and thus appears to contradict the normal process in which CO2 is generated in the soil zone and diffuses upward to the atmosphere and downward to the water table. The δ13C of the CO2 gas was quite uniform and averaged −17.9 per mil. PO2 declined with depth, suggesting in situ generation of CO2 by the oxidation of carbon. Several hypotheses were considered to explain the origin of the CO2 at depth. It was concluded that the most probable hypothesis was that dissolved and particulate organic carbon introduced by recharging water was oxidized to CO2 by the aerobic microbial community that utilized oxygen diffusing in from the atmosphere. This hypothesis is consistent with the CO2 concentration profile, calculated production profile of CO2, δ13C values of CO2 gas, caliche, soil humic acid fraction, and dissolved carbonate in groundwater. The abundance of CO2, its concentration profile, and its probable origin provide information for evaluating the observed complex sequence of caliche dissolution and precipitation known to occur in the aquifer.

Analysis of ligand-protein exchange by Clustering of Ligand Diffusion Coefficient Pairs (CoLD-CoP)

NASA Astrophysics Data System (ADS)

Snyder, David A.; Chantova, Mihaela; Chaudhry, Saadia

2015-06-01

NMR spectroscopy is a powerful tool in describing protein structures and protein activity for pharmaceutical and biochemical development. This study describes a method to determine weak binding ligands in biological systems by using hierarchic diffusion coefficient clustering of multidimensional data obtained with a 400 MHz Bruker NMR. Comparison of DOSY spectrums of ligands of the chemical library in the presence and absence of target proteins show translational diffusion rates for small molecules upon interaction with macromolecules. For weak binders such as compounds found in fragment libraries, changes in diffusion rates upon macromolecular binding are on the order of the precision of DOSY diffusion measurements, and identifying such subtle shifts in diffusion requires careful statistical analysis. The "CoLD-CoP" (Clustering of Ligand Diffusion Coefficient Pairs) method presented here uses SAHN clustering to identify protein-binders in a chemical library or even a not fully characterized metabolite mixture. We will show how DOSY NMR and the "CoLD-CoP" method complement each other in identifying the most suitable candidates for lysozyme and wheat germ acid phosphatase.

Ethanol electrooxidation on a carbon-supported Pt catalyst at elevated temperature and pressure: A high-temperature/high-pressure DEMS study

NASA Astrophysics Data System (ADS)

Sun, S.; Halseid, M. Chojak; Heinen, M.; Jusys, Z.; Behm, R. J.

The electrooxidation of ethanol on a Pt/Vulcan catalyst was investigated in model studies by on-line differential electrochemical mass spectrometry (DEMS) over a wide range of reaction temperatures (23-100 °C). Potentiodynamic and potentiostatic measurements of the Faradaic current and the CO 2 formation rate, performed at 3 bar overpressure under well-defined transport and diffusion conditions reveal significant effects of temperature, potential and ethanol concentration on the total reaction activity and on the selectivity for the pathway toward complete oxidation to CO 2. The latter pathway increasingly prevails at higher temperature, lower concentration and lower potentials (∼90% current efficiency for CO 2 formation at 100 °C, 0.01 M, 0.48 V), while at higher ethanol concentrations (0.1 M), higher potentials or lower temperatures the current efficiency for CO 2 formation drops, reaching values of a few percent at room temperature. These trends result in a significantly higher apparent activation barrier for complete oxidation to CO 2 (68 ± 2 kJ mol -1 at 0.48 V, 0.1 M) compared to that of the overall ethanol oxidation reaction determined from the Faradaic current (42 ± 2 kJ mol -1 at 0.48 V, 0.1 M). The mechanistic implications of these results and the importance of relevant reaction and mass transport conditions in model studies for reaction predictions in fuel cell applications are discussed.

Theory of the formation of the electric double layer at the ion exchange membrane-solution interface.

PubMed

Moya, A A

2015-02-21

This work aims to extend the study of the formation of the electric double layer at the interface defined by a solution and an ion-exchange membrane on the basis of the Nernst-Planck and Poisson equations, including different values of the counter-ion diffusion coefficient and the dielectric constant in the solution and membrane phases. The network simulation method is used to obtain the time evolution of the electric potential, the displacement electric vector, the electric charge density and the ionic concentrations at the interface between a binary electrolyte solution and a cation-exchange membrane with total co-ion exclusion. The numerical results for the temporal evolution of the interfacial electric potential and the surface electric charge are compared with analytical solutions derived in the limit of the shortest times by considering the Poisson equation for a simple cationic diffusion process. The steady-state results are justified from the Gouy-Chapman theory for the diffuse double layer in the limits of similar and high bathing ionic concentrations with respect to the fixed-charge concentration inside the membrane. Interesting new physical insights arise from the interpretation of the process of the formation of the electric double layer at the ion exchange membrane-solution interface on the basis of a membrane model with total co-ion exclusion.

Eco-Efficient Synthesis of Highly Porous CoCO3 Anodes from Supercritical CO2 for Li+ and Na+ Storage.

PubMed

Li, Hui-Ying; Tseng, Chuan-Ming; Yang, Cheng-Hsien; Lee, Tai-Chou; Su, Ching-Yuan; Hsieh, Chien-Te; Chang, Jeng-Kuei

2017-06-09

An eco-efficient synthetic route for the preparation of high-performance carbonate anodes for Li + and Na + batteries is developed. With supercritical CO 2 (scCO 2 ) as the precursor, which has gas-like diffusivity, extremely low viscosity, and near-zero surface tension, CoCO 3 particles are uniformly formed and tightly connected on graphene nanosheets (GNSs). This synthesis can be conducted at 50 °C, which is considerably lower than the temperature required for conventional preparation methods, minimizing energy consumption. The obtained CoCO 3 particles (ca. 20 nm in diameter), which have a unique interpenetrating porous structure, can increase the number of electroactive sites, promote electrolyte accessibility, shorten ion diffusion length, and readily accommodate the strain generated upon charging/discharging. With a reversible capacity of 1105 mAh g -1 , the proposed CoCO 3 /GNS anode shows an excellent rate capability, as it can deliver 745 mAh g -1 in 7.5 min. More than 98 % of the initial capacity is retained after 200 cycles. These properties are clearly superior to those of previously reported CoCO 3 -based electrodes for Li + storage, indicating the merit of our scCO 2 -based synthesis, which is facile, green, and can be easily scaled up for mass production. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fractional Ablative Laser Followed by Transdermal Acoustic Pressure Wave Device to Enhance the Drug Delivery of Aminolevulinic Acid: In Vivo Fluorescence Microscopy Study.

PubMed

Waibel, Jill S; Rudnick, Ashley; Nousari, Carlos; Bhanusali, Dhaval G

2016-01-01

Topical drug delivery is the foundation of all dermatological therapy. Laser-assisted drug delivery (LAD) using fractional ablative laser is an evolving modality that may allow for a greater precise depth of penetration by existing topical medications, as well as more efficient transcutaneous delivery of large drug molecules. Additional studies need to be performed using energy-driven methods that may enhance drug delivery in a synergistic manner. Processes such as iontophoresis, electroporation, sonophoresis, and the use of photomechanical waves aid in penetration. This study evaluated in vivo if there is increased efficacy of fractional CO2 ablative laser with immediate acoustic pressure wave device. Five patients were treated and biopsied at 4 treatment sites: 1) topically applied aminolevulinic acid (ALA) alone; 2) fractional ablative CO2 laser and topical ALA alone; 3) fractional ablative CO2 laser and transdermal acoustic pressure wave device delivery system; and 4) topical ALA with transdermal delivery system. The comparison of the difference in the magnitude of diffusion with both lateral spread of ALA and depth diffusion of ALA was measured by fluorescence microscopy. For fractional ablative CO2 laser, ALA, and transdermal acoustic pressure wave device, the protoporphyrin IX lateral fluorescence was 0.024 mm on average vs 0.0084 mm for fractional ablative CO2 laser and ALA alone. The diffusion for the acoustic pressure wave device was an order of magnitude greater. We found that our combined approach of fractional ablative CO2 laser paired with the transdermal acoustic pressure wave device increased the depth of penetration of ALA.

Modeling the chemistry of the dense interstellar clouds. I - Observational constraints for the chemistry

NASA Technical Reports Server (NTRS)

Federman, S. R.; Huntress, W. T., Jr.; Prasad, S. S.

1990-01-01

A search for correlations arising from molecular line data is made in order to place constraints on the chemical models of interstellar clouds. At 10 to the 21st H2/sq cm, N(CO) for dark clouds is a factor of six greater than the value for diffuse clouds. This implies that the strength of the UV radiation field where CO shields itself from dissociation is about one-half the strength of the average Galactic field. The dark cloud data indicate that the abundance of CO continues to increase with A(V) for directions with A(V) of 4 mag or less, although less steeply with N(H2) than for diffuse clouds. For H2CO, a quadratic relationship is obtained in plots versus H2 column density. The data suggest a possible turnover at the highest values for A(V). NH3 shows no correlation with H2, C(O-18), HC3N, or HC5N; a strong correlation is found between HC5N and HC3N, indicating a chemical link between the cyanopolyynes.

The kinetics of ulvoespinel reduction - Synthetic study and applications to lunar rocks.

NASA Technical Reports Server (NTRS)

Mccallister, R. H.; Taylor, L. A.

1973-01-01

The kinetics of Fe2TiO4 reduction to FeTiO3 + Fe were studied using CO-CO2 gas mixtures with fO2 measured by a solid ceramic (calcia-zirconia) oxygen electrolyte cell. Isothermal rate studies at 900 C suggest that the mechanism of Fe2TiO4 reduction is one of nucleation and growth, where the growth stage may be controlled by the diffusion of the reactant through the product layer or volume diffusion. The activation energy for the growth stage of the process was determined to be 46 plus or minus 4 kcal/mole.

Influence of Structural Heterogeneity on Diffusion of CH4 and CO2 in Silicon Carbide-Derived Nanoporous Carbon

PubMed Central

2015-01-01

We investigate the influence of structural heterogeneity on the transport properties of simple gases in a Hybrid Reverse Monte Carlo (HRMC) constructed model of silicon carbide-derived carbon (SiC-DC). The energy landscape of the system is determined based on free energy analysis of the atomistic model. The overall energy barriers of the system for different gases are computed along with important properties, such as Henry constant and differential enthalpy of adsorption at infinite dilution, and indicate hydrophobicity of the SiC-DC structure and its affinity for CO2 and CH4 adsorption. We also study the effect of molecular geometry, pore structure and energy heterogeneity considering different hopping scenarios for diffusion of CO2 and CH4 through ultramicropores using the Nudged Elastic Band (NEB) method. It is shown that the energy barrier of a hopping molecule is very sensitive to the shape of the pore entry. We provide evidence for the influence of structural heterogeneity on self-diffusivity of methane and carbon dioxide using molecular dynamics simulation, based on a maximum in the variation of self-diffusivity with loading. A comparison of the MD simulation results with self-diffusivities from quasi-elastic neutron scattering (QENS) measurements and, with macroscopic uptake-based low-density transport coefficients, reveals the existence of internal barriers not captured in MD simulation and QENS experiments. Nevertheless, the simulation and macroscopic uptake-based diffusion coefficients agree within a factor of 2–3, indicating that our HRMC model structure captures most of the important energy barriers affecting the transport of CH4 in the nanostructure of SiC-DC. PMID:24932319

Influence of Structural Heterogeneity on Diffusion of CH4 and CO2 in Silicon Carbide-Derived Nanoporous Carbon.

PubMed

Farmahini, Amir H; Shahtalebi, Ali; Jobic, Hervé; Bhatia, Suresh K

2014-06-05

We investigate the influence of structural heterogeneity on the transport properties of simple gases in a Hybrid Reverse Monte Carlo (HRMC) constructed model of silicon carbide-derived carbon (SiC-DC). The energy landscape of the system is determined based on free energy analysis of the atomistic model. The overall energy barriers of the system for different gases are computed along with important properties, such as Henry constant and differential enthalpy of adsorption at infinite dilution, and indicate hydrophobicity of the SiC-DC structure and its affinity for CO 2 and CH 4 adsorption. We also study the effect of molecular geometry, pore structure and energy heterogeneity considering different hopping scenarios for diffusion of CO 2 and CH 4 through ultramicropores using the Nudged Elastic Band (NEB) method. It is shown that the energy barrier of a hopping molecule is very sensitive to the shape of the pore entry. We provide evidence for the influence of structural heterogeneity on self-diffusivity of methane and carbon dioxide using molecular dynamics simulation, based on a maximum in the variation of self-diffusivity with loading. A comparison of the MD simulation results with self-diffusivities from quasi-elastic neutron scattering (QENS) measurements and, with macroscopic uptake-based low-density transport coefficients, reveals the existence of internal barriers not captured in MD simulation and QENS experiments. Nevertheless, the simulation and macroscopic uptake-based diffusion coefficients agree within a factor of 2-3, indicating that our HRMC model structure captures most of the important energy barriers affecting the transport of CH 4 in the nanostructure of SiC-DC.

Responses of Picea mariana to elevated CO2 concentration during growth, cold hardening and dehardening: phenology, cold tolerance, photosynthesis and growth.

PubMed

Bigras, F J; Bertrand, A

2006-07-01

Seedlings from a northern and a southern provenance of black spruce (Picea mariana Mill. BSP) from eastern Canada were exposed to 37 or 71 Pa of carbon dioxide (CO2) during growth, cold hardening and dehardening in a greenhouse. Bud phenology, cold tolerance and photosynthetic efficiency were assessed during the growing and over-wintering periods. Bud set occurred earlier in elevated [CO2] than in ambient [CO2], but it was later in the southern provenance than in the northern provenance. An increase in seedling cold tolerance in early fall was related to early bud set in elevated [CO2]. Maximal photosystem II (PSII) photochemical efficiency (F(v)/F(m)), effective quantum yield (phi(PSII)), photochemical quenching (q(P)), light-saturated photosynthesis (Amax), apparent quantum efficiency (alpha'), light-saturated rate of carboxylation (Vcmax) and electron transport (Jmax) decreased during hardening and recovered during dehardening. Although Amax and alpha' were higher in elevated [CO2] when measured at the growth [CO2], down-regulation of photosynthesis occurred in elevated [CO2] as shown by lower F(v)/F(m), phi(PSII), Vcmax and Jmax. Elevated [CO2] reduced gene expression of the small subunit of Rubisco and also decreased chlorophyll a/chlorophyll b ratio and nitrogen concentration in needles, confirming our observation of down-regulation of photosynthesis. Elevated [CO2] increased the CO2 diffusion gradient and decreased photorespiration, which may have contributed to enhance Amax despite down-regulation of photosynthesis. Total seedling dry mass was higher in elevated [CO2] than in ambient [CO2] at the end of the growing season. However, because of earlier bud formation and cold hardening, and down-regulation of photosynthesis during fall and winter in elevated [CO2], the treatment difference in dry mass increment was less by the end of the winter than during the growing season. Differences in photosynthetic rate observed during fall, winter and spring account for the inter-annual variations in carbon assimilation of black spruce seedlings: our results demonstrate that these variations need to be considered in carbon budget studies.

Using satellite-derived optical thickness to assess the influence of clouds on terrestrial carbon uptake

Treesearch

S.J. Cheng; A.L. Steiner; D.Y. Hollinger; G. Bohrer; K.J. Nadelhoffer

2016-01-01

Clouds scatter direct solar radiation, generating diffuse radiation and altering the ratio of direct to diffuse light. If diffuse light increases plant canopy CO2 uptake, clouds may indirectly influence climate by altering the terrestrial carbon cycle. However, past research primarily uses proxies or qualitative categories of clouds to connect...

Analysis of factors affecting gas exchange in intravascular blood gas exchanger.

PubMed

Niranjan, S C; Clark, J W; San, K Y; Zwischenberger, J B; Bidani, A

1994-10-01

A mathematical model of an intravascular hollow-fiber gas-exchange device, called IVOX, has been developed using a Krogh cylinder-like approach with a repeating unit structure comprised of a single fiber with gas flowing through its lumen surrounded by a coaxial cylinder of blood flowing in the opposite direction. Species mass balances on O2 and CO2 result in a nonlinear coupled set of convective-diffusion parabolic partial differential equations that are solved numerically using an alternating-direction implicit finite-difference method. Computed results indicated the presence of a large resistance to gas transport on the external (blood) side of the hollow-fiber exchanger. Increasing gas flow through the device favored CO2 removal from but not O2 addition to blood. Increasing blood flow over the device favored both CO2 removal as well as O2 addition. The rate of CO2 removal increased linearly with the transmural PCO2 gradient imposed across the device. The effect of fiber crimping on blood phase mass transfer resistance was evaluated indirectly by varying species blood diffusivity. Computed results indicated that CO2 excretion by IVOX can be significantly enhanced with improved bulk mixing of vena caval blood around the IVOX fibers.

Long-term viability of carbon sequestration in deep-sea sediments

NASA Astrophysics Data System (ADS)

Teng, Y.; Zhang, D.

2017-12-01

Sequestration of carbon dioxide in deep-sea sediments has been proposed for the long-term storage of anthropogenic CO2, due to the negative buoyancy effect and hydrate formation under conditions of high pressure and low temperature. However, the multi-physics process of injection and post-injection fate of CO2 and the feasibility of sub-seabed disposal of CO2 under different geological and operational conditions have not been well studied. On the basis of a detailed study of the coupled processes, we investigate whether storing CO2 into deep-sea sediments is viable, efficient, and secure over the long term. Also studied are the evolution of the multiphase and multicomponent flow and the impact of hydrate formation on storage efficiency during the upward migration of the injected CO2. It is shown that low buoyancy and high viscosity slow down the ascending plume and the forming of the hydrate cap effectively reduces the permeability and finally becomes an impermeable seal, thus limiting the movement of CO2 towards the seafloor. Different flow patterns at varied time scales are identified through analyzing the mass distribution of CO2 in different phases over time. Observed is the formation of a fluid inclusion, which mainly consists of liquid CO2 and is encapsulated by an impermeable hydrate film in the diffusion-dominated stage. The trapped liquid CO2 and CO2 hydrate finally dissolve into the pore water through diffusion of the CO2 component. Sensitivity analyses are performed on storage efficiency under variable geological and operational conditions. It is found that under a deep-sea setting, CO2 sequestration in intact marine sediments is generally safe and permanent.

Temporal and spatial patterns of internal and external stem CO2 fluxes in a sub-Mediterranean oak.

PubMed

Salomón, Roberto L; Valbuena-Carabaña, María; Gil, Luis; McGuire, Mary Anne; Teskey, Robert O; Aubrey, Doug P; González-Doncel, Inés; Rodríguez-Calcerrada, Jesús

2016-11-01

To accurately estimate stem respiration (R S ), measurements of both carbon dioxide (CO 2 ) efflux to the atmosphere (E A ) and internal CO 2 flux through xylem (F T ) are needed because xylem sap transports respired CO 2 upward. However, reports of seasonal dynamics of F T and E A are scarce and no studies exist in Mediterranean species under drought stress conditions. Internal and external CO 2 fluxes at three stem heights, together with radial stem growth, temperature, sap flow and shoot water potential, were measured in Quercus pyrenaica Willd. in four measurement campaigns during one growing season. Substantial daytime depressions in temperature-normalized E A were observed throughout the experiment, including prior to budburst, indicating that diel hysteresis between stem temperature and E A cannot be uniquely ascribed to diversion of CO 2 in the transpiration stream. Low internal [CO 2 ] (<0.5%) resulted in low contributions of F T to R S throughout the growing season, and R S was mainly explained by E A (>90%). Internal [CO 2 ] was found to vary vertically along the stems. Seasonality in resistance to radial CO 2 diffusion was related to shoot water potential. The low internal [CO 2 ] and F T observed in our study may result from the downregulation of xylem respiration in response to a legacy of coppicing as well as high radial diffusion of CO 2 through cambium, phloem and bark tissues, which was related to low water content of stems. Long-term studies analyzing temporal and spatial variation in internal and external CO 2 fluxes and their interactions are needed to mechanistically understand and model respiration of woody tissues. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Measurement and interpretation of the oxygen isotope composition of carbon dioxide respired by leaves in the dark.

PubMed

Cernusak, Lucas A; Farquhar, Graham D; Wong, S Chin; Stuart-Williams, Hilary

2004-10-01

We measured the oxygen isotope composition (delta(18)O) of CO(2) respired by Ricinus communis leaves in the dark. Experiments were conducted at low CO(2) partial pressure and at normal atmospheric CO(2) partial pressure. Across both experiments, the delta(18)O of dark-respired CO(2) (delta(R)) ranged from 44 per thousand to 324 per thousand (Vienna Standard Mean Ocean Water scale). This seemingly implausible range of values reflects the large flux of CO(2) that diffuses into leaves, equilibrates with leaf water via the catalytic activity of carbonic anhydrase, then diffuses out of the leaf, leaving the net CO(2) efflux rate unaltered. The impact of this process on delta(R) is modulated by the delta(18)O difference between CO(2) inside the leaf and in the air, and by variation in the CO(2) partial pressure inside the leaf relative to that in the air. We developed theoretical equations to calculate delta(18)O of CO(2) in leaf chloroplasts (delta(c)), the assumed location of carbonic anhydrase activity, during dark respiration. Their application led to sensible estimates of delta(c), suggesting that the theory adequately accounted for the labeling of CO(2) by leaf water in excess of that expected from the net CO(2) efflux. The delta(c) values were strongly correlated with delta(18)O of water at the evaporative sites within leaves. We estimated that approximately 80% of CO(2) in chloroplasts had completely exchanged oxygen atoms with chloroplast water during dark respiration, whereas approximately 100% had exchanged during photosynthesis. Incorporation of the delta(18)O of leaf dark respiration into ecosystem and global scale models of C(18)OO dynamics could affect model outputs and their interpretation.

Magnetic properties influenced by interfaces in ultrathin Co/Ge(1 0 0) and Co/Ge(1 1 1) films

NASA Astrophysics Data System (ADS)

Tsay, J. S.; Yao, Y. D.; Cheng, W. C.; Tseng, T. K.; Wang, K. C.; Yang, C. S.

2003-10-01

Magnetic properties influenced by interfaces in ultrathin Co/Ge(1 0 0) and Co/Ge(1 1 1) films with thickness below 28 monolayers (ML) have been studied using the surface magneto-optic Kerr effect (SMOKE) technique. In both systems, the nonferromagnetic layer, as an interface between Co and Ge, plays an important role during annealing. In general, ultrathin Co films with fixed total thickness but fabricated at different temperatures on the same substrate, their Kerr hysteresis loops disappear roughly at the same temperature. This suggests that the thickness of the interfacial layer could inversely prevent the diffusion between Co and Ge substrate. From the annealing studies for both systems with total film thickness of 28 monolayers, we have found that Kerr signal disappears at 375 K for Co/Ge(1 1 1) and 425 K for Co/Ge(1 0 0) films. This suggests that Co/Ge(1 1 1) films possess a lower thermal stability than that of the Co/Ge(1 0 0) films. Our experimental data could be explained by different interfacial condition between Ge(1 0 0) and Ge(1 1 1), the different onset of interdiffusion, and the surface structure condition of Ge(1 0 0) and Ge(1 1 1).

Carbon dioxide and light responses of photosynthesis in cowpea and pigeonpea during water deficit and recovery

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

Lopez, F.B.; Setter, T.L.; McDavid, C.R.

Greenhouse-grown pigeonpea (Cajunus cajan, (L.)) and cowpea (Vigna unguiculata, (L.)) were well-watered or subjected to low water potential by withholding water to compare their modes of adaptation to water-limited conditions. Leaf CO/sub 2/ exchange rate (CER), leaf diffusive conductance to CO/sub 2/ (g/sub L/), and CO/sub 2/ concentration in the leaf intercellular air space (C/sub i/) were determined at various CO/sub 2/ concentrations and photon flux densities (PFD) of photosynthetically active radiation. In cowpea, g/sub L/ declined to less than 15% of controls and total water potential (Psi/sub w/) at midafternoon declined to -0.8 megapascal after 5 days of withholdingmore » water, whereas g/sub L/ in pigeonpea was about 40% of controls even though midafternoon Psi/sub w/ was -1.9 megapascal. After 8 days of withholding water, Psi/sub w/ at midafternoon decline to -0.9 and -2.4 megapascals in cowpea and pigeonpea, respectively. The solute component of water potential (Psi/sub s/) decreased substantially less in cowpea than pigeonpea. Photosynthetic CER at saturation photon flux density (PFD) and ambient external CO/sub 2/ concentration on day 5 of withholding decreased by 83 and 55% in cowpea and pigeonpea, respectively. When measured at external, CO/sub 2/ concentration in bulk air of 360 microliters per liter, the CER of cowpea had fully recovered to control levels 3 days after rewatering; however, at 970 microliters per liter the PFD-saturated CERS of both species were substantially lower than in controls, indicating residual impairment.« less

Segregating gas from melt: an experimental study of the Ostwald ripening of vapor bubbles in magmas

USGS Publications Warehouse

Lautze, Nicole C.; Sisson, Thomas W.; Mangan, Margaret T.; Grove, Timothy L.

2011-01-01

Diffusive coarsening (Ostwald ripening) of H2O and H2O-CO2 bubbles in rhyolite and basaltic andesite melts was studied with elevated temperature–pressure experiments to investigate the rates and time spans over which vapor bubbles may enlarge and attain sufficient buoyancy to segregate in magmatic systems. Bubble growth and segregation are also considered in terms of classical steady-state and transient (non-steady-state) ripening theory. Experimental results are consistent with diffusive coarsening as the dominant mechanism of bubble growth. Ripening is faster in experiments saturated with pure H2O than in those with a CO2-rich mixed vapor probably due to faster diffusion of H2O than CO2 through the melt. None of the experimental series followed the time1/3 increase in mean bubble radius and time-1 decrease in bubble number density predicted by classical steady-state ripening theory. Instead, products are interpreted as resulting from transient regime ripening. Application of transient regime theory suggests that bubbly magmas may require from days to 100 years to reach steady-state ripening conditions. Experimental results, as well as theory for steady-state ripening of bubbles that are immobile or undergoing buoyant ascent, indicate that diffusive coarsening efficiently eliminates micron-sized bubbles and would produce mm-sized bubbles in 102–104 years in crustal magma bodies. Once bubbles attain mm-sizes, their calculated ascent rates are sufficient that they could transit multiple kilometers over hundreds to thousands of years through mafic and silicic melt, respectively. These results show that diffusive coarsening can facilitate transfer of volatiles through, and from, magmatic systems by creating bubbles sufficiently large for rapid ascent.

Computational characterization of lightweight multilayer MXene Li-ion battery anodes

NASA Astrophysics Data System (ADS)

Ashton, Michael; Hennig, Richard G.; Sinnott, Susan B.

2016-01-01

MXenes, a class of two-dimensional transition metal carbides and nitrides, have shown promise experimentally and computationally for use in energy storage applications. In particular, the most lightweight members of the monolayer MXene family (M = Sc, Ti, V, or Cr) are predicted to have gravimetric capacities above 400 mAh/g, higher than graphite. Additionally, intercalation of ions into multilayer MXenes can be accomplished at low voltages, and low diffusion barriers exist for Li diffusing across monolayer MXenes. However, large discrepancies have been observed between the calculated and experimental reversible capacities of MXenes. Here, dispersion-corrected density functional theory calculations are employed to predict reversible capacities and other battery-related properties for six of the most promising members of the MXene family (O-functionalized Ti- and V-based carbide MXenes) as bilayer structures. The calculated reversible capacities of the V2CO2 and Ti2CO2 bilayers agree more closely with experiment than do previous calculations for monolayers. Additionally, the minimum energy paths and corresponding energy barriers along the in-plane [1000] and [0100] directions for Li travelling between neighboring MXene layers are determined. V4C3O2 exhibits the lowest diffusion barrier of the compositions considered, at 0.42 eV, but its reversible capacity (148 mAh/g) is dragged down by its heavy formula unit. Conversely, the V2CO2 MXene shows good reversible capacity (276 mAh/g), but a high diffusion barrier (0.82 eV). We show that the diffusion barriers of all bilayer structures are significantly higher than those calculated for the corresponding monolayers, advocating the use of dispersed monolayer MXenes instead of multilayers in high performance anodes.

Spatial and Temporal Variations in the Partial Pressure and Emission of CO2 and CH4 in and Amazon Floodplain Lake

NASA Astrophysics Data System (ADS)

Forsberg, B. R.; Amaral, J. H.; Barbosa, P.; Kasper, D.; MacIntyre, S.; Cortes, A.; Sarmento, H.; Borges, A. V.; Melack, J. M.; Farjalla, V.

2015-12-01

The Amazon floodplain contains a variety of wetland environments which contribute CO2 and CH4 to the regional and global atmospheres. The partial pressure and emission of these greenhouse gases (GHGs) varies: 1) between habitats, 2) seasonally, as the characteristics these habitats changes and 3) diurnally, in response to diurnal stratification. In this study, we investigated the combined influence of these factors on the partial pressure and emission of GHGs in Lago Janauacá, a central Amazon floodplain lake (3o23' S; 60o18' O). All measurements were made between August of 2014 and April of 2015 at two different sites and in three distinct habitats: open water, flooded forest, flooded macrophytes. Concentrations of CO2 and CH4 in air were measured continuously with a cavity enhanced absorption spectrometer, Los Gatos Research´s Ultraportable Greenhouse Gas Analyzer (UGGA). Vertical profiles o pCO2 and pCH4 were measured using the UGGA connected to an electric pump and equilibrator. Diffusive surface emissions were estimated with the UGGA connected to a static floating chamber. To investigate the influence of vertical stratification and mixing on GHG partial pressure and emissions, a meteorological station and submersible sensor chain were deployed at each site. Meteorological sensors included wind speed and direction. The submersible chains included thermistors and oxygen sensors. Depth profiles of partial pressure and diffusive emissions for both CO2 and CH4 varied diurnally, seasonally and between habitats. Both pCO2 and pCH4 were consistently higher in bottom than surface waters with the largest differences occurring at high water when thermal stratification was most stable. Methane emissions and partial pressures were highest at low water while pCO2 and CO2 fluxes were highest during high water periods, with 35% of CO2 fluxes at low water being negative. The highest average surface value of pCO2 (5491 μatm), encountered during rising water, was ~3 times higher than that encountered at low water (1708 μatm). Partial pressures and emissions of both CO2 and CH4 were greatest in open water habitats and consistently higher at night. These patterns reflected the higher levels of wind driven mixing and turbulence in open water environments and higher convective mixing at night which promoted diffusive emission.

Numerical cell model investigating cellular carbon fluxes in Emiliania huxleyi.

PubMed

Holtz, Lena-Maria; Wolf-Gladrow, Dieter; Thoms, Silke

2015-01-07

Coccolithophores play a crucial role in the marine carbon cycle and thus it is interesting to know how they will respond to climate change. After several decades of research the interplay between intracellular processes and the marine carbonate system is still not well understood. On the basis of experimental findings given in literature, a numerical cell model is developed that describes inorganic carbon fluxes between seawater and the intracellular sites of calcite precipitation and photosynthetic carbon fixation. The implemented cell model consists of four compartments, for each of which the carbonate system is resolved individually. The four compartments are connected to each other via H(+), CO2, and HCO3(-) fluxes across the compartment-confining membranes. For CO2 accumulation around RubisCO, an energy-efficient carbon concentrating mechanism is proposed that relies on diffusive CO2 uptake. At low external CO2 concentrations and high light intensities, CO2 diffusion does not suffice to cover the carbon demand of photosynthesis and an additional uptake of external HCO3(-) becomes essential. The model is constrained by data of Emiliania huxleyi, the numerically most abundant coccolithophore species in the present-day ocean. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

In situ speciation of uranium in treated acid mine drainage using the diffusion gradients in thin films technique (DGT).

PubMed

Pedrobom, Jorge Henrique; Eismann, Carlos Eduardo; Menegário, Amauri A; Galhardi, Juliana Aparecida; Luko, Karen Silva; Dourado, Thiago de Araujo; Kiang, Chang Hung

2017-02-01

The exchange membranes P81 and DE81 and Chelex-100 resin were used to perform in situ speciation of uranium in treated acid mine drainage at the Osamu Utsumi mining site, Poços de Caldas city, Southeast Brazil. To investigate possible chemical modifications in the samples during analysis, the three ligands were deployed in situ and in a laboratory (in lab). The results obtained in situ were also compared to a speciation performed using Visual MINTEQ software. Chelex-100 retained total labile U for a period of up to 48 h. The labile U fraction determined by Chelex 100 ranged from 107 ± 6% to 147 ± 44% in situ and from 115 ± 22% to 191 ± 5% in lab. DE81 retained anionic U species up to 8 h, with labile fractions ranging from 37 ± 2% to 76 ± 3% in situ and 34 ± 12% to 180 ± 17% in lab. P81 exhibited a lower efficiency in retaining U species, with concentrations ranging from 6± 2% to 19± 2% in situ and 3± 2% to 18± 2% in lab. The speciation obtained from MINTEQ suggests that the major U species were UO 2 OH + , UO 2 (OH) 3- , UO 2 (OH) 2(aq) , Ca 2 UO 2 (CO 3 ) 3(aq) , CaUO 2 (CO 3 ) 3 2- , UO 2 (CO 3 ) 2 2- , and UO 2 (CO 3 ) 3 4- . This result is in accordance with the results obtained in situ. Differences concerning speciation and the total and soluble U concentrations were observed between the deployments performed in situ and in the laboratory, indicating that U speciation must be performed in situ. Copyright © 2016 Elsevier Ltd. All rights reserved.

EGRET Observations of the Diffuse Gamma-Ray Emission in Orion: Analysis Through Cycle 6

NASA Technical Reports Server (NTRS)

Digel, S. W.; Aprile, E.; Hunter, S. D.; Mukherjee, R.; Xu, F.

1999-01-01

We present a study of the high-energy diffuse emission observed toward Orion by the Energetic Gamma-Ray Experiment Telescope (EGRET) on the Compton Gamma-Ray Observatory. The total exposure by EGRET in this region has increased by more than a factor of two since a previous study. A simple model for the diffuse emission adequately fits the data; no significant point sources are detected in the region studied (1 = 195 deg to 220 deg and b = -25 deg to -10 deg) in either the composite dataset or in two separate groups of EGRET viewing periods considered. The gamma-ray emissivity in Orion is found to be (1.65 +/- 0.11) x 10(exp -26)/s.sr for E > 100 MeV, and the differential emissivity is well-described as a combination of contributions from cosmic-ray electrons and protons with approximately the local density. The molecular mass calibrating ratio is N(H2)/W(sub CO) = (1.35 +/- 0.15) x 10(exp 20)/sq cm.(K.km/s).

Availability of phosphate for phytoplankton and bacteria and of glucose for bacteria at different pCO2 levels in a mesocosm study

NASA Astrophysics Data System (ADS)

Tanaka, T.; Thingstad, T. F.; Løvdal, T.; Grossart, H.-P.; Larsen, A.; Allgaier, M.; Meyerhöfer, M.; Schulz, K. G.; Wohlers, J.; Zöllner, E.; Riebesell, U.

2008-05-01

Availability of phosphate for phytoplankton and bacteria and of glucose for bacteria at different pCO2 levels were studied in a mesocosm experiment (PeECE III). Using nutrient-depleted SW Norwegian fjord waters, three different levels of pCO2 (350 μatm: 1×CO2; 700 μatm: 2×CO2; 1050 μatm: 3×CO2) were set up, and nitrate and phosphate were added at the start of the experiment in order to induce a phytoplankton bloom. Despite similar responses of total particulate P concentration and phosphate turnover time at the three different pCO2 levels, the size distribution of particulate P and 33PO4 uptake suggested that phosphate transferred to the >10 μm fraction was greater in the 3×CO2 mesocosm during the first 6-10 days when phosphate concentration was high. During the period of phosphate depletion (after Day 12), specific phosphate affinity and specific alkaline phosphatase activity (APA) suggested a P-deficiency (i.e. suboptimal phosphate supply) rather than a P-limitation for the phytoplankton and bacterial community at the three different pCO2 levels. Specific phosphate affinity and specific APA tended to be higher in the 3×CO2 than in the 2×CO2 and 1×CO2 mesocosms during the phosphate depletion period, although no statistical differences were found. Glucose turnover time was correlated significantly and negatively with bacterial abundance and production but not with the bulk DOC concentration. This suggests that even though constituting a small fraction of the bulk DOC, glucose was an important component of labile DOC for bacteria. Specific glucose affinity of bacteria behaved similarly at the three different pCO2 levels with measured specific glucose affinities being consistently much lower than the theoretical maximum predicted from the diffusion-limited model. This suggests that bacterial growth was not severely limited by the glucose availability. Hence, it seems that the lower availability of inorganic nutrients after the phytoplankton bloom reduced the bacterial capacity to consume labile DOC in the upper mixed layer of the stratified mesocosms.

Complete p-type activation in vertical-gradient freeze GaAs co-implanted with gallium and carbon

NASA Astrophysics Data System (ADS)

Horng, S. T.; Goorsky, M. S.

1996-03-01

High-resolution triple-axis x-ray diffractometry and Hall-effect measurements were used to characterize damage evolution and electrical activation in gallium arsenide co-implanted with gallium and carbon ions. Complete p-type activation of GaAs co-implanted with 5×1014 Ga cm-2 and 5×1014 C cm-2 was achieved after rapid thermal annealing at 1100 °C for 10 s. X-ray diffuse scattering was found to increase after rapid thermal annealing at 600-900 °C due to the aggregation of implantation-induced point defects. In this annealing range, there was ˜10%-72% activation. After annealing at higher annealing temperatures, the diffuse scattered intensity decreased drastically; samples that had been annealed at 1000 °C (80% activated) and 1100 °C (˜100% activated) exhibited reciprocal space maps that were indicative of high crystallinity. The hole mobility was about 60 cm2/V s for all samples annealed at 800 °C and above, indicating that the crystal perfection influences dopant activation more strongly than it influences mobility. Since the high-temperature annealing simultaneously increases dopant activation and reduces x-ray diffuse scattering, we conclude that point defect complexes which form at lower annealing temperatures are responsible for both the diffuse scatter and the reduced activation.

From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes

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

Han, Binghong; Key, Baris; Lapidus, Saul H.

Surface alumina coatings have been shown to be an effective way to improve the stability and cyclability of cathode materials. However, a detailed understanding of the relationship between the surface coatings and the bulk layered oxides is needed to better define the critical cathode–electrolyte interface. In this work, we systematically studied the effect of the composition of Ni-rich LiNi xMn yCo 1–x–yO 2 (NMC) on the surface alumina coatings. Changing cathode composition from LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) to LiNi 0.6Mn 0.2Co 0.2O 2 (NMC622) and LiNi 0.8Mn 0.1Co 0.1O 2 (NMC811) was found to facilitate the diffusion ofmore » surface alumina into the bulk after high-temperature annealing. By use of a variety of spectroscopic techniques, Al was seen to have a high bulk compatibility with higher Ni/Co content, and low bulk compatibility was associated with Mn in the transition metal layer. It was also noted that the cathode composition affected the observed morphology and surface chemistry of the coated material, which has an effect on electrochemical cycling. The presence of a high surface Li concentration and strong alumina diffusion into the bulk led to a smoother surface coating on NMC811 with no excess alumina aggregated on the surface. Structural characterization of pristine NMC particles also suggests surface Co segregation, which may act to mediate the diffusion of the Al from the surface to the bulk. The diffusion of Al into the bulk was found to be detrimental to the protection function of surface coatings leading to poor overall cyclability, indicating the importance of compatibility between surface coatings and bulk oxides on the electrochemical performance of coated cathode materials.In conclusion, these results are important in developing a better coating method for synthesis of next-generation cathode materials for lithium-ion batteries.« less

From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes

DOE PAGES

Han, Binghong; Key, Baris; Lapidus, Saul H.; ...

2017-11-01

Surface alumina coatings have been shown to be an effective way to improve the stability and cyclability of cathode materials. However, a detailed understanding of the relationship between the surface coatings and the bulk layered oxides is needed to better define the critical cathode–electrolyte interface. In this work, we systematically studied the effect of the composition of Ni-rich LiNi xMn yCo 1–x–yO 2 (NMC) on the surface alumina coatings. Changing cathode composition from LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) to LiNi 0.6Mn 0.2Co 0.2O 2 (NMC622) and LiNi 0.8Mn 0.1Co 0.1O 2 (NMC811) was found to facilitate the diffusion ofmore » surface alumina into the bulk after high-temperature annealing. By use of a variety of spectroscopic techniques, Al was seen to have a high bulk compatibility with higher Ni/Co content, and low bulk compatibility was associated with Mn in the transition metal layer. It was also noted that the cathode composition affected the observed morphology and surface chemistry of the coated material, which has an effect on electrochemical cycling. The presence of a high surface Li concentration and strong alumina diffusion into the bulk led to a smoother surface coating on NMC811 with no excess alumina aggregated on the surface. Structural characterization of pristine NMC particles also suggests surface Co segregation, which may act to mediate the diffusion of the Al from the surface to the bulk. The diffusion of Al into the bulk was found to be detrimental to the protection function of surface coatings leading to poor overall cyclability, indicating the importance of compatibility between surface coatings and bulk oxides on the electrochemical performance of coated cathode materials.In conclusion, these results are important in developing a better coating method for synthesis of next-generation cathode materials for lithium-ion batteries.« less

Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model

NASA Astrophysics Data System (ADS)

Hansen, Maximilian; Scholz, Denis; Froeschmann, Marie-Louise; Schöne, Bernd R.; Spötl, Christoph

2017-08-01

Speleothem stable carbon isotope (δ13C) records provide important paleoclimate and paleo-environmental information. However, the interpretation of these records in terms of past climate or environmental change remains challenging because of various processes affecting the δ13C signals. A process that has only been sparsely discussed so far is carbon isotope exchange between the gaseous CO2 of the cave atmosphere and the dissolved inorganic carbon (DIC) contained in the thin solution film on the speleothem, which may be particularly important for strongly ventilated caves. Here we present a novel, complete reaction diffusion model describing carbon isotope exchange between gaseous CO2 and the DIC in thin solution films. The model considers all parameters affecting carbon isotope exchange, such as diffusion into, out of and within the film, the chemical reactions occurring within the film as well as the dependence of diffusion and the reaction rates on isotopic mass and temperature. To verify the model, we conducted laboratory experiments under completely controlled, cave-analogue conditions at three different temperatures (10, 20, 30 °C). We exposed thin (≈0.1 mm) films of a NaHCO3 solution with four different concentrations (1, 2, 5 and 10 mmol/l, respectively) to a nitrogen atmosphere containing a specific amount of CO2 (1000 and 3000 ppmV). The experimentally observed temporal evolution of the pH and δ13C values of the DIC is in good agreement with the model predictions. The carbon isotope exchange times in our experiments range from ca. 200 to ca. 16,000 s and strongly depend on temperature, film thickness, atmospheric pCO2 and the concentration of DIC. For low pCO2 (between 500 and 1000 ppmV, as for strongly ventilated caves), our time constants are substantially lower than those derived in a previous study, suggesting a potentially stronger influence of carbon isotope exchange on speleothem δ13C values. However, this process should only have an influence in case of very long drip intervals and slow precipitation rates.

Examination of the effect of differential molecular diffusion in DNS of turbulent non-premixed flames

DOE PAGES

Han, Chao; Lignell, David O.; Hawkes, Evatt R.; ...

2017-02-09

Here, the effect of differential molecular diffusion (DMD) in turbulent non-premixed flames is studied by examining two previously reported DNS of temporally evolving planar jet flames, one with CO/H 2 as the fuel and the other with C 2H 4 as the fuel. The effect of DMD in the CO/H 2 DNS flames in which H 2 is part of fuel is found to behave similar to laminar flamelet, while in the C 2H 4 DNS flames in which H 2 is not present in the fuel it is similar to laminar flamelet in early stages but becomes different frommore » laminar flamelet later. The scaling of the effect of DMD with respect to the Reynolds number Re is investigated in the CO/H 2 DNS flames, and an evident power law scaling (~Re –a with a a positive constant) is observed. The scaling of the effect of DMD with respect to the Damkohler number Da is explored in both laminar counter-flow jet C 2H 4 diffusion flames and the C 2H 4 DNS flames. A power law scaling (~ Daa with a a positive constant) is clearly demonstrated for C 2H 4 nonpremixed flames.« less

Li-ion diffusion kinetics in LiCoPO 4 thin films deposited on NASICON-type glass ceramic electrolytes by magnetron sputtering

NASA Astrophysics Data System (ADS)

Xie, J.; Imanishi, N.; Zhang, T.; Hirano, A.; Takeda, Y.; Yamamoto, O.

LiCoPO 4 thin films were deposited on Li 1+ x+ yAl xTi 2- xSi yP 3- yO 12 (LATSP) solid electrolyte by radio frequency magnetron sputtering and were characterized by X-ray diffraction and scanning electron microscope. The films show a (1 1 1) preferred orientation upon annealing and are chemically stable with LATSP up to 600 °C in air. An all-solid-state Li/PEO 18-Li(CF 3SO 2) 2N/LATSP/LiCoPO 4/Au cell was fabricated to investigate the electrochemical performance and Li-ion chemical diffusion coefficients, D˜Li , of the LiCoPO 4 thin films. The potential dependence of D˜Li values of the LiCoPO 4 thin film was investigated by potentiostatic intermittent titration technique and was compared with those of the LiFePO 4 thin film. These results showed that the intercalation mechanism of Li-ion in LiCoPO 4 is different from that in LiFePO 4.

Lake Metabolism: Comparison of Lake Metabolic Rates Estimated from a Diel CO2- and the Common Diel O2-Technique.

PubMed

Peeters, Frank; Atamanchuk, Dariia; Tengberg, Anders; Encinas-Fernández, Jorge; Hofmann, Hilmar

2016-01-01

Lake metabolism is a key factor for the understanding of turnover of energy and of organic and inorganic matter in lake ecosystems. Long-term time series on metabolic rates are commonly estimated from diel changes in dissolved oxygen. Here we present long-term data on metabolic rates based on diel changes in total dissolved inorganic carbon (DIC) utilizing an open-water diel CO2-technique. Metabolic rates estimated with this technique and the traditional diel O2-technique agree well in alkaline Lake Illmensee (pH of ~8.5), although the diel changes in molar CO2 concentrations are much smaller than those of the molar O2 concentrations. The open-water diel CO2- and diel O2-techniques provide independent measures of lake metabolic rates that differ in their sensitivity to transport processes. Hence, the combination of both techniques can help to constrain uncertainties arising from assumptions on vertical fluxes due to gas exchange and turbulent diffusion. This is particularly important for estimates of lake respiration rates because these are much more sensitive to assumptions on gradients in vertical fluxes of O2 or DIC than estimates of lake gross primary production. Our data suggest that it can be advantageous to estimate respiration rates assuming negligible gradients in vertical fluxes rather than including gas exchange with the atmosphere but neglecting vertical mixing in the water column. During two months in summer the average lake net production was close to zero suggesting at most slightly autotrophic conditions. However, the lake emitted O2 and CO2 during the entire time period suggesting that O2 and CO2 emissions from lakes can be decoupled from the metabolism in the near surface layer.

Lake Metabolism: Comparison of Lake Metabolic Rates Estimated from a Diel CO2- and the Common Diel O2-Technique

PubMed Central

Peeters, Frank; Atamanchuk, Dariia; Tengberg, Anders; Encinas-Fernández, Jorge; Hofmann, Hilmar

2016-01-01

Lake metabolism is a key factor for the understanding of turnover of energy and of organic and inorganic matter in lake ecosystems. Long-term time series on metabolic rates are commonly estimated from diel changes in dissolved oxygen. Here we present long-term data on metabolic rates based on diel changes in total dissolved inorganic carbon (DIC) utilizing an open-water diel CO2-technique. Metabolic rates estimated with this technique and the traditional diel O2-technique agree well in alkaline Lake Illmensee (pH of ~8.5), although the diel changes in molar CO2 concentrations are much smaller than those of the molar O2 concentrations. The open-water diel CO2- and diel O2-techniques provide independent measures of lake metabolic rates that differ in their sensitivity to transport processes. Hence, the combination of both techniques can help to constrain uncertainties arising from assumptions on vertical fluxes due to gas exchange and turbulent diffusion. This is particularly important for estimates of lake respiration rates because these are much more sensitive to assumptions on gradients in vertical fluxes of O2 or DIC than estimates of lake gross primary production. Our data suggest that it can be advantageous to estimate respiration rates assuming negligible gradients in vertical fluxes rather than including gas exchange with the atmosphere but neglecting vertical mixing in the water column. During two months in summer the average lake net production was close to zero suggesting at most slightly autotrophic conditions. However, the lake emitted O2 and CO2 during the entire time period suggesting that O2 and CO2 emissions from lakes can be decoupled from the metabolism in the near surface layer. PMID:28002477

Modeling the radiative effects of biomass burning aerosols on carbon fluxes in the Amazon region

NASA Astrophysics Data System (ADS)

Moreira, Demerval S.; Longo, Karla M.; Freitas, Saulo R.; Yamasoe, Marcia A.; Mercado, Lina M.; Rosário, Nilton E.; Gloor, Emauel; Viana, Rosane S. M.; Miller, John B.; Gatti, Luciana V.; Wiedemann, Kenia T.; Domingues, Lucas K. G.; Correia, Caio C. S.

2017-12-01

Every year, a dense smoke haze covers a large portion of South America originating from fires in the Amazon Basin and central parts of Brazil during the dry biomass burning season between August and October. Over a large portion of South America, the average aerosol optical depth at 550 nm exceeds 1.0 during the fire season, while the background value during the rainy season is below 0.2. Biomass burning aerosol particles increase scattering and absorption of the incident solar radiation. The regional-scale aerosol layer reduces the amount of solar energy reaching the surface, cools the near-surface air, and increases the diffuse radiation fraction over a large disturbed area of the Amazon rainforest. These factors affect the energy and CO2 fluxes at the surface. In this work, we applied a fully integrated atmospheric model to assess the impact of biomass burning aerosols in CO2 fluxes in the Amazon region during 2010. We address the effects of the attenuation of global solar radiation and the enhancement of the diffuse solar radiation flux inside the vegetation canopy. Our results indicate that biomass burning aerosols led to increases of about 27 % in the gross primary productivity of Amazonia and 10 % in plant respiration as well as a decline in soil respiration of 3 %. Consequently, in our model Amazonia became a net carbon sink; net ecosystem exchange during September 2010 dropped from +101 to -104 TgC when the aerosol effects are considered, mainly due to the aerosol diffuse radiation effect. For the forest biome, our results point to a dominance of the diffuse radiation effect on CO2 fluxes, reaching a balance of 50-50 % between the diffuse and direct aerosol effects for high aerosol loads. For C3 grasses and savanna (cerrado), as expected, the contribution of the diffuse radiation effect is much lower, tending to zero with the increase in aerosol load. Taking all biomes together, our model shows the Amazon during the dry season, in the presence of high biomass burning aerosol loads, changing from being a source to being a sink of CO2 to the atmosphere.

Soil Aeration deficiencies in urban sites

NASA Astrophysics Data System (ADS)

Weltecke, Katharina; Gaertig, Thorsten

2010-05-01

Soil aeration deficiencies in urban sites Katharina Weltecke and Thorsten Gaertig On urban tree sites reduction of soil aeration by compaction or sealing is an important but frequently underestimated factor for tree growth. Up to 50% of the CO2 assimilated during the vegetation period is respired in the root space (Qi et al. 1994). An adequate supply of the soil with oxygen and a proper disposal of the exhaled carbon dioxide are essential for an undisturbed root respiration. If the soil surface is smeared, compacted or sealed, soil aeration is interrupted. Several references show that root activity and fine root growth are controlled by the carbon dioxide concentration in soil air (Qi et al.1994, Burton et al. 1997). Gaertig (2001) found that decreasing topsoil gas permeability leads to reduced fine root density and hence to injury in crown structure of oaks. In forest soils a critical CO2 concentration of more than 0.6 % indicates a bad aeration status (Gaertig 2001). The majority of urban tree sites are compacted or sealed. The reduction of soil aeration may lead to dysfunctions in the root space and consequently to stress during periods of drought, which has its visible affects in crown structure. It is reasonable to assume that disturbances in soil aeration lead to reduced tree vigour and roadworthiness, resulting in high maintenance costs. The assessment of soil aeration in urban sites is difficult. In natural ecosystems the measurement of gas diffusivity and the gas-chromatical analysis of CO2 in soil air are accepted procedures in analyzing the state of aeration (Schack-Kirchner et al. 2001, Gaertig 2001). It has been found that these methods can also be applied for analyzing urban sites. In particular CO2 concentration in the soil atmosphere can be considered as a rapidly assessable, relevant and integrating indicator of the aeration situation of urban soils. This study tested the working hypothesis that soil aeration deficiencies lead to a decrease of fine root density and tree vigour on urban soils. For that purpose gas diffusivity, soil CO2 concentrations and fine root density were measured on typical urban sites in the German cities of Göttingen, Mannheim, and Kassel. The known characteristics of soil aeration on forest sites could be affirmed for urban soils. A negative correlation was found between gas diffusion coefficients and CO2 concentration as well as between fine root extension and CO2 concentration. Changes in crown structure of beech indicating a loss of vigour were found at sites with disturbed aeration. Diffusivity patterns and CO2 concentrations of different specific urban soil sealing types were found. On more natural sites (mulch, grass) increased gas diffusion and low CO2 concentration were present. In contrast, on more compacted or sealed areas (asphalt, paving stone, macadamised road surface) the exchange between soil air and atmosphere was nearly disconnected and soil CO2 concentrations partly exceeded the known critical value of 0.6 % up to tenfold. Literature Burton, A. J.; Pregitzer, K. S.; Zogg, G. P. und Zak D. R. (1997): Effect of measurement CO2 concentrations on sugar maple root respiration. In: Canadian journal of Forest Research, H. 17, S. 421-427. Gaertig, T. (2001): Bodengashaushalt, Feinwurzeln und Vitalität von Eichen. In: Freiburger Bodenkundliche Abhandlungen, H. 40, S. 157. Qi, J.; Marshall, J. D.; Mattson, K. G. (1994): High soil carbon dioxide concentrations inhibit root respiration of Douglas fir. In: New Phytol., Jg. 128, H. 3, S. 435-442. Schack-Kirchner, H.; Gaertig, T.; Wilpert, K. v.; Hildebrand, E. E. (2001): A modified McIntyre and Phillip approach to measure top-soil gas diffusivity in-situ. In: J. Plant Nutr. Soil Sci., Jg. 164, S. 253-258.

Determination of Magma Ascent Rates From D/H Fractionation in Olivine-Hosted Melt Inclusions

NASA Astrophysics Data System (ADS)

Gaetani, G. A.; Bucholz, C. E.; Le Roux, V.; Klein, F.; Ghiorso, M. S.; Wallace, P. J.; Sims, K. W. W.

2016-12-01

The depths at which magmas are stored and the rates at which they ascend to Earth's surface are important controls on the dynamics of volcanic eruptions. Eruptive style is influenced by the rate at which magma ascends from the reservoir to the surface through its effect on vapor bubble nucleation, growth, and coalescence. However, ascent rates are difficult to quantify because few accurate geospeedometers are appropriate for a process occurring on such short timescales. We developed a new approach to determining ascent rates on the basis of D/H fraction associated with diffusive H2O loss from olivine-hosted melt inclusions. The utility of this approach was demonstrated on olivine-hosted melt inclusions in a hyaloclastite recovered from within Dry Valley Drilling Project core 3 from Hut Point Peninsula, Antarctica. All of the melt inclusions are glassy and contain vapor bubbles. The volumes of melt inclusions and vapor bubbles were determined by X-ray microtomography, and the density of CO2 within each bubble was determined using Raman spectroscopy. Olivines were then polished to expose individual inclusions and analyzed for volatiles and dDVSMOW by secondary ion mass spectrometry. Total CO2 was reconstructed by summing CO2 in the included glass and vapor bubble. Entrapment pressures calculated on the basis of reconstructed CO2 and maximum H2O concentrations using the MagmaSat solubility model [1] indicate a depth of origin of 24 km - in good agreement with the seismically determined depth to the Moho beneath Ross Island [2]. Magma ascent rates were determined using a finite difference model for melt inclusion dehydration during magma ascent. The positive correlation between H2O and CO2 is consistent with diffusive loss during ascent, but does not provide direct information on magma ascent rate. In contrast, the slope of the negative correlation between H2O and dDVSMOW is a reflection of transport time and, therefore, ascent rate. If it is assumed that magmas did not stall between the Moho and the surface, our results indicate an ascent rate of 0.1 m/s. Our new approach has broad applicability to determining magma ascent rates for both active and extinct volcanic centers in all tectonic environments. References: [1] Ghiorso and Gualda (2015) Cont Miner Pet 169; [2] Finotello et al. (2011) Geophys J Int 185:85-92.

Ultrafast atomic layer-by-layer oxygen vacancy-exchange diffusion in double-perovskite LnBaCo2O5.5+δ thin films.

PubMed

Bao, Shanyong; Ma, Chunrui; Chen, Garry; Xu, Xing; Enriquez, Erik; Chen, Chonglin; Zhang, Yamei; Bettis, Jerry L; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qingyu

2014-04-22

Surface exchange and oxygen vacancy diffusion dynamics were studied in double-perovskites LnBaCo2O5.5+δ (LnBCO) single-crystalline thin films (Ln = Er, Pr; -0.5 < δ < 0.5) by carefully monitoring the resistance changes under a switching flow of oxidizing gas (O2) and reducing gas (H2) in the temperature range of 250 ~ 800 °C. A giant resistance change ΔR by three to four orders of magnitude in less than 0.1 s was found with a fast oscillation behavior in the resistance change rates in the ΔR vs. t plots, suggesting that the oxygen vacancy exchange diffusion with oxygen/hydrogen atoms in the LnBCO thin films is taking the layer by layer oxygen-vacancy-exchange mechanism. The first principles density functional theory calculations indicate that hydrogen atoms are present in LnBCO as bound to oxygen forming O-H bonds. This unprecedented oscillation phenomenon provides the first direct experimental evidence of the layer by layer oxygen vacancy exchange diffusion mechanism.

Local Osmosis and Isotonic Transport

PubMed Central

Mathias, R.T.; Wang, H.

2006-01-01

Osmotically driven water flow, u (cm/s), between two solutions of identical osmolarity, co (300 mM in mammals), has a theoretical isotonic maximum given by u = j/co, where j (moles/cm2/s) is the rate of salt transport. In many experimental studies, transport was found to be indistinguishable from isotonic. The purpose of this work is to investigate the conditions for u to approach isotonic. A necessary condition is that the membrane salt/ water permeability ratio, ε, must be small: typical physiological values are ε = 10−3 to 10−5, so ε is generally small but this is not sufficient to guarantee near-isotonic transport. If we consider the simplest model of two series membranes, which secrete a tear or drop of sweat (i.e., there are no externally-imposed boundary conditions on the secretion), diffusion is negligible and the predicted osmolarities are: basal = co, intracellular ≈ (1 + ε)co, secretion ≈ (1 + 2ε)co, and u ≈ (1 – 2ε)j/co. Note that this model is also appropriate when the transported solution is experimentally collected. Thus, in the absence of external boundary conditions, transport is experimentally indistinguishable from isotonic. However, if external boundary conditions set salt concentrations to co on both sides of the epithelium, then fluid transport depends on distributed osmotic gradients in lateral spaces. If lateral spaces are too short and wide, diffusion dominates convection, reduces osmotic gradients and fluid flow is significantly less than isotonic. Moreover, because apical and basolateral membrane water fluxes are linked by the intracellular osmolarity, water flow is maximum when the total water permeability of basolateral membranes equals that of apical membranes. In the context of the renal proximal tubule, data suggest it is transporting at near optimal conditions. Nevertheless, typical physiological values suggest the newly filtered fluid is reabsorbed at a rate u ≈ 0.86 j/co, so a hypertonic solution is being reabsorbed. The osmolarity of the filtrate cF (M) will therefore diminish with distance from the site of filtration (the glomerulus) until the solution being transported is isotonic with the filtrate, u = j/cF.With this steady- state condition, the distributed model becomes approximately equivalent to two membranes in series. The osmolarities are now: cF ≈ (1 – 2ε)j/co, intracellular ≈ (1 – ε)co, lateral spaces ≈ co, and u ≈(1 + 2ε)j/co. The change in cF is predicted to occur with a length constant of about 0.3 cm. Thus, membrane transport tends to adjust transmembrane osmotic gradients toward εco, which induces water flow that is isotonic to within order ε. These findings provide a plausible hypothesis on how the proximal tubule or other epithelia appear to transport an isotonic solution. PMID:16596445

Syntheses, characterization and nonlinear optical properties of sodium-scandium carbonate Na5Sc(CO3)4·2H2O

NASA Astrophysics Data System (ADS)

Chen, Jie; Luo, Min; Ye, Ning

2014-10-01

A novel nonlinear optical (NLO) material Na5Sc(CO3)4·2H2O has been synthesized under a subcritical hydrothermal condition. The structure is determined by single-crystal X-ray diffraction and further characterized by TG analyses and UV-vis-NIR diffuse reflectance spectrum. It crystallizes in the tetragonal space group P-421c, with a = b = 7.4622(6) Å, C = 11.5928(15) Å. The Second-harmonic generation (SHG) on polycrystalline samples was measured using the Kurtz and Perry technique, which indicated that Na5Sc(CO3)4·2H2O was a phase-matchable material, and its measured SHG coefficient was about 1.8 times as large as that of d36 (KDP). The results from the UV-vis diffuse reflectance spectroscopy study of the powder samples indicated that the short-wavelength absorption edges of Na5Sc(CO3)4·2H2O is about 220 nm, suggesting that this crystal is a promising UV nonlinear optical (NLO) materials.

Temperature dependence of magneto-transport properties in Co{sub 2}Fe(Ga{sub 0.5}Ge{sub 0.5})/Cu lateral spin valves

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

Ikhtiar,; Mitani, S.; Hono, K.

2016-02-08

The non-local spin signals of Co{sub 2}Fe(Ga{sub 0.5}Ge{sub 0.5})/Cu lateral spin valves with sub-micron size dimensions were measured with varying temperatures. The non-local spin signal reaches 54 mΩ at 4 K, while it degrades down to 13 mΩ at room temperature. Analysis based on the one-dimensional spin diffusion model clarifies the dominant source for degrading of the spin signal is suppression of the spin diffusion length in Cu, not the spin polarization, indicating Co{sub 2}Fe(Ga{sub 0.5}Ge{sub 0.5}) keeps half-metallic nature even at room temperature. The temperature dependence of non-local spin signal was found to exhibit a downturn at 36 K. The presence of magneticmore » impurities, detrimental effect of which becomes more pronounced for diffusive transport in long Cu wires, is suggested to cause the observed downturn in non-local spin signals.« less

A Multiwavelength Study of the Nature of Diffuse Atomic and Molecular Gas

NASA Astrophysics Data System (ADS)

Federman, Steven

2015-10-01

Our proposed observations under the UV Initiative form a key component of a multiwavelength study of diffuse atomic and molecular clouds. The Herschel GOT C+ survey associated [C II] emission at 158 microns with emission from H I at 21 cm and CO at 2.6 mm, revealing the presence of warm neutral gas, cold neutral gas, CO-dark H2 gas, and molecular clouds. Ground-based measurements of Ca II, CH+, CH, and CN at visible wavelengths show absorption at the same velocities as the components seen in the GOT C+ survey. A main focus of our project is a detailed investigation of the nature of CO-dark H2 gas, interstellar material not associated with H I and CO emission. The presence of this additional material alters our view of molecular gas in galaxies and its connection to star formation rates. We propose ultraviolet observations of three targets with STIS that probe two of the pointings in the GOT C+ survey. Absorption from CO, at much greater sensitivies than is possible from surveying CO emission, will be sought. Analysis of CO, C I, and C2 absorption will yield the physical conditions (gas density and temperature) along the sight lines. The results will be compared with those inferred from CN chemistry based on the observations at visible wavelengths. Other probes seen at UV wavelengths, such as O I, Cu II, and Cl I, will provide a more complete picture of the environment seen in the atomic components of the GOT C+ survey. The outcome of the project will be the most detailed study of diffuse atomic and molecular gas from spectral measurements spanning nearly seven orders of magnitude in wavelength.

Reactivity and oxygen diffusion property of resistive barriers for Bi-2223/Ag tapes

NASA Astrophysics Data System (ADS)

Kováč, P.; Hušek, I.

2002-12-01

Reactivity of several oxide materials (OM) with BSCCO powder and oxygen diffusion through OM layer has been tested at temperature ≈840 °C in air. The OM (e.g.: BaZrO 3, SrCO 3, MgO and ZrO 2) showing the low or no reactivity with BSCCO have been mixed (10 wt.%) with precursor powder and used for single-core tapes. Bi-2223/Ag/OM/Ag single-core tapes with oxide barriers made of BaZrO 3, SrCO 3, ZrO 2 and Al 2O 3 have been also prepared by a standard powder-in-tube technique. The used OM in the direct contact with BSCCO influences the electrical properties of Bi-2223 phase differently. These is because the oxides react with BSCCO during the heat treatment and simultaneously affect the 2212→2223 phase transformation, the Bi-2223 grain growth and so also grain connectivity. SrCO 3 powder has been evaluated as the best material from the point of no destructive effect on 2223 phase transport current property. The oxide barrier controls the oxygen diffusion during the tape heat treatment and simultaneously the HTS phase formation kinetics, its purity and content within the superconducting core. For single-core Bi-2223/Ag/OM/Ag tapes, the highest current density was measured for Al 2O 3 due to only slightly reduced oxygen diffusion through the barrier.

Recent developments in CO2 lasers

NASA Astrophysics Data System (ADS)

Du, Keming

1993-05-01

CO2 lasers have been used in industry mainly for such things as cutting, welding, and surface processing. To conduct a broad spectrum of high-speed and high-quality applications, most of the developments in industrial CO2 lasers at the ILT are aimed at increasing the output power, optimizing the beam quality, and reducing the production costs. Most of the commercial CO2 lasers above 5 kW are transverse-flow systems using dc excitation. The applications of these lasers are limited due to the lower beam quality, the poor point stability, and the lower modulation frequency. To overcome the problems we developed a fast axial- flow CO2 laser using rf excitation with an output of 13 kW. In section 2 some of the results are discussed concerning the gas flow, the discharge, the resonator design, optical effects of active medium, the aerodynamic window, and the modulation of the output power. The first CO2 lasers ever built are diffusion-cooled systems with conventional dc excited cylindrical discharge tubes surrounded by cooling jackets. The output power per unit length is limited to 50 W/m by those lasers with cylindrical tubes. In the past few years considerable increases in the output power were achieved, using new mechanical geometries, excitation- techniques, and resonator designs. This progress in diffusion-cooled CO2 lasers is presented in section 3.

Analysis of ligand-protein exchange by Clustering of Ligand Diffusion Coefficient Pairs (CoLD-CoP).

PubMed

Snyder, David A; Chantova, Mihaela; Chaudhry, Saadia

2015-06-01

NMR spectroscopy is a powerful tool in describing protein structures and protein activity for pharmaceutical and biochemical development. This study describes a method to determine weak binding ligands in biological systems by using hierarchic diffusion coefficient clustering of multidimensional data obtained with a 400 MHz Bruker NMR. Comparison of DOSY spectrums of ligands of the chemical library in the presence and absence of target proteins show translational diffusion rates for small molecules upon interaction with macromolecules. For weak binders such as compounds found in fragment libraries, changes in diffusion rates upon macromolecular binding are on the order of the precision of DOSY diffusion measurements, and identifying such subtle shifts in diffusion requires careful statistical analysis. The "CoLD-CoP" (Clustering of Ligand Diffusion Coefficient Pairs) method presented here uses SAHN clustering to identify protein-binders in a chemical library or even a not fully characterized metabolite mixture. We will show how DOSY NMR and the "CoLD-CoP" method complement each other in identifying the most suitable candidates for lysozyme and wheat germ acid phosphatase. Copyright © 2015 Elsevier Inc. All rights reserved.

Climate warming due to increasing atmospheric CO2 - Simulations with a multilayer coupled atmosphere-ocean seasonal energy balance model

NASA Technical Reports Server (NTRS)

Li, Peng; Chou, Ming-Dah; Arking, Albert

1987-01-01

The transient response of the climate to increasing CO2 is studied using a modified version of the multilayer energy balance model of Peng et al. (1982). The main characteristics of the model are described. Latitudinal and seasonal distributions of planetary albedo, latitude-time distributions of zonal mean temperatures, and latitudinal distributions of evaporation, water vapor transport, and snow cover generated from the model and derived from actual observations are analyzed and compared. It is observed that in response to an atmospheric doubling of CO2, the model reaches within 1/e of the equilibrium response of global mean surface temperature in 9-35 years for the probable range of vertical heat diffusivity in the ocean. For CO2 increases projected by the National Research Council (1983), the model's transient response in annually and globally averaged surface temperatures is 60-75 percent of the corresponding equilibrium response, and the disequilibrium increases with increasing heat diffusivity of the ocean.

CoMn2O4 Spinel Hierarchical Microspheres Assembled with Porous Nanosheets as Stable Anodes for Lithium-ion Batteries

PubMed Central

Hu, Lin; Zhong, Hao; Zheng, Xinrui; Huang, Yimin; Zhang, Ping; Chen, Qianwang

2012-01-01

Herein, we report the feasibility to enhance the capacity and stability of CoMn2O4 anode materials by fabricating hierarchical mesoporous structure. The open space between neighboring nanosheets allows for easy diffusion of the electrolyte. The hierarchical microspheres assembled with nanosheets can ensure that every nanosheet participates in the electrochemical reaction, because every nanosheet is contacted with the electrolyte solution. The hierarchical structure and well interconnected pores on the surface of nanosheets will enhance the CoMn2O4/electrolyte contact area, shorten the Li+ ion diffusion length in the nanosheets, and accommodate the strain induced by the volume change during the electrochemical reaction. The last, hierarchical architecture with spherical morphology possesses relatively low surface energy, which results in less extent of self-aggregation during charge/discharge process. As a result, CoMn2O4 hierarchical microspheres can achieve a good cycle ability and high rate capability. PMID:23248749

Ternary CNTs@TiO2/CoO Nanotube Composites: Improved Anode Materials for High Performance Lithium Ion Batteries

PubMed Central

Madian, Mahmoud; Ummethala, Raghunandan; Abo El Naga, Ahmed Osama; Ismail, Nahla; Rümmeli, Mark Hermann; Eychmüller, Alexander; Giebeler, Lars

2017-01-01

TiO2 nanotubes (NTs) synthesized by electrochemical anodization are discussed as very promising anodes for lithium ion batteries, owing to their high structural stability, high surface area, safety, and low production cost. However, their poor electronic conductivity and low Li+ ion diffusivity are the main drawbacks that prevent them from achieving high electrochemical performance. Herein, we report the fabrication of a novel ternary carbon nanotubes (CNTs)@TiO2/CoO nanotubes composite by a two-step synthesis method. The preparation includes an initial anodic fabrication of well-ordered TiO2/CoO NTs from a Ti-Co alloy, followed by growing of CNTs horizontally on the top of the oxide films using a simple spray pyrolysis technique. The unique 1D structure of such a hybrid nanostructure with the inclusion of CNTs demonstrates significantly enhanced areal capacity and rate performances compared to pure TiO2 and TiO2/CoO NTs, without CNTs tested under identical conditions. The findings reveal that CNTs provide a highly conductive network that improves Li+ ion diffusivity, promoting a strongly favored lithium insertion into the TiO2/CoO NT framework, and hence resulting in high capacity and an extremely reproducible high rate capability. PMID:28773032

Fabrication of Polyimide Membrane Incorporated with Functional Graphene Oxide for CO2 Separation: The Effects of GO Surface Modification on Membrane Performance.

PubMed

Wang, Ting; Cheng, Cheng; Wu, Li-Guang; Shen, Jiang-Nan; Van der Bruggen, Bart; Chen, Qian; Chen, Di; Dong, Chun-Ying

2017-06-06

Two kinds of isocyanate were used to modify graphene oxide (GO) samples. Then, polyimide (PI) hybrid membranes containing GO and modified GO were prepared by in situ polymerization. The permeation of CO 2 and N 2 was studied using these novel membranes. The morphology experiments showed that the isocyanate groups were successfully grafted on the surface of GO by replacement of the oxygen-containing functional groups. After modification, the surface polarity of the GO increased, and more defect structures were introduced into the GO surface. This resulted in a good distribution of more modified GO samples in the PI polymer matrix. Thus, the PI hybrid membranes incorporated by modified GO samples showed a high gas permeability and ideal selectivity of membranes. In addition, enhancement of the selectivity due to the solubility of CO 2 played a major role in the increase in the separation performance of the hybrid membranes for CO 2 , although the diffusion coefficients for CO 2 also increased. Both the higher condensability and the strong affinity between CO 2 molecules and GO in the polymer matrix caused an enhancement of the solubility selectivity higher than the diffusion selectivity after GO surface modification.

Kinetic Monte Carlo (kMC) simulation of carbon co-implant on pre-amorphization process.

PubMed

Park, Soonyeol; Cho, Bumgoo; Yang, Seungsu; Won, Taeyoung

2010-05-01

We report our kinetic Monte Carlo (kMC) study of the effect of carbon co-implant on the pre-amorphization implant (PAL) process. We employed BCA (Binary Collision Approximation) approach for the acquisition of the initial as-implant dopant profile and kMC method for the simulation of diffusion process during the annealing process. The simulation results implied that carbon co-implant suppresses the boron diffusion due to the recombination with interstitials. Also, we could compare the boron diffusion with carbon diffusion by calculating carbon reaction with interstitial. And we can find that boron diffusion is affected from the carbon co-implant energy by enhancing the trapping of interstitial between boron and interstitial.

Improving breast cancer diagnosis by reducing chest wall effect in diffuse optical tomography

NASA Astrophysics Data System (ADS)

Zhou, Feifei; Mostafa, Atahar; Zhu, Quing

2017-02-01

We have developed ultrasound (US)-guided diffuse optical tomography (DOT) technique to assist US diagnosis of breast cancer and to predict neoadjuvant chemotherapy response of breast cancer patients. The technique was implemented using a hand-held hybrid probe consisting co-registered US transducer and optical source and detector fibers which couple the light illumination from laser diodes and photon detection to PMT detectors. With the US guidance, diffused light measurements were made at the breast lesion site and the normal contralateral reference site which was used to estimate the background tissue optical properties for imaging reconstruction. However, background optical properties were affected by the chest wall underneath the breast tissue. In this study, we have analyzed data from 297 female patients and results have shown statistical significant correlation between fitted optical properties (μa and μs') and the chest wall depth detected by a boundary detection algorithm applied to co-registered US images (r < 0.27, p < 1.0 x 10-4). After subtracting the background total hemoglobin (tHb) computed with μa at each wavelength, the difference between malignant and benign lesion groups has improved. The Area-under-the- ROC curve (AUC) has improved from 88.5% to 91.5% (sensitivity improved from 85.0% to 87.5% and specificity from 90.2% to 92.6%). Statistical test has revealed significant difference of the AUC improvements after subtracting background tHb values.

Hemoglobin encapsulation in vesicles retards NO and CO binding and O2 release when perfused through narrow gas-permeable tubes.

PubMed

Sakai, Hiromi; Okuda, Naoto; Sato, Atsushi; Yamaue, Tatsuya; Takeoka, Shinji; Tsuchida, Eishun

2010-03-01

Intravenous administration of cell-free Hb induces vasoconstriction and circulatory disorders, presumably because of the intrinsic affinities to endogenous nitric oxide (NO) and carbon monoxide (CO) as vasorelaxation factors and because of the facilitated O(2) release that might induce autoregulatory vasoconstriction. We examined these gas reactions when Hb-containing solutions of four kinds were perfused through artificial narrow tubes at a practical Hb concentration (10 g/dl). Purified Hb solution, polymerized bovine Hb (Poly(B)Hb), encapsulated Hb [Hb-vesicles (HbV), 279 nm], and red blood cells (RBCs) were perfused through a gas-permeable narrow tube (25 microm inner diameter) at 1 mm/s centerline velocity. The level of reactions was determined microscopically based on the visible-light absorption spectrum of Hb. When the tube was immersed in NO and CO atmospheres, both NO binding and CO binding of deoxygenated Hb (deoxy-Hb) and Poly(B)Hb in the tube was faster than those of HbV and RBCs, and HbV and RBCs showed almost identical binding rates. When the tube was immersed in a N(2) atmosphere, oxygenated Hb and Poly(B)Hb showed much faster O(2) release than did HbV and RBCs. Poly(B)Hb showed a faster reaction than Hb because of the lower O(2) affinity of Poly(B)Hb than Hb. The diffusion process of the particles was simulated using Navier-Stokes and Maxwell-Stefan equations. Results clarified that small Hb (6 nm) diffuses laterally and mixes rapidly. However, the large-dimension HbV shows no such rapid diffusion. The purely physicochemical differences in diffusivity of the particles and the resulting reactivity with gas molecules are one factor inducing biological vasoconstriction of Hb-based oxygen carriers.

Carbon Dioxide Exchange and Acidity Levels in Detached Pineapple, Ananas comosus (L.), Merr., Leaves during the Day at Various Temperatures, Oxygen and Carbon Dioxide Concentrations.

PubMed

Moradshahi, A; Vines, H M; Black, C C

1977-02-01

The effects of temperature, O(2), and CO(2) on titratable acid content and on CO(2) exchange were measured in detached pineapple (Ananas comosus) leaves during the daily 15-hour light period. Comparative measurements were made in air and in CO(2)-free air. Increasing the leaf temperature from 20 to 35 C decreased the total CO(2) uptake in air and slightly increased the total CO(2) released into CO(2)-free air. Between 25 and 35 C, the activation energy for daily acid loss was near 12 kcal mol(-1), but at lower temperatures the activation energy was much greater.Increasing O(2) or decreasing the CO(2) concentration decreased the total CO(2) fixation in air, whereas the total CO(2) released in CO(2)-free air was increased. The total acid content remained constant at 20 C, but it decreased progressively with increasing temperature both in air and in CO(2)-free air. The total acid content at 30 C remained constant in 2% O(2) irrespective of CO(2) concentration. The total acid content decreased in 21 and 50% O(2) as the CO(2) increased from 0 to 300, and 540 mul/l of CO(2). The data indicate that photorespiration is present in pineapple. The lack of acid loss in 2% O(2) suggests that light deacidification is dependent upon respiration and that higher O(2) concentrations are required to saturate deacidification.

Impact of Changes in Diffuse Radiation on the Global Land Carbon Sink, 1901-2100

NASA Astrophysics Data System (ADS)

Mercado, L.; Bellouin, N.; Sitch, S.; Boucher, O.; Huntingford, C.; Wild, M.; Cox, P. M.

2009-04-01

Recent observational and theoretical studies have shown that changes in surface radiation that lead to increasing diffuse surface irradiance, enhance plant photosynthesis (Gu et al., 2003, Niyogi et al., 2004, Oliveira et al., 2007, Roderick et al., 2001). Solar radiation reaching the land surface has changed over the industrial era due to aerosols emitted from volcanoes and various anthropogenic sources (Kvalevag and Myhre, 2007). Such changes in total surface radiation are accompanied by changes in direct and diffuse surface solar radiation. Current global climate-carbon models do include the effects of changes in total surface radiation on the land biosphere but neglect the positive effects of increasing diffuse fraction on plant photosynthesis. In this study we estimate for the first time, the impact of variations in diffuse fraction on the land carbon sink using a global model (Mercado et al., 2007) modified to account for the effects of variations in both direct and diffuse radiation on canopy photosynthesis. We use meteorological forcing from the Climate Research Unit Data set. Additionally short wave and photosynthetic active radiation are reconstructed from the Hadley centre climate model, which accounts for the scattering and absorption of light by tropospheric and stratospheric aerosols and change in cloud properties due to indirect aerosol effects. References Gu L.H., Baldocchi D.D., Wofsy S.C., Munger J.W., Michalsky J.J., Urbanski S.P. & Boden T.A. (2003) Response of a deciduous forest to the Mount Pinatubo eruption: Enhanced photosynthesis. Science, 299, 2035-2038. M. M. Kvalevag and G. Myhre, J. Clim. 20, 4874 (2007). Mercado L.M., Huntingford C., Gash J.H.C., Cox P.M. & Jogireddy V. (2007) Improving the representation of radiation interception and photosynthesis for climate model applications. Tellus Series B-Chemical and Physical Meteorology, 59, 553-565. Niyogi D., Chang H.I., Saxena V.K., Holt T., Alapaty K., Booker F., Chen F., Davis K.J., Holben B., Matsui T., Meyers T., Oechel W.C., Pielke R.A., Wells R., Wilson K. & Xue Y.K. (2004) Direct observations of the effects of aerosol loading on net ecosystem CO2 exchanges over different landscapes. Geophysical Research Letters, 31. Oliveira P.H.F., Artaxo P., Pires C., De Lucca S., Procopio A., Holben B., Schafer J., Cardoso L.F., Wofsy S.C. & Rocha H.R. (2007) The effects of biomass burning aerosols and clouds on the CO2 flux in Amazonia. Tellus Series B-Chemical and Physical Meteorology, 59, 338-349. Roderick M.L., Farquhar G.D., Berry S.L. & Noble I.R. (2001) On the direct effect of clouds and atmospheric particles on the productivity and structure of vegetation. Oecologia, 129, 21-30.

The relationship between bedding and face-down death in infancy: mathematical analysis of a respiratory simulation system using an infant mannequin to assess gas diffusibility in bedding.

PubMed

Sakai, Jun; Funayama, Masato; Kanetake, Jun

2007-02-14

Rebreathing is a model for the relationship between a prone sleeping position and sudden infant death syndrome. This study used a mechanical simulation model to establish the relationship between types of bedding and rebreathing potential for an infant placed prone (face down) at different postnatal ages. The infant mannequin was connected to a respirator set to deliver physiologically appropriate combinations of tidal volume (V(T)) and respiratory rates (RR) across a range of postnatal ages (0-18 months). Before measurements were made, CO(2) flow was regulated to 5+/-0.1% of end-tidal PCO(2) (EtCO(2)). After the model was placed in a prone position, any increase in the fractional concentration of inspired CO(2) (FiCO(2)) was measured. FiCO(2) increased immediately and rapidly, and reached a maximum value within a few minutes. The maximum FiCO(2) ranged from under 2% to over 10%, depending on the bedding. FiCO(2) was also affected by V(T) and RR. This model is not applicable to actual infants because of the large tissue stores of CO(2) in infants; however, it is useful for evaluation of gas diffusibility of bedding and will simplify the investigation of sleeping environments when a baby is found dead with its face covered by soft bedding. In general, the higher the FiCO(2), the greater the rebreathing potential. Theoretically, considering the paucity of body stores of O(2), changes in FiO(2) would be affected not by changes in FiCO(2), but by CO(2) production and gas movement around the infant's face. The rapid decrease of FiO(2) is approximated at the inverse of the FiCO(2) timecourse, suggesting the significance of not only CO(2) accumulation but also O(2) deprivation in the potential space around the baby's face.

Inhibiting polysulfides diffusion of lithium-sulfur batteries using an acetylene black-CoS2 modified separator: Mechanism research and performance improvement

NASA Astrophysics Data System (ADS)

Zeng, Pan; Huang, Liwu; Zhang, Xinling; Han, Yamiao; Chen, Yungui

2018-01-01

Lithium-sulfur (Li-S) batteries are considered as one of the most promising chemistries in secondary energy storage field owing to their high energy density. However, the poor electrochemical performance mainly associated with the polysulfides shuttle has greatly hampered their practical application. Herein, a simple acetylene black (AB)-CoS2 coated separator is first designed to suppress the migration of polysulfides. The AB-CoS2 modified separator can not only efficiently capture the polysulfides by forming strong chemical bonding but also guarantee the rapid lithium ions diffusion. Moreover, the AB-CoS2 coating could serve as an upper current collector to accelerate electron transport for reinforcing the utilization of sulfur and ensuring the reactivation of the trapped active material. Consequently, the Li-S cell using AB-CoS2 modified separator shows a long-term cycling stability with an extremely low decay rate (0.09% per cycle) up to 450 cycles at a high rate of 2 C (3350 mA g-1). It also exhibits excellent rate capabilities, which maintains a capacity of 475 mAh g-1 even at 4.0 C rate.

Gas diffusion liquid storage bag and method of use for storing blood

NASA Technical Reports Server (NTRS)

Bank, H.; Cleland, E. L. (Inventor)

1979-01-01

The shelf life of stored whole blood may be doubled by adding a buffer which maintains a desired pH level. However, this buffer causes the generation of CO2 which, if not removed at a controlled rate, causes the pH value of the blood to decrease, which shortens the useful life of the blood. A blood storage bag is described which permits the CO2 to be diffused out at a controlled rate into the atmosphere, thereby maintaining the desired pH value and providing a bag strong enough to permit handling.

Effects of solar dimming and brightening on the terrestrial carbon sink

NASA Astrophysics Data System (ADS)

Mercado, L.; Bellouin, N.; Sitch, S.; Boucher, O.; Huntingford, C.; Wild, M.; Cox, P. M.

2009-04-01

Plant photosynthesis increases with solar radiation. Recent studies have shown that photosynthesis is more efficient under diffuse light conditions (Gu et al., 2003, Niyogi et al., 2004, Oliveira et al., 2007, Roderick et al., 2001). Changes in cloud cover and atmospheric aerosol loadings from either volcanic and anthropogenic sources, modify the total radiation reaching the surface and the fraction of this radiation which is diffuse, with uncertain overall effects on plant productivity and the global land carbon sink. A decrease in total solar radiation (Liepert, 2002, Stanhill and Cohen, 2001, Wild et al., 2005) has been observed at the Earth surface over the 1950-1990 period, called solar dimming. Such dimming gradually started to transform into brightening in some regions of the world since the late 1980s (Wild et al. 2005). The effect of these changes in total solar radiation and associated changes in diffuse radiation and diffuse fraction on the land biosphere has not yet been accounted for in global carbon cycle simulations because such models lack the mechanism that includes the diffuse irradiance effects on photosynthesis In this study we estimate the total impact of variations in clouds and atmospheric aerosols on the land carbon sink using a global land carbon cycle model modified to account for the effects of variations in both direct and diffuse radiation on canopy photosynthesis (Mercado et al., 2007) during the global dimming and brightening period. References Gu L.H., Baldocchi D.D., Wofsy S.C., Munger J.W., Michalsky J.J., Urbanski S.P. & Boden T.A. (2003) Response of a deciduous forest to the Mount Pinatubo eruption: Enhanced photosynthesis. Science, 299, 2035-2038. Liepert B.G. (2002) Observed reductions of surface solar radiation at sites in the United States and worldwide from 1961 to 1990. 29, 1421. Mercado L.M., Huntingford C., Gash J.H.C., Cox P.M. & Jogireddy V. (2007) Improving the representation of radiation interception and photosynthesis for climate model applications. Tellus Series B-Chemical and Physical Meteorology, 59, 553-565. Niyogi D., Chang H.I., Saxena V.K., Holt T., Alapaty K., Booker F., Chen F., Davis K.J., Holben B., Matsui T., Meyers T., Oechel W.C., Pielke R.A., Wells R., Wilson K. & Xue Y.K. (2004) Direct observations of the effects of aerosol loading on net ecosystem CO2 exchanges over different landscapes. Geophysical Research Letters, 31. Oliveira P.H.F., Artaxo P., Pires C., De Lucca S., Procopio A., Holben B., Schafer J., Cardoso L.F., Wofsy S.C. & Rocha H.R. (2007) The effects of biomass burning aerosols and clouds on the CO2 flux in Amazonia. Tellus Series B-Chemical and Physical Meteorology, 59, 338-349. Roderick M.L., Farquhar G.D., Berry S.L. & Noble I.R. (2001) On the direct effect of clouds and atmospheric particles on the productivity and structure of vegetation. Oecologia, 129, 21-30. Stanhill G. & Cohen S. (2001) Global dimming: a review of the evidence for a widespread and significant reduction in global radiation with discussion of its probable causes and possible agricultural consequences. 107, 255-278. Wild M., Gilgen H., Roesch A., Ohmura A., Long C.N., Dutton E.G., Forgan B., Kallis A., Russak V. & Tsvetkov A. (2005) From dimming to brightening: Decadal changes in solar radiation at Earth's surface. Science, 308, 847-850.

Interannual Variability In the Atmospheric CO2 Rectification Over Boreal Forests Based On A Coupled Ecosystem-Atmosphere Model

NASA Astrophysics Data System (ADS)

Chen, B.; Chen, J. M.; Worthy, D.

2004-05-01

Ecosystem CO2 exchange and the planetary boundary layer (PBL) are correlated diurnally and seasonally. The simulation of this atmospheric rectifier effect is important in understanding the global CO2 distribution pattern. A 12-year (1990-1996, 1999-2003), continuous CO2 measurement record from Fraserdale, Ontario (located ~150 km north of Timmons), along with a coupled Vertical Diffusion Scheme (VDS) and ecosystem model (Boreal Ecosystem Productivity Simulator, BEPS), is used to investigate the interannual variability in this effect over a boreal forest region. The coupled model performed well in simulating CO2 vertical diffusion processes. Simulated annual atmospheric rectifier effects, (including seasonal and diurnal), quantified as the variation in the mean CO2 concentration from the surface to the top of the PBL, varied from 2.8 to 4.1 ppm, even though the modeled seasonal variations in the PBL depth were similar throughout the 12-year period. The differences in the interannual rectifier effect primarily resulted from changes in the biospheric CO2 uptake and heterotrophic respiration. Correlations in the year-to year variations of the CO2 rectification were found with mean annual air temperatures, simulated gross primary productivity (GPP) and heterotrophic respiration (Rh) (r2=0.5, 0.46, 0.42, respectively). A small increasing trend in the CO2 rectification was also observed. The year-to-year variation in the vertical distribution of the monthly mean CO2 mixing ratios (reflecting differences in the diurnal rectifier effect) was related to interannual climate variability, however, the seasonal rectifier effects were found to be more sensitive to climate variability than the diurnal rectifier effects.

Reduction of CO2 diffuse emissions from the traditional ceramic industry by the addition of Si-Al raw material.

PubMed

González, I; Barba-Brioso, C; Campos, P; Romero, A; Galán, E

2016-09-15

The fabrication of ceramics can produce the emission of several gases, denominated exhaust gases, and also vapours resulting from firing processes, which usually contain metals and toxic substances affecting the environment and the health of workers. Especially harmful are the diffuse emissions of CO2, fluorine, chlorine and sulphur from the ceramics industry, which, in highly industrialized areas, can suppose an important emission focus of dangerous effects. Concerning CO2, factories that use carbonate-rich raw materials (>30% carbonates) can emit high concentrations of CO2 to the atmosphere. Thus, carbonate reduction or substitution with other raw materials would reduce the emissions. In this contribution, we propose the addition of Al-shales to the carbonated ceramic materials (marls) for CO2 emission reduction, also improving the quality of the products. The employed shales are inexpensive materials of large reserves in SW-Spain. The ceramic bodies prepared with the addition of selected Al-shale to marls in variable proportions resulted in a 40%-65% CO2 emission reduction. In addition, this research underlines at the same time that the use of a low-price raw material can also contribute to obtaining products with higher added value. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sulfides from Martian and Lunar Basalts: Comparative Chemistry for Ni Co Cu and Se

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

J Papike; P Burger; C Shearer

2011-12-31

Here Mars and Moon are used as 'natural laboratories' with Moon displaying lower oxygen fugacities ({approx}IW-1) than Mars ({approx}IW to FMQ). Moon has lower concentrations of Ni and Co in basaltic melts than does Mars. The major sulfides are troilite (FeS) in lunar basalts and pyrrhotite (Fe{sub 1-x}S) in martian basalts. This study focuses on the concentrations of Ni, Co, Cu, and Se. We chose these elements because of their geochemical importance and the feasibility of analyzing them with a combination of synchrotron X-ray fluorescence (SXRF) and electron microprobe (EPMA) techniques. The selenium concentrations could only be analyzed, at highmore » precision, with SXRF techniques as they are <150 ppm, similar to concentrations seen in carbonaceous chondrites and interplanetary dust particles (IDPs). Nickel and Co are in higher concentrations in martian sulfides than lunar and are higher in martian olivine-bearing lithologies than olivine-free varieties. The sulfides in individual samples show very large ranges in concentration (e.g., Ni ranges from 50 000 ppm to <5 ppm). These large ranges are mainly due to compositional heterogeneities within individual grains due to diffusion and phase separation. Electron microprobe wavelength-dispersive (WDS) mapping of Ni, Co, and Cu show the diffusion trajectories. Nickel and Co have almost identical diffusion trajectories leading to the likely nucleation of pentlandite (Ni,Co,Fe){sub 9}S{sub 8}, and copper diffuses along separate pathways likely toward chalcopyrite nucleation sites (CuFeS{sub 2}). The systematics of Ni and Co in lunar and martian sulfides clearly distinguish the two parent bodies, with martian sulfides displaced to higher Ni and Co values.« less

Graphene-based porous silica sheets impregnated with polyethyleneimine for superior CO2 capture.

PubMed

Yang, Shubin; Zhan, Liang; Xu, Xiaoyue; Wang, Yanli; Ling, Licheng; Feng, Xinliang

2013-04-18

It is demonstrated that graphene-based porous silica sheets can serve as an efficient carrier support for PEI via a simple nanocasting technology. The resulting materials possess thin nature, high PEI loading content and high thermal-conductivity. Such features are favorable for the efficient diffusion and adsorption of CO2 as well as the rapid thermal transfer during the CO2 capture process. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Distance-dependent radiation chemistry: Oxidation versus hydrogenation of CO in electron-irradiated H2O/CO/H2O ices

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

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflection-absorption spectroscopy (IRAS) as function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than ~ 15 ML, CO oxidation dominates over the sequential hydrogenation of CO to methanol (CH3OH), and CO2 is the major product of CO oxidation, consistent with previous observations. At its highest yield, CO2 accounts for ~45% of all the reactedmore » CO. Another oxidation product is identified as the formate anion (HCO2-). In contrast, for CO buried more than ~ 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate are not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on pre-irradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.« less

Thermal diffusivity of Bi 2Sr 2CaCu 2O 8 single crystals

NASA Astrophysics Data System (ADS)

Wu, X. D.; Fanton, J. G.; Kino, G. S.; Ryu, S.; Mitzi, D. B.; Kapitulnik, A.

1993-12-01

We have made direct measurements of the temperature dependence of the thermal diffusivity along all three axes of a single- crystal Bi 2Ca 2SrCu 2O 8 superconductor. We find that the thermal diffusivity is enhanced dramatically along the Cu-O planes below Tc. From our results, we estimate a 40% electronic contribution to the diffusivity along the Cu-O planes. At room temperature the total anisotropy in thermal diffusivity is 7:1, while the lattice contribution has only a 4.2:1 anisotropy.

Ultrahigh-density sub-10 nm nanowire array formation via surface-controlled phase separation.

PubMed

Tian, Yuan; Mukherjee, Pinaki; Jayaraman, Tanjore V; Xu, Zhanping; Yu, Yongsheng; Tan, Li; Sellmyer, David J; Shield, Jeffrey E

2014-08-13

We present simple, self-assembled, and robust fabrication of ultrahigh density cobalt nanowire arrays. The binary Co-Al and Co-Si systems phase-separate during physical vapor deposition, resulting in Co nanowire arrays with average diameter as small as 4.9 nm and nanowire density on the order of 10(16)/m(2). The nanowire diameters were controlled by moderating the surface diffusivity, which affected the lateral diffusion lengths. High resolution transmission electron microscopy reveals that the Co nanowires formed in the face-centered cubic structure. Elemental mapping showed that in both systems the nanowires consisted of Co with undetectable Al or Si and that the matrix consisted of Al with no distinguishable Co in the Co-Al system and a mixture of Si and Co in the Co-Si system. Magnetic measurements clearly indicate anisotropic behavior consistent with shape anisotropy. The dynamics of nanowire growth, simulated using an Ising model, is consistent with the experimental phase and geometry of the nanowires.

Gallium diffusion in zinc oxide via the paired dopant-vacancy mechanism

NASA Astrophysics Data System (ADS)

Sky, T. N.; Johansen, K. M.; Riise, H. N.; Svensson, B. G.; Vines, L.

2018-02-01

Isochronal and isothermal diffusion experiments of gallium (Ga) in zinc oxide (ZnO) have been performed in the temperature range of 900-1050 °C. The samples used consisted of a sputter-deposited and highly Ga-doped ZnO film at the surface of a single-crystal bulk material. We use a novel reaction diffusion (RD) approach to demonstrate that the diffusion behavior of Ga in ZnO is consistent with zinc vacancy (VZn) mediation via the formation and dissociation of GaZnVZn complexes. In the RD modeling, experimental diffusion data are fitted utilizing recent density-functional-theory estimates of the VZn formation energy and the binding energy of GaZnVZn. From the RD modeling, a migration energy of 2.3 eV is deduced for GaZnVZn, and a total/effective activation energy of 3.0 eV is obtained for the Ga diffusion. Furthermore, and for comparison, employing the so-called Fair model, a total/effective activation energy of 2.7 eV is obtained for the Ga diffusion, reasonably close to the total value extracted from the RD-modeling.

Alveolar ventilation to perfusion heterogeneity and diffusion impairment in a mathematical model of gas exchange

NASA Technical Reports Server (NTRS)

Vidal Melo, M. F.; Loeppky, J. A.; Caprihan, A.; Luft, U. C.

1993-01-01

This study describes a two-compartment model of pulmonary gas exchange in which alveolar ventilation to perfusion (VA/Q) heterogeneity and impairment of pulmonary diffusing capacity (D) are simultaneously taken into account. The mathematical model uses as input data measurements usually obtained in the lung function laboratory. It consists of two compartments and an anatomical shunt. Each compartment receives fractions of alveolar ventilation and blood flow. Mass balance equations and integration of Fick's law of diffusion are used to compute alveolar and blood O2 and CO2 values compatible with input O2 uptake and CO2 elimination. Two applications are presented. The first is a method to partition O2 and CO2 alveolar-arterial gradients into VA/Q and D components. The technique is evaluated in data of patients with chronic obstructive pulmonary disease (COPD). The second is a theoretical analysis of the effects of blood flow variation in alveolar and blood O2 partial pressures. The results show the importance of simultaneous consideration of D to estimate VA/Q heterogeneity in patients with diffusion impairment. This factor plays an increasing role in gas alveolar-arterial gradients as severity of COPD increases. Association of VA/Q heterogeneity and D may produce an increase of O2 arterial pressure with decreasing QT which would not be observed if only D were considered. We conclude that the presented computer model is a useful tool for description and interpretation of data from COPD patients and for performing theoretical analysis of variables involved in the gas exchange process.

Experimental study on effects of geologic heterogeneity in enhancing dissolution trapping of supercritical CO2

NASA Astrophysics Data System (ADS)

Agartan, Elif; Trevisan, Luca; Cihan, Abdullah; Birkholzer, Jens; Zhou, Quanlin; Illangasekare, Tissa H.

2015-03-01

Dissolution trapping is one of the primary mechanisms that enhance the storage security of supercritical carbon dioxide (scCO2) in saline geologic formations. When scCO2 dissolves in formation brine produces an aqueous solution that is denser than formation brine, which leads to convective mixing driven by gravitational instabilities. Convective mixing can enhance the dissolution of CO2 and thus it can contribute to stable trapping of dissolved CO2. However, in the presence of geologic heterogeneities, diffusive mixing may also contribute to dissolution trapping. The effects of heterogeneity on mixing and its contribution to stable trapping are not well understood. The goal of this experimental study is to investigate the effects of geologic heterogeneity on mixing and stable trapping of dissolved CO2. Homogeneous and heterogeneous media experiments were conducted in a two-dimensional test tank with various packing configurations using surrogates for scCO2 (water) and brine (propylene glycol) under ambient pressure and temperature conditions. The results show that the density-driven flow in heterogeneous formations may not always cause significant convective mixing especially in layered systems containing low-permeability zones. In homogeneous formations, density-driven fingering enhances both storage in the deeper parts of the formation and contact between the host rock and dissolved CO2 for the potential mineralization. On the other hand, for layered systems, dissolved CO2 becomes immobilized in low-permeability zones with low-diffusion rates, which reduces the risk of leakage through any fault or fracture. Both cases contribute to the permanence of the dissolved plume in the formation.

Atomistic Simulation Studies of Cholesteryl Oleates: Model for the Core of Lipoprotein Particles

PubMed Central

Heikelä, Mikko; Vattulainen, Ilpo; Hyvönen, Marja T.

2006-01-01

We have conducted molecular dynamics simulations to gain insight into the atomic-scale properties of an isotropic system of cholesteryl oleate (CO) molecules. Cholesteryl esters are major constituents of low density lipoprotein particles, the key players in the formation of atherosclerosis, as well as the storage form of cholesterol. Here the aim is to clarify structural and dynamical properties of CO molecules under conditions, which are suggestive of those in the core of low density lipoprotein particles. The simulations in the fluid phase indicate that the system of CO molecules is characterized by an absence of translational order, as expected, while the orientational order between distinct CO molecules is significant at short distances, persisting over a molecular size. As for intramolecular properties, the bonds along the oleate chain are observed to be weakly ordered with respect to the sterol structure, unlike the bonds along the short hydrocarbon chain of cholesterol where the ordering is significant. The orientational distribution of the oleate chain as a whole with respect to the sterol moiety is of broad nature, having a major amount of extended and a less considerable proportion of bended structures. Distinct transient peaks at specific angles also appear. The diffusion of CO molecules is found to be a slow process and characterized by a diffusion coefficient of the order of 2 × 10−9 cm2/s. This is considerably slower than diffusion, e.g., in ordered domains of lipid membranes rich in sphingomyelin and cholesterol. Analysis of the rotational diffusion rates and trans-to-gauche transition rates yield results consistent with experiments. PMID:16399839

Consequences of switching from a fixed 2 : 1 ratio of amoxicillin/clavulanate (CLSI) to a fixed concentration of clavulanate (EUCAST) for susceptibility testing of Escherichia coli.

PubMed

Leverstein-van Hall, Maurine A; Waar, Karola; Muilwijk, Jan; Cohen Stuart, James

2013-11-01

The CLSI recommends a fixed 2 : 1 ratio of co-amoxiclav for broth microdilution susceptibility testing of Enterobacteriaceae, while EUCAST recommends a fixed 2 mg/L clavulanate concentration. The aims of this study were: (i) to determine the influence of a switch from CLSI to EUCAST methodology on Escherichia coli susceptibility rates; (ii) to compare susceptibility results obtained using EUCAST-compliant microdilution with those from disc diffusion and the Etest; and (iii) to evaluate the clinical outcome of patients with E. coli sepsis treated with co-amoxiclav in relation to the susceptibility results obtained using either method. Resistance rates were determined in three laboratories that switched from CLSI to EUCAST cards with the Phoenix system (Becton Dickinson) as well as in 17 laboratories that continued to use CLSI cards with the VITEK 2 system (bioMérieux). In one laboratory, isolates were simultaneously tested by both the Phoenix system and either disc diffusion (n = 471) or the Etest (n = 113). Medical and laboratory records were reviewed for E. coli sepsis patients treated with co-amoxiclav monotherapy. Only laboratories that switched methodology showed an increase in resistance rates - from 19% in 2010 to 31% in 2011 (P < 0.0001). All isolates that tested susceptible by microdilution were also susceptible by disc diffusion or the Etest, but of 326 isolates that tested resistant by microdilution, 43% and 59% tested susceptible by disc diffusion and the Etest, respectively. Among the 89 patients included there was a better correlation between clinical response and measured MICs using the Phoenix system than the Etest. EUCAST methodology resulted in higher co-amoxiclav E. coli resistance rates than CLSI methodology, but correlated better with clinical outcome. EUCAST-compliant microdilution and disc diffusion provided discrepant results.

Crustal migration of CO2-rich magmatic fluids recorded by tree-ring radiocarbon and seismicity at Mammoth Mountain, CA, USA

USGS Publications Warehouse

Lewicki, Jennifer L.; Hilley, George E.; Shelly, David R.; King, John C.; McGeehin, John P.; Mangan, Margaret T.; Evans, William C.

2014-01-01

Unrest at Mammoth Mountain over the past several decades, manifest by seismicity, ground deformation, diffuse CO2 emissions, and elevated 3He/4He ratios in fumarolic gases has been driven by the release of CO2-rich fluids from basaltic intrusions in the middle to lower crust. Recent unrest included the occurrence of three lower-crustal (32–19 km depth) seismic swarms beneath Mammoth Mountain in 2006, 2008 and 2009 that were consistently followed by peaks in the occurrence rate of shallow (≤10 km depth) earthquakes. We measured 14C in the growth rings (1998–2012) of a tree growing in the largest (∼0.3 km2) area of diffuse CO2 emissions on Mammoth Mountain (the Horseshoe Lake tree kill; HLTK) and applied atmospheric CO2 concentration source area modeling to confirm that the tree was a reliable integrator of magmatic CO2 emissions over most of this area. The tree-ring 14C record implied that magmatic CO2 emissions from the HLTK were relatively stable from 1998 to 2009, nearly doubled from 2009 to 2011, and then declined by the 2012 growing season. The initial increase in CO2 emissions was detected during the growing season that immediately followed the largest (February 2010) peak in the occurrence rate of shallow earthquakes. Migration of CO2-rich magmatic fluids may have driven observed patterns of elevated deep, then shallow seismicity, while the relationship between pore fluid pressures within a shallow (upper 3 km of crust) fluid reservoir and permeability structure of the reservoir cap rock may have controlled the temporal pattern of surface CO2 emissions.

Gas sensing properties and in situ diffuse reflectance infrared Fourier transform spectroscopy study of trichloroethylene adsorption and reactions on SnO2 films

NASA Astrophysics Data System (ADS)

Zhang, Zhenxin; Huang, Kaijin; Yuan, Fangli; Xie, Changsheng

2014-05-01

The detection of trichloroethylene has attracted much attention because it has an important effect on human health. The sensitivity of the SnO2 flat-type coplanar gas sensor arrays to 100 ppm trichloroethylene in air was investigated. The adsorption and surface reactions of trichloroethylene were investigated at 100-200 °C by in-situ diffuse reflection Fourier transform infrared spectroscopy (DIRFTS) on SnO2 films. Molecularly adsorbed trichloroethylene, dichloroacetyl chloride (DCAC), phosgene, HCl, CO, H2O, CHCl3, Cl2 and CO2 surface species are formed during trichloroethylene adsorption at 100-200 °C. A possible mechanism of the reaction process is discussed.

Diffuse X-ray scattering from benzil, C(14)H(10)O(2): analysis via automatic refinement of a Monte Carlo model.

PubMed

Welberry, T R; Goossens, D J; Edwards, A J; David, W I

2001-01-01

A recently developed method for fitting a Monte Carlo computer-simulation model to observed single-crystal diffuse X-ray scattering has been used to study the diffuse scattering in benzil, diphenylethanedione, C(6)H(5)-CO-CO-C(6)H(5). A model involving 13 parameters consisting of 11 intermolecular force constants, a single intramolecular torsional force constant and a local Debye-Waller factor was refined to give an agreement factor, R = [summation operator omega(Delta I)(2)/summation operator omega I(obs)(2)](1/2), of 14.5% for 101,324 data points. The model was purely thermal in nature. The analysis has shown that the diffuse lines, which feature so prominently in the observed diffraction patterns, are due to strong longitudinal displacement correlations. These are transmitted from molecule to molecule via a network of contacts involving hydrogen bonding of an O atom on one molecule and the para H atom of the phenyl ring of a neighbouring molecule. The analysis also allowed the determination of a torsional force constant for rotations about the single bonds in the molecule. This is the first diffuse scattering study in which measurement of such internal molecular torsion forces has been attempted.

Effects of H{sub 2} and H preferential diffusion and unity Lewis number on superadiabatic flame temperatures in rich premixed methane flames

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

Liu, Fengshan; Guelder, OEmer L.

2005-11-01

The structures of freely propagating rich CH{sub 4}/air and CH{sub 4}/O{sub 2} flames were studied numerically using a relatively detailed reaction mechanism. Species diffusion was modeled using five different methods/assumptions to investigate the effects of species diffusion, in particular H{sub 2} and H, on superadiabatic flame temperature. With the preferential diffusion of H{sub 2} and H accounted for, significant amount of H{sub 2} and H produced in the flame front diffuse from the reaction zone to the preheat zone. The preferential diffusion of H{sub 2} from the reaction zone to the preheat zone has negligible effects on the phenomenon ofmore » superadiabatic flame temperature in both CH{sub 4}/air and CH{sub 4}/O{sub 2} flames. It is therefore demonstrated that the superadiabatic flame temperature phenomenon in rich hydrocarbon flames is not due to the preferential diffusion of H{sub 2} from the reaction zone to the preheat zone as recently suggested by Zamashchikov et al. [V.V. Zamashchikov, I.G. Namyatov, V.A. Bunev, V.S. Babkin, Combust. Explosion Shock Waves 40 (2004) 32]. The suppression of the preferential diffusion of H radicals from the reaction zone to the preheat zone drastically reduces the degree of superadiabaticity in rich CH{sub 4}/O{sub 2} flames. The preferential diffusion of H radicals plays an important role in the occurrence of superadiabatic flame temperature. The assumption of unity Lewis number for all species leads to the suppression of H radical diffusion from the reaction zone to the preheat zone and significant diffusion of CO{sub 2} from the postflame zone to the reaction zone. Consequently, the degree of superadiabaticity of flame temperature is also significantly reduced. Through reaction flux analyses and numerical experiments, the chemical nature of the superadiabatic flame temperature phenomenon in rich CH{sub 4}/air and CH{sub 4}/O{sub 2} flames was identified to be the relative scarcity of H radical, which leads to overshoot of H{sub 2}O and CH{sub 2}CO in CH{sub 4}/air flames and overshoot of H{sub 2}O in CH{sub 4}/O{sub 2} flames.« less

Gas hazard assessment in the touristic area of Levante Beach (Vulcano island, Italy)

NASA Astrophysics Data System (ADS)

Carapezza, Maria Luisa; Di Piazza, Andrea; Gattuso, Alessandro; Ranaldi, Massimo; Sortino, Francesco; Tarchini, Luca

2016-04-01

Since the last eruption occurred at "La Fossa" in 1888-1890, Vulcano remained in a quiescence state characterized by an intense fumarolic activity. The main degassing manifestations are concentrated in La Fossa crater area (high temperature fumaroles) and in the area of Vulcano Porto, between Levante Beach and Faraglioni (medium-low temperature fumaroles). In addition the entire volcanic edifice of La Fossa, its base and the area of Vulcano Porto are characterized by en extensive soil CO2 diffuse degassing. In the last century episodic "crises" have occurred with increase of temperature, gas output and compositional changes of the crater fumaroles indicating an increase of the magmatic component in the discharged fluids. These episodic crises occurred in 1916-1924, in 1988-1993, in 1996 and in 2004-2006. During the period 1988-1990, the accumulation of CO2 in morphological depressions or excavation provoked the death for asphyxiation of two children in the area of Vulcano Porto and of some small animals at the base of the crater area. In April 2015, a child lost his senses while playing at Levante Beach; he was rescued by an air ambulance to the hospital of Lipari. According to the national chronicle (La Repubblica, 22 June 2015), doctors attributed the malaise to a high CO2 air concentration. Soon after this event the Major of Lipari installed at Levante Beach some panels informing tourists on gas hazard. In summer 2015 we performed a geochemical survey of the Levante Beach sector (onshore and offshore) and of the mud pool, estimating the diffuse and viscous gas flux and the air gas concentration in order to evaluate the degassing level. The total gas flux in the Levante Beach area, from 0.3 km2, has been estimated in 1 t/day of CO2 and 16,1 kg/day of H2S; values comparable with those of the 2009 and 2011 campaigns. In addition, a soil CO2 flux survey of the target area at La Fossa crater was performed, ascertaining that the degassing rate was within the range of the inter-crisis period (CO2 = 200 t/day). In the mud pool area, continuous measurements of CO2 and H2S air concentration were also carried out for a period of a week. The CO2 concentration was almost always higher than in the normal unpolluted air. Concentration of H2S displayed high values (maximum of 43 ppm), with the TWA (10 ppm) and STEL (15 ppm) H2S thresholds frequently exceeded. Offshore, gas concentration in atmosphere over the submarine vents of the Levante Beach, displayed extremely high concentrations of H2S (values up to 1000 ppm) and CO2 (8.6 vol.%). these values may cause serious adverse health consequences on the exposed people even in periods when the volcanic activity is not considered high or anomalous.

A MASSIVE MOLECULAR GAS RESERVOIR IN THE z = 5.3 SUBMILLIMETER GALAXY AzTEC-3

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

Riechers, Dominik A.; Scoville, Nicholas Z.; Capak, Peter L.

2010-09-10

We report the detection of CO J = 2{yields}1, 5{yields}4, and 6{yields}5 emission in the highest-redshift submillimeter galaxy (SMG) AzTEC-3 at z = 5.298, using the Expanded Very Large Array and the Plateau de Bure Interferometer. These observations ultimately confirm the redshift, making AzTEC-3 the most submillimeter-luminous galaxy in a massive z {approx_equal} 5.3 protocluster structure in the COSMOS field. The strength of the CO line emission reveals a large molecular gas reservoir with a mass of 5.3 x 10{sup 10}({alpha}{sub CO}/0.8) M {sub sun}, which can maintain the intense 1800 M {sub sun} yr{sup -1} starburst in this systemmore » for at least 30 Myr, increasing the stellar mass by up to a factor of six in the process. This gas mass is comparable to 'typical' z {approx} 2 SMGs and constitutes {approx_gt}80% of the baryonic mass (gas+stars) and 30%-80% of the total (dynamical) mass in this galaxy. The molecular gas reservoir has a radius of <4 kpc and likely consists of a 'diffuse', low-excitation component, containing (at least) 1/3 of the gas mass (depending on the relative conversion factor {alpha}{sub CO}), and a 'dense', high-excitation component, containing {approx}2/3 of the mass. The likely presence of a substantial diffuse component besides highly excited gas suggests different properties between the star-forming environments in z > 4 SMGs and z > 4 quasar host galaxies, which perhaps trace different evolutionary stages. The discovery of a massive, metal-enriched gas reservoir in an SMG at the heart of a large z = 5.3 protocluster considerably enhances our understanding of early massive galaxy formation, pushing back to a cosmic epoch where the universe was less than 1/12 of its present age.« less

Selective Metal Exsolution in BaFe 2-yMy(PO 4) 2 (M = Co 2+, Ni 2+) Solid Solutions

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

Alcover, Ignacio Blazquez; Daviero-Minaud, Sylvie; David, Rénald

2015-08-19

The 2D-Ising ferromagnetic phase BaFe 2+ 2(PO 4) 2 shows exsolution of up to one-third of its iron content (giving BaFe 3+ 1.33(PO 4) 2) under mild oxidation conditions, leading to nanosized Fe 2O 3 exsolved clusters. Here we have prepared BaFe 2–yMy(PO 4) 2 (M = Co 2+, Ni 2+; y = 0, 0.5, 1, 1.5) solid solutions to investigate the feasibility and selectivity of metal exsolution in these mixed metallic systems. For all the compounds, after 600 °C thermal treatment in air, a complete oxidation of Fe 2+ to Fe 3+ leaves stable M 2+ ions, as verifiedmore » by 57Fe Mössbauer spectroscopy, TGA, TEM, microprobe, and XANES. Furthermore, the size of the nanometric α-Fe 2O 3clusters coating the main phase strongly depends on the y M metal concentration. For M-rich phases the iron diffusion is hampered so that a significant fraction of superparamagnetic α-Fe2O3 particles (100% for BaFe 0.5–xCo 1.5(PO 4) 2) was detected even at 78 K. Although Ni 2+and Co 2+ ions tend to block Fe diffusion, the crystal structure of BaFe 0.67Co 1(PO 4) 2demonstrates a fully ordered rearrangement of Fe 3+ and Co 2+ ions after Fe exsolution. We found that the magnetic behaviors of the Fe-depleted materials are mostly dominated by antiferromagnetic exchange, while Co 2+-rich compounds show metamagnetic transitions reminiscent of the BaCo 2(PO 4) 2 soft helicoidal magnet.« less

Gas emission from diffuse degassing structures (DDS) of the Cameroon volcanic line (CVL): Implications for the prevention of CO2-related hazards

NASA Astrophysics Data System (ADS)

Issa; Ohba, T.; Chako Tchamabé, B.; Padrón, E.; Hernández, P.; Eneke Takem, E. G.; Barrancos, J.; Sighomnoun, D.; Ooki, S.; Nkamdjou, Sigha; Kusakabe, M.; Yoshida, Y.; Dionis, S.

2014-08-01

In the mid-1980s, lakes Nyos and Monoun violently released massive gas, mainly magmatic CO2 killing about 1800 people. Subsequent geochemical surveys and social studies indicate that lakes Nyos and Monoun event is cyclic in nature and may occur anywhere in the about 37 other volcanic lakes located in the corridor of the Cameroon volcanic line (CVL). This potential threat motivated us to check if, alike Nyos and Monoun, the internal dynamic of the other lakes is also controlled by inputs of deep-seated-derived CO2 and attempt to measure and provide comprehensive insights on the passive gas emission along the CVL. This knowledge shall contribute to the prevention of volcanic lake-related hazards in Cameroon and the refinement of the Global Carbon Cycle. We used in situ fixation and dry gas phase sampling methods to determine CO2 origin and the concentration, and the accumulation chamber technique to measure diffuse CO2 emission from nine lakes and on soil at Nyos Valley and Mount Manenguba Caldera. The results suggest that, although in minor concentrations (compared to Nyos and Monoun), ranging from 0.56 mmol kg- 1 to 8.75 mmol kg- 1, the bottom waters of some lakes also contain measurable magmatic CO2 with δ13C varies from - 4.42‰ to - 9.16‰ vs. PDB. That finding implies that, under certain circumstances, e.g. increase to volcanic and/or tectonic activities along the CVL, the concerned lakes could develop a Nyos-type behavioural scheme. The diffuse gas emission results indicate that the nine surveyed lakes release approximately 3.69 ± 0.37 kt km- 2 yr- 1 of CO2 to the atmosphere; extrapolation to the approximately 39 volcanic lakes located on the CVL yields an approximate CO2 output of 27.37 ± 0.5 kt km- 2 yr- 1, representing 0.023% of the global CO2 output from volcanic lakes. In addition to the precedent value, the gas removal operation in lakes Nyos and Monoun released approximately 2.52 ± 0.46 × 108 mol km- 2 yr- 1 CO2 to the atmosphere from January 2001 to March 2013, more than double the per-area CO2 released by the Yellowstone volcanic system. The CO2 emission from soil was estimated to be 4.57 ± 1.30 kt km- 2 yr- 1; the soil gas geochemistry of the Mount Manenguba Caldera also indicates a dominant magma-derived CO2 (mean δ13C = - 8.6‰ vs. VPDB).

Studies of the Terrestrial Molecular Oxygen and Carbon Cycles in Sand Dune Gases and in Biosphere 2.

NASA Astrophysics Data System (ADS)

Severinghaus, Jeffrey Peck

Molecular oxygen in the atmosphere is coupled tightly to the terrestrial carbon cycle by the processes of photosynthesis, respiration, and burning. This dissertation examines different aspects of this coupling in four chapters. Chapter 1 explores the feasibility of using air from sand dunes to reconstruct atmospheric O_2 composition centuries ago. Such a record would reveal changes in the mass of the terrestrial biosphere, after correction for known fossil fuel combustion, and constrain the fate of anthropogenic CO_2. Test drilling in sand dunes shows that sand dunes do contain old air, as shown by the concentrations of chlorofluorocarbons and ^{85}Kr. Diffusion is shown to dominate mixing rather than advection. However, biological respiration in dunes corrupts the signal, and isotopic analysis of O_2 and N _2 shows that fractionation of the gases precludes use of sand dunes as archives. Chapter 2 further explores this fractionation, revealing a previously unknown "water vapor flux fractionation" process. A flux of water vapor out of the moist dune into the dry desert air sweeps out the other gases, forcing them to diffuse back into the dune. The heavy isotopes of N_2 and O_2 diffuse more slowly, creating a steady state depletion of heavy isotopes in the dune interior. Molecular diffusion theory and a laboratory simulation of the effect agree well with the observations. Additional fractionation of the dune air occurs via thermal diffusion and gravitational settling, and it is predicted that soil gases in general will enjoy all three effects. Chapter 3 examines the cause of a mysterious drop in O _2 concentrations in the closed ecosystem of Biosphere 2, located near Tucson, Arizona. The organic -rich soil manufactured for the experiment is shown to be the culprit, with CO_2 produced by bacterial respiration of the organic matter reacting with the extensive concrete surfaces inside. Chapter 4 examines the O_2:C stoichiometry of terrestrial soil respiration and photosynthesis, in the context of using atmospheric O_2 measurements to constrain the size of the "missing sink" of CO_2. Direct measurements of soil respiration and biomatter elemental abundance suggest a value of 1.1 +/- 0.05 oxygen molecules per CO_2 molecule.

The abundance of CO in diffuse interstellar clouds - An ultraviolet survey

NASA Technical Reports Server (NTRS)

Federman, S. R.; Glassgold, A. E.; Jenkins, E. B.; Shaya, E. J.

1980-01-01

CO was detected in 17 directions and its upper limits were estimated in 21 directions by a UV survey carried out with the Copernicus satellite in the C-X 1088 A and E-X 1076 A lines toward 48 bright stars. The CO column densities range from 10 to the 12th to 10 to the 17th/sq cm and correlate with C I and H2. The tendency of the C I/CO ratio to be about 10 follows the ratio of particular atomic and molecular cross-sections and the physical parameters of interstellar clouds. Finally, the connection between UV observations in diffuse clouds and radio observations of (C-13)O in dark clouds is discussed.

Encapsulation of concentrated hemoglobin solution in phospholipid vesicles retards the reaction with NO, but not CO, by intracellular diffusion barrier.

PubMed

Sakai, Hiromi; Sato, Atsushi; Masuda, Kaoru; Takeoka, Shinji; Tsuchida, Eishun

2008-01-18

One physiological significance of the red blood cell (RBC) structure is that NO binding of Hb is retarded by encapsulation with the cell membrane. To clarify the mechanism, we analyzed Hb-vesicles (HbVs) with different intracellular Hb concentrations, [Hb](in), and different particle sizes using stopped-flow spectrophotometry. The apparent NO binding rate constant, k(on)('(NO)), of HbV at [Hb](in) = 1 g/dl was 2.6 x 10(7) m(-1) s(-1), which was almost equal to k(on)((NO)) of molecular Hb, indicating that the lipid membrane presents no obstacle for NO binding. With increasing [Hb](in) to 35 g/dl, k(on)('(NO)) decreased to 0.9 x 10(7) m(-1) s(-1), which was further decreased to 0.5 x 10(7) m(-1) s(-1) with enlarging particle diameter from 265 to 452 nm. For CO binding, which is intrinsically much slower than NO binding, k(on)('(CO)) did not change greatly with [Hb](in) and the particle diameter. Results obtained using diffusion simulations coupled with elementary binding reactions concur with these tendencies and clarify that NO is trapped rapidly by Hb from the interior surface region to the core of HbV at a high [Hb](in), retarding NO diffusion toward the core of HbV. In contrast, slow CO binding allows time for further CO-diffusion to the core. Simulations extrapolated to larger particles (8 mum) showing retardation even for CO binding. The obtained k(on)('(NO)) and k(on)('(NO)) yield values similar to those reported for RBCs. In summary, the intracellular, not extracellular, diffusion barrier is predominant due to the rapid NO binding that induces a rapid sink of NO from the interior surface to the core, retarding further NO diffusion and binding.

Experimental dehydration of natural obsidian and estimation of DH2O at low water contents

NASA Technical Reports Server (NTRS)

Jambon, A.; Zhang, Y.; Stolper, E. M.

1992-01-01

Water diffusion experiments were carried out by dehydrating rhyolitic obsidian from Valles Caldera (New Mexico, USA) at 510-980 degrees C. The starting glass wafers contained approximately 0.114 wt% total water, lower than any glasses previously investigated for water diffusion. Weight loss due to dehydration was measured as a function of experiment duration, which permits determination of mean bulk water diffusivity, mean Dw. These diffusivities are in the range of 2.6 to 18 X 10(-14) m2/s and can be fit with the following Arrhenius equation: ln mean Dw (m2/s) = -(25.10 +/- 1.29) - (46,480 +/- 11,400) (J/mol) / RT, except for two replicate runs at 510 degrees C which give mean Dw values much lower than that defined by the above equation. When interpreted according to a model of water speciation in which molecular H2O is the diffusing species with concentration-independent diffusivity while OH units do not contribute to the transport but react to provide H2O, the data (except for the 510 degrees C data) are in agreement with extrapolation from previous results and hence extend the previous data base and provide a test of the applicability of the model to very low water contents. Mean bulk water diffusivities are about two orders of magnitude less than molecular H2O diffusivities because the fraction of molecular H2O out of total water is very small at 0.114 wt% total water and less. The 510 degrees C experimental results can be interpreted as due to slow kinetics of OH to H2O interconversion at low temperatures.

Experimental dehydration of natural obsidian and estimation of DH2O at low water contents.

PubMed

Jambon, A; Zhang, Y; Stolper, E M

1992-01-01

Water diffusion experiments were carried out by dehydrating rhyolitic obsidian from Valles Caldera (New Mexico, USA) at 510-980 degrees C. The starting glass wafers contained approximately 0.114 wt% total water, lower than any glasses previously investigated for water diffusion. Weight loss due to dehydration was measured as a function of experiment duration, which permits determination of mean bulk water diffusivity, mean Dw. These diffusivities are in the range of 2.6 to 18 X 10(-14) m2/s and can be fit with the following Arrhenius equation: ln mean Dw (m2/s) = -(25.10 +/- 1.29) - (46,480 +/- 11,400) (J/mol) / RT, except for two replicate runs at 510 degrees C which give mean Dw values much lower than that defined by the above equation. When interpreted according to a model of water speciation in which molecular H2O is the diffusing species with concentration-independent diffusivity while OH units do not contribute to the transport but react to provide H2O, the data (except for the 510 degrees C data) are in agreement with extrapolation from previous results and hence extend the previous data base and provide a test of the applicability of the model to very low water contents. Mean bulk water diffusivities are about two orders of magnitude less than molecular H2O diffusivities because the fraction of molecular H2O out of total water is very small at 0.114 wt% total water and less. The 510 degrees C experimental results can be interpreted as due to slow kinetics of OH to H2O interconversion at low temperatures.

Novel mesoporous MnCo2O4 nanorods as oxygen reduction catalyst at neutral pH in microbial fuel cells.

PubMed

Kumar, Ravinder; Singh, Lakhveer; Wahid, Zularisam Ab; Mahapatra, Durga Madhab; Liu, Hong

2018-04-01

The aim of this work was to evaluate the comparative performance of hybrid metal oxide nanorods i.e. MnCo 2 O 4 nanorods (MCON) and single metal oxide nanorods i.e. Co 3 O 4 nanorods (CON) as oxygen reduction catalyst in microbial fuel cells (MFC). Compared to the single metal oxide, the hybrid MCON exhibited a higher BET surface area and provided additional positively charged ions, i.e., Co 2+ /Co 3+ and Mn 3+ /Mn 4+ on its surfaces, which increased the electro-conductivity of the cathode and improved the oxygen reduction kinetics significantly, achieved an i o of 6.01 A/m 2 that was 12.4% higher than CON. Moreover, the porous architecture of MCON facilitated the diffusion of electrolyte, reactants and electrons during the oxygen reduction, suggested by lower diffusion (R d ), activation (R act ) and ohmic resistance (R ohm ) values. This enhanced oxygen reduction by MCON boosted the power generation in MFC, achieving a maximum power density of 587 mW/m 2 that was ∼29% higher than CON. Published by Elsevier Ltd.

In-vehicle carbon dioxide concentration in commuting cars in Bangkok, Thailand.

PubMed

Luangprasert, Maytat; Vasithamrong, Chainarin; Pongratananukul, Suphasit; Chantranuwathana, Sunhapos; Pumrin, Suree; De Silva, I P D

2017-05-01

It is known that in-vehicle carbon dioxide (CO 2 ) concentration tends to increase due to occupant exhalation when the HVAC (heating, ventilation, and air conditioning) air is in recirculation mode. Field experiments were conducted to measure CO 2 concentration during typical commute in Bangkok, Thailand. The measured concentrations agreed with the concentration predicted using first-order mass balance equation, in both recirculating and outside air modes. The long-term transient decay of the concentration when the vehicle was parked and the HVAC system was turned off was also studied. This decay was found to follow Fickian diffusion process. The paper also provides useful operational details of the automotive HVAC system and fresh air ventilation exchange between cabin interior and exterior. Drivers in tropical Asian countries typically use HVAC recirculation mode in their automobiles. This behavior leads to excessive buildup of cabin CO 2 concentration levels. The paper describes the CO 2 buildup in a typical commute in Bangkok, Thailand. Auto manufacturers can potentially take measures to alleviate such high concentration levels. The paper also discusses the diffusion of CO 2 through the vehicle envelope, an area that has never been investigated before.

Infrared study of CO{sub 2} sorption over 'molecular basket' sorbent consisting of polyethylenimine-modified mesoporous molecular sieve

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

Wang, X.X.; Schwartz, V.; Clark, J.C.

2009-04-15

An infrared study has been conducted on CO{sub 2} sorption into nanoporous CO{sub 2} 'molecular basket' sorbents prepared by loading polyethylenimine (PEI) into mesoporous molecular sieve SBA-15. IR results from DRIFTS showed that a part of loaded PEI is anchored on the surface of SBA-15 through the interaction between amine groups and isolated surface silanol groups. Raising the temperature from 25 to 75{sup o}C increased the molecular flexibility of PEI loaded in the mesopore channels, which may partly contribute to the increase of CO{sub 2} sorption capacity at higher temperatures. CO{sub 2} sorption/desorption behavior studied by in situ transmission FTIRmore » showed that CO{sub 2} is sorbed on amine sites through the formation of alkylammonium carbamates and absorbed into the multiple layers of PEI located in mesopores of SBA-15. A new observation by in situ IR is that two broad IR bands emerged at 2450 and 2160 cm{sup -1} with CO{sub 2} flowing over PEI(50)/SBA-15, which could be attributed to chemically sorbed CO{sub 2} species on PEI molecules inside the mesopores of SBA-15. The intensities of these two bands also increased with increasing CO{sub 2} exposure time and with raising CO{sub 2} sorption temperature. By comparison of the CO{sub 2} sorption rate at 25 and 75{sup o}C in terms of differential IR intensities, it was found that CO{sub 2} sorption over molecular basket sorbent includes two rate regimes which suggest two distinct steps: rapid sorption on exposed outer surface layers of PEI (controlled by sorption affinity or thermodynamics) and the diffusion and sorption inside the bulk of multiple layers of PEI (controlled by diffusion). The sorption of CO{sub 2} is reversible at 75{sup o}C.« less

A practical CO2 flux remote sensing technique

NASA Astrophysics Data System (ADS)

Queisser, Manuel; Burton, Mike

2017-04-01

An accurate quantification of CO2 flux from both natural and anthropogenic sources is of great interest in various areas of the Earth, environmental and atmospheric sciences. As emitted excess CO2 quickly dilutes into the 400 ppm ambient CO2 concentration and degassing often occurs diffusively, measuring CO2 fluxes is challenging. Therefore, fluxes are usually derived from grids of in-situ measurements, which are labour intensive measurements. Other than a safe measurement distance, remote sensing offers quick, spatially integrated and thus a more thorough measurement of gas fluxes. Active remote sensing combines these merits with operation independent of sunlight or clear sky conditions. Due to their weight and size, active remote sensing platforms for CO2, such as LIDAR, cannot easily be applied in the field or transported overseas. Moreover, their complexity requires a rather lengthy setup procedure to be undertaken by skilled personal. To meet the need for a rugged, practical CO2 remote sensing technique to scan volcanic plumes, we have developed the CO2 LIDAR. It measures 1-D column densities of CO2 with sufficient sensitivity to reveal the contribution of magmatic CO2. The CO2 LIDAR has been mounted inside a small aircraft and used to measure atmospheric column CO2 concentrations between the aircraft and the ground. It was further employed on the ground, measuring CO2 emissions from mud volcanism. During the measurement campaign the CO2 LIDAR demonstrated reliability, portability, quick set-up time (10 to 15 min) and platform independence. This new technique opens the possibility of rapid, comprehensive surveys of point source, open-vent CO2 emissions, as well as emissions from more diffuse sources such as lakes and fumarole fields. Currently, within the proof-of-concept ERC project CarbSens, a further reduction in size, weight and operational complexity is underway with the goal to commercialize the platform. Areas of potential applications include fugitive CO2 detection at carbon capture and storage sites, volcano monitoring and bottom-up quantification of CO2 fluxes, such as from urban areas or natural sources.

First principles calculations of ceramics surfaces and interfaces: Examples from beta-silicon nitride and alpha-alumina

NASA Astrophysics Data System (ADS)

Dunn, Jennifer Synowczynski

The goal of this thesis was to use first principles calculations to provide a fundamental understanding at the atomistic level of the mechanisms (e.g. structural relaxations of ceramic surfaces/interfaces, charge transfer reactions, adsorption and dissociation phenomena, localized debonding) behind macroscopic behavior in ceramics (e.g. fracture toughness, corrosion, catalysis). This thesis includes the results from three independent Density Functional Theory (DFT) studies of beta-Si3N4 and alpha-Al2O 3. Due to the computational complexity of first principles calculations, the models in this thesis do not consider temperature or pressure effects and are limited to describing the behavior of systems containing less than 200 atoms. In future studies, these calculations can be used to train a reactive molecular dynamics force field (REAXFF) so that larger scale phenomena including temperature effects can be explicitly simulated. In the first study, the effect of over 30 dopants on the stability of the interface between beta-Si3N4 grains and the intergranular glassy SiON film (IGF) was investigated. The dopants chosen not only represented commonly known glass modifiers and sintering aides but also enabled us to search for dependencies based on atomic size and electronic orbital configuration. To ensure that the approximations used in our model captured the key physical phenomena occurring on the beta-Si3N4 (100) surface and at the Si3N4/ IGF interface, we compared to experimental data (i.e. High Angle Annual Dark Field-Scanning Transmission Electron Microscopy atomic positions and fracture toughness values (Mikijelj B., 2009)). We identified a computational metric (the interfacial stability factor S) which correlates with experimentally measured fracture toughness values. The interfacial stability factor S is defined as the binding energy of the doped system minus the binding energy of the undoped system, where the binding energy is the total energy of the system minus the sum of the energies of the constituent atoms. In the second study, we performed constrained geometry barrier calculations of the interaction of CO with the (001) beta-Si3N4 surface to answer the following questions: (1) Does the CO combustion product interact with the Si3N4 surface and if so, what is the mechanism? (2) Once adsorbed, can CO further dissociate into isolated surface active C and O species? (3) Is it more energetically favorable for C to diffuse into the bulk beta-Si3N4 or along its surface? and (4) What is the barrier to C diffusing into an amorphous SiO2 intergranular film? Our calculations indicated that CO spontaneously adsorbs to the (001) beta-Si 3N4 surface. However, at ambient temperatures, further dissociation into isolated surface adsorbed C and O species was not thermodynamically or kinetically feasible. The barrier to C diffusing interstitially 1A and 5A into the bulk crystalline lattice is 2.12 and 4.42 eV respectively for a defect free, clean surface. However, the barrier for C surface diffusion is much smaller, ˜ 0.87 eV. Therefore, we concluded that surface is rich in C which can diffuse to the Si3N4/SiO2 interface and contribute to chemical erosion near the grain boundary interface. In the final study, we created a DFT model to investigate the 'inverse spillover effect' that occurs during hydrogen combustion on catalytically active Pt clusters supported by alpha-Al2O3. Our results indicated that the dissociation of O2 was not thermodynamically favored on the alpha-Al2O3 surface. However, both H2 and H2O dissociated, forming hydroxyls with oxygen atoms in the second atomic layer. Once dissociated, the oxygen species could diffuse locally but encountered a large barrier to long-range surface diffusion in the absence of defects or other species. In contrast, the barrier to the long-range surface diffusion of hydrogen was modest under ideal conditions. We also identified several adsorption and dissociation products for Pt, Pt-O [ads] Pt3, O, H, O2, H2, and H 2O on the alpha-Al2O3 (0001) surface and described how these structures changed the surface reconstruction. Specifically, we concluded that the adsorption of molecular H2O, atomic Pt, and Pt trimers changed the termination for the alpha-Al2O3 (0001) surface from aluminum to oxygen terminated in the vicinity of the adsorption products. This should have a dramatic affect on catalytic activity and surface diffusion. We confirmed this for O surface diffusion near surface Al where the presence of atomic Pt decreased the diffusion barrier from 1.17 to 0.22 eV.

Simulation of gas diffusion and sorption in nanoceramic semiconductors

NASA Astrophysics Data System (ADS)

Skouras, E. D.; Burganos, V. N.; Payatakes, A. C.

1999-05-01

Gas diffusion and sorption in nanoceramic semiconductors are studied using atomistic simulation techniques and numerical results are presented for a variety of sorbate-sorbent systems. SnO2, BaTiO3, CuO, and MgO substrates are built on the computer using lattice constants and atomic parameters that have been either measured or computed by ab initio methods. The Universal force field is employed here for the description of both intramolecular and nonbonded interactions for various gas sorbates, including CH4, CO, CO2, and O2, pure and in binary mixtures. Mean residence times are determined by molecular dynamics computations, whereas the Henry constant and the isosteric heat of adsorption are estimated by a Monte Carlo technique. The effects of surface hydroxylation on the diffusion and sorption characteristics are quantified and discussed in view of their significance in practical gas sensing applications. The importance of fast diffusion on the response time of the sensitive layer and of the sorption efficiency on the overall sensitivity as well as the potential synergy of the two phenomena are discussed.

Excess Diffuse Light Absorption in Upper Mesophyll Limits CO2 Drawdown and Depresses Photosynthesis1[OPEN

PubMed Central

Gilbert, Matthew E.; McElrone, Andrew J.

2017-01-01

In agricultural and natural systems, diffuse light can enhance plant primary productivity due to deeper penetration into and greater irradiance of the entire canopy. However, for individual sun-grown leaves from three species, photosynthesis is actually less efficient under diffuse compared with direct light. Despite its potential impact on canopy-level productivity, the mechanism for this leaf-level diffuse light photosynthetic depression effect is unknown. Here, we investigate if the spatial distribution of light absorption relative to electron transport capacity in sun- and shade-grown sunflower (Helianthus annuus) leaves underlies its previously observed diffuse light photosynthetic depression. Using a new one-dimensional porous medium finite element gas-exchange model parameterized with light absorption profiles, we found that weaker penetration of diffuse versus direct light into the mesophyll of sun-grown sunflower leaves led to a more heterogenous saturation of electron transport capacity and lowered its CO2 concentration drawdown capacity in the intercellular airspace and chloroplast stroma. This decoupling of light availability from photosynthetic capacity under diffuse light is sufficient to generate an 11% decline in photosynthesis in sun-grown but not shade-grown leaves, primarily because thin shade-grown leaves similarly distribute diffuse and direct light throughout the mesophyll. Finally, we illustrate how diffuse light photosynthetic depression could overcome enhancement in canopies with low light extinction coefficients and/or leaf area, pointing toward a novel direction for future research. PMID:28432257

Excess Diffuse Light Absorption in Upper Mesophyll Limits CO2 Drawdown and Depresses Photosynthesis.

PubMed

Earles, J Mason; Théroux-Rancourt, Guillaume; Gilbert, Matthew E; McElrone, Andrew J; Brodersen, Craig R

2017-06-01

In agricultural and natural systems, diffuse light can enhance plant primary productivity due to deeper penetration into and greater irradiance of the entire canopy. However, for individual sun-grown leaves from three species, photosynthesis is actually less efficient under diffuse compared with direct light. Despite its potential impact on canopy-level productivity, the mechanism for this leaf-level diffuse light photosynthetic depression effect is unknown. Here, we investigate if the spatial distribution of light absorption relative to electron transport capacity in sun- and shade-grown sunflower ( Helianthus annuus ) leaves underlies its previously observed diffuse light photosynthetic depression. Using a new one-dimensional porous medium finite element gas-exchange model parameterized with light absorption profiles, we found that weaker penetration of diffuse versus direct light into the mesophyll of sun-grown sunflower leaves led to a more heterogenous saturation of electron transport capacity and lowered its CO 2 concentration drawdown capacity in the intercellular airspace and chloroplast stroma. This decoupling of light availability from photosynthetic capacity under diffuse light is sufficient to generate an 11% decline in photosynthesis in sun-grown but not shade-grown leaves, primarily because thin shade-grown leaves similarly distribute diffuse and direct light throughout the mesophyll. Finally, we illustrate how diffuse light photosynthetic depression could overcome enhancement in canopies with low light extinction coefficients and/or leaf area, pointing toward a novel direction for future research. © 2017 American Society of Plant Biologists. All Rights Reserved.

Can we relate respiration rates of bark and wood with tissue nitrogen concentrations and branch-level CO2 fluxes across woody species?

NASA Astrophysics Data System (ADS)

Eller, A. S.; Wright, I.; Cernusak, L. A.

2013-12-01

Respiration from above-ground woody tissue is generally responsible for 5-15% of ecosystem respiration (~ 30% of total above-ground respiration). The CO2 respired by branches comes from both the sapwood and the living layers within the bark, but because there is considerable movement of respired CO2 within woody tissues (e.g. in the transpiration stream), and because the bark can present a considerable barrier to CO2 diffusion, it can be difficult to interpret measured CO2 efflux from intact branches in relation to the respiration rates of the component tissues, and to relative mass allocation to each. In this study we investigated these issues in 15 evergreen tree and shrub species native to the Sydney area in eastern Australia. We measured CO2 efflux and light-dependent refixation of respired CO2 in photosynthetic bark from the exterior surfaces of branches (0.5-1.5 cm in diameter), and measured the tissue-specific respiration rates of the bark and wood from those same branches. We also measured the nitrogen content and tissue density of the wood and bark to determine: 1) Among species, what is the relationship between %N and tissue respiration? 2) How is photosynthetic refixation of CO2 related to respiration and %N in the bark and underlying wood? and 3) What is the relationship between branch CO2 efflux and the respiration rates of the underlying wood and bark that make up the branch? Across the 15 species %N was a better predictor of respiration in wood than in bark. CO2 efflux measured from the exterior of the stem in the dark was positively correlated with photosynthetic refixation and explained ~40% of the variation in rates of refixation. Refixation rates were not strongly related to bark or wood %N. Differences among species in CO2 efflux rates were not well explained by differences in bark or wood %N and there was a stronger relationship between bark respiration and CO2 efflux than between wood respiration and CO2 efflux. These results suggest that the CO2 efflux rates measured on branch exterior surfaces may be driven more strongly by bark respiration than wood respiration and a better understanding of bark respiration will increase our ability to predict CO2 efflux from branches

Carbon isotope discrepancy between precambrian stromatolites and their modern analogs: Inferences from hypersaline microbial mats of the sinai coast

NASA Astrophysics Data System (ADS)

Schidlowski, Manfred

1985-12-01

The isotopic composition of organic carbon from extant stromatolite-type microbial ecosystems is commonly slanted toward heavy δ13 C values as compared to respective compositions of average organic matter (including that from Precambrian stromatolites). This seems the more enigmatic as the bulk of primary producers from benthic microbial communities are known to fix carbon via the C3 pathway normally entailing the sizable fractionations of the RuBP carboxylase reaction. There is reason to believe that the small fractionations displayed by aquatic microorganisms result from the limitations of a diffusion-controlled assimilatory pathway in which the isotope effect of the enzymatic reaction is largely suppressed. Apart from the diffusion-control exercised by the aqueous environment, transport of CO2 to the photosynthetically active sites will be further impeded by the protective slime (polysaccharide) coatings commonly covering microbial mats in which gas diffusivities are extremely low. Ineffective discrimination against13C becomes, however, most pronounced in hypersaline environments where substantially reduced CO2 solubilities tend to push carbon into the role of a limiting nutrient (brine habitats constitute preferential sanctuaries of mat-forming microbenthos since the emergence of Metazoan grazers ˜ 0.7 Ga ago). As the same microbial communities had been free to colonize normal marine environments during the Precambrian, the CO2 concentration effect was irrelevant to the carbon-fixing pathway of these ancient forms. Therefore, it might not surprise that organic matter from Precambrian stromatolites displays the large fractionations commonly associated with C3 photosynthesis. Increased mixing ratios of CO2 in the Precambrian atmosphere may have additionally contributed to the elimination of the diffusion barrier in the carbon-fixing pathways of ancient mat-forming microbiota.

Production and Extraction of [10C]-CO2 From Proton Bombardment of Molten 10B2O3

NASA Astrophysics Data System (ADS)

Schueller, M. J.; Nickles, R. J.; Roberts, A. D.; Jensen, M.

2003-08-01

This work describes the production of 10C (t1/2 = 19 s) from an enriched 10B2O3 target using a CTI RDS-112 11 MeV proton cyclotron. Proton beam heating is used to raise the target to a molten state (˜ 1300 °C), enabling the activity to diffuse to the surface of the melt. An infrared thermocouple monitors the melt temperature. Helium sweep gas then transports the activity to flow-through chemistry processing for human inhalation of 10CO2 for blood flow imaging with Positron Emission Tomography. The temperature-related diffusion of activity out of the white-hot molten glass target is discussed.

On the potential for CO2 mineral storage in continental flood basalts – PHREEQC batch- and 1D diffusion–reaction simulations

PubMed Central

2012-01-01

Continental flood basalts (CFB) are considered as potential CO2 storage sites because of their high reactivity and abundant divalent metal ions that can potentially trap carbon for geological timescales. Moreover, laterally extensive CFB are found in many place in the world within reasonable distances from major CO2 point emission sources. Based on the mineral and glass composition of the Columbia River Basalt (CRB) we estimated the potential of CFB to store CO2 in secondary carbonates. We simulated the system using kinetic dependent dissolution of primary basalt-minerals (pyroxene, feldspar and glass) and the local equilibrium assumption for secondary phases (weathering products). The simulations were divided into closed-system batch simulations at a constant CO2 pressure of 100 bar with sensitivity studies of temperature and reactive surface area, an evaluation of the reactivity of H2O in scCO2, and finally 1D reactive diffusion simulations giving reactivity at CO2 pressures varying from 0 to 100 bar. Although the uncertainty in reactive surface area and corresponding reaction rates are large, we have estimated the potential for CO2 mineral storage and identified factors that control the maximum extent of carbonation. The simulations showed that formation of carbonates from basalt at 40 C may be limited to the formation of siderite and possibly FeMg carbonates. Calcium was largely consumed by zeolite and oxide instead of forming carbonates. At higher temperatures (60 – 100 C), magnesite is suggested to form together with siderite and ankerite. The maximum potential of CO2 stored as solid carbonates, if CO2 is supplied to the reactions unlimited, is shown to depend on the availability of pore space as the hydration and carbonation reactions increase the solid volume and clog the pore space. For systems such as in the scCO2 phase with limited amount of water, the total carbonation potential is limited by the amount of water present for hydration of basalt. PMID:22697910

Electrochemically influenced cation inter-diffusion and Co 3O 4 formation on La 0.6Sr 0.4CoO 3 infiltrated into SOFC cathodes

DOE PAGES

Song, Xueyan; Lee, Shiwoo; Chen, Yun; ...

2015-06-18

Nanosized LSC electrocatalyst was infiltrated into a porous scaffold cathode composed of Sm 2O 3-doped CeO 2 (SDC) and La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) in a commercial button solid oxide fuel cell (SOFC). To understand the stability of cathodes infiltrated with LSC, the infiltrated composite cells were subjected to both electrochemical operating and thermal aging states at 750 °C for 1500 h. Nanostructure and local chemistry evolution of La 0.6Sr 0.4CoO 3 (LSC) infiltrated cathodes upon operation and aging were investigated by transmission electron microscopy. After operation, the LSC remained a cubic perovskite, and the crystal grains exhibitmore » comparable size to as-infiltrated LSC grains. Inter-diffusion of Fe from the LSCF to a Fe-incorporated LSC layer developed on the LSCF backbone. However, only sharp interfaces were observed between LSC and SDC backbone in the as-infiltrated cathode and such interfaces remain after operation. The infiltrated LSC on the SDC backbone also retains granular particle morphology. Furthermore, newly grown Co 3O 4 nanocrystals were found in the operated cathode. After thermal aging, on the other hand, cation inter-diffusion across the interfaces of the infiltrate particles and the cathode backbones is less than that from the operated cells. Lastly, the following hypothesis is proposed: Co 3O 4 forms on LSC arising from local charge balancing between cobalt and oxygen vacancies.« less

Parametric studies with an atmospheric diffusion model that assesses toxic fuel hazards due to the ground clouds generated by rocket launches

NASA Technical Reports Server (NTRS)

Stewart, R. B.; Grose, W. L.

1975-01-01

Parametric studies were made with a multilayer atmospheric diffusion model to place quantitative limits on the uncertainty of predicting ground-level toxic rocket-fuel concentrations. Exhaust distributions in the ground cloud, cloud stabilized geometry, atmospheric coefficients, the effects of exhaust plume afterburning of carbon monoxide CO, assumed surface mixing-layer division in the model, and model sensitivity to different meteorological regimes were studied. Large-scale differences in ground-level predictions are quantitatively described. Cloud alongwind growth for several meteorological conditions is shown to be in error because of incorrect application of previous diffusion theory. In addition, rocket-plume calculations indicate that almost all of the rocket-motor carbon monoxide is afterburned to carbon dioxide CO2, thus reducing toxic hazards due to CO. The afterburning is also shown to have a significant effect on cloud stabilization height and on ground-level concentrations of exhaust products.

Spatial and temporal distribution of Au and other trace elements in an estuary using the diffusive gradients in thin films technique and grab sampling

NASA Astrophysics Data System (ADS)

Lucas, Andrew R.; Salmon, S. Ursula; Rate, Andrew W.; Larsen, Sarah; Kilminster, Kieryn

2015-12-01

This study reports the first surface water evaluation of the temporal and spatial variability of Au in an estuary, using recently developed modifications to the diffusive gradients in thin films (DGT) and grab sampling techniques. At the two study sites in the Swan River estuary that were more marine in character, the DGT-measured concentrations of Au (26.3 and 31.3 ng/L) were within the range of total concentrations measured on individual days (13.2-30.6 ng/L and 11.2-37.2 ng/L, respectively). In contrast, at an upstream site, Au concentrations measured by DGT were significantly lower than totals (3.9 ng/L for DGT, compared with 13.2-28.8 ng/L for grab sampling), likely due to either size exclusion of colloids (>70 nm) by DGT or formation of a dissolved, non-DGT-labile Au species (<0.45 μm). DGT-measured concentrations of other metals (Cu, Co, Cr, U, V, Mo and As) were also lower than total concentrations, although in contrast to DGT-measured Au, this phenomenon occurred at all sites. Furthermore, daily grab samples for Au, taken over the 10-day deployment (which included a rain event), showed that Au concentrations could spike substantially (from 15.1 ng/L to 37.2 ng/L) over intervals as short as one day. The combination of simultaneous deployment of different DGT devices and grab sampling represents a new development in efforts to understand the transport and fate of Au together with other elements in dynamic environments such as estuaries.

Mineralization of the textile dye acid yellow 42 by solar photoelectro-Fenton in a lab-pilot plant.

PubMed

Espinoza, Carolina; Romero, Julio; Villegas, Loreto; Cornejo-Ponce, Lorena; Salazar, Ricardo

2016-12-05

A complete mineralization of a textile dye widely used in the Chilean textile industry, acid yellow 42 (AY42), was studied. Degradation was carried out in an aqueous solution containing 100mgL(-1) of total organic carbon (TOC) of dye using the advanced solar photoelectro-Fenton (SPEF) process in a lab-scale pilot plant consisting of a filter press cell, which contains a boron doped diamond electrode and an air diffusion cathode (BDD/air-diffusion cell), coupled with a solar photoreactor for treat 8L of wastewater during 270min of electrolysis. The main results obtained during the degradation of the textile dye were that a complete transformation to CO2 depends directly on the applied current density, the concentration of Fe(2+) used as catalyst, and the solar radiation intensity. The elimination of AY42 and its organic intermediates was due to hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between electrogenerated H2O2 and added Fe(2+). The application of solar radiation in the process (SPEF) yield higher current efficiencies and lower energy consumptions than electro-Fenton (EF) and electro-oxidation with electrogenerated H2O2 (E OH2O2) by the additional production of hydroxyl radicals from the photolysis of Fe(III) hydrated species and the photodecomposition of Fe(III) complexes with organic intermediates. Moreover, some products and intermediates formed during mineralization of dye, such as inorganic ions, carboxylic acids and aromatic compounds were determined by photometric and chromatographic methods. An oxidation pathway is proposed for the complete conversion to CO2. Copyright © 2016 Elsevier B.V. All rights reserved.

Precursory diffuse carbon dioxide degassing signature related to a 5.1 magnitude earthquake in El Salvador, Central America

NASA Astrophysics Data System (ADS)

Salazar, J. M. L.; Pérez, N. M.; Hernández, P. A.; Soriano, T.; Barahona, F.; Olmos, R.; Cartagena, R.; López, D. L.; Lima, R. N.; Melián, G.; Galindo, I.; Padrón, E.; Sumino, H.; Notsu, K.

2002-12-01

Anomalous changes in the diffuse emission of carbon dioxide have been observed before some of the aftershocks of the 13 February 2001 El Salvador earthquake (magnitude 6.6). A significant increase in soil CO 2 efflux was detected 8 days before a 5.1 magnitude earthquake on 8 May 2001 25 km away from the observation site. In addition, pre- and co-seismic CO 2 efflux variations have also been observed related to the onset of a seismic swarm beneath San Vicente volcano on May 2001. Strain changes and/or fluid pressure fluctuations prior to earthquakes in the crust are hypothesized to be responsible for the observed variations in gas efflux at the surface environment of San Vicente volcano.

Monte Carlo Study of the Diffusion of CO Molecules inside Anthraquinone Hexagons on Cu(111)

NASA Astrophysics Data System (ADS)

Kim, Kwangmoo; Einstein, T. L.; Wyrick, Jon; Bartels, Ludwig

2010-03-01

Using Monte Carlo calculations of the two-di-men-sion-al (2D) lattice gas model, we study the diffusion of CO molecules inside anthraquinone (AQ) hexagons on a Cu(111) plane. We use experimentally-derived CO-CO interactionsfootnotetextK.L. Wong, , L. Bartels, J. Chem.Phys.123, 201102 (2005) and the analytic expression for the long-range surface-state- mediated interactionsfootnotetextK. Berland, TLE, and P. Hyldgaard, Phys.Rev. B 80, 155431 (2009) to describe the CO-AQ interactions. We assume that the CO-CO interactions are not affected by the presence of AQ's and that the CO-AQ interactions can be controlled by varying the intra-surface-state (ISS) reflectance r and the ISS phase shift δ of the indirect-electronic adsorbate-pair interactions. Comparing our results with experimental observations, we find that not only pair but also surface-state-mediated trio interactionsfootnotetextP. Hyldgaard and T.L. Einstein, EPL 59, 265 (2002) are needed to understand the data.

Multiparametric comparison of CARvedilol, vs. NEbivolol, vs. BIsoprolol in moderate heart failure: the CARNEBI trial.

PubMed

Contini, Mauro; Apostolo, Anna; Cattadori, Gaia; Paolillo, Stefania; Iorio, Annamaria; Bertella, Erika; Salvioni, Elisabetta; Alimento, Marina; Farina, Stefania; Palermo, Pietro; Loguercio, Monica; Mantegazza, Valentina; Karsten, Marlus; Sciomer, Susanna; Magrì, Damiano; Fiorentini, Cesare; Agostoni, Piergiuseppe

2013-10-03

Several β-blockers, with different pharmacological characteristics, are available for heart failure (HF) treatment. We compared Carvedilol (β1-β2-α-blocker), Bisoprolol (β1-blocker), and Nebivolol (β1-blocker, NO-releasing activity). Sixty-one moderate HF patients completed a cross-over randomized trial, receiving, for 2 months each, Carvedilol, Nebivolol, Bisoprolol (25.6 ± 12.6, 5.0 ± 2.4 and 5.0 ± 2.4 mg daily, respectively). At the end of each period, patients underwent: clinical evaluation, laboratory testing, echocardiography, spirometry (including total DLCO and membrane diffusion), O2/CO2 chemoreceptor sensitivity, constant workload, in normoxia and hypoxia (FiO2=16%), and maximal cardiopulmonary exercise test. No significant differences were observed for clinical evaluation (NYHA classification, Minnesota questionnaire), laboratory findings (including kidney function and BNP), echocardiography, and lung mechanics. DLCO was lower on Carvedilol (18.3 ± 4.8*mL/min/mmHg) compared to Nebivolol (19.9 ± 5.1) and Bisoprolol (20.0 ± 5.0) due to membrane diffusion 20% reduction (*=p<0.0001). Constant workload exercise showed in hypoxia a faster VO2 kinetic and a lower ventilation with Carvedilol. Peripheral and central sensitivity to CO2 was lower in Carvedilol while response to hypoxia was higher in Bisoprolol. Ventilation efficiency (VE/VCO2 slope) was 26.9 ± 4.1* (Carvedilol), 28.8 ± 4.0 (Nebivolol), and 29.0 ± 4.4 (Bisoprolol). Peak VO2 was 15.8 ± 3.6*mL/kg/min (Carvedilol), 16.9 ± 4.1 (Nebivolol), and 16.9 ± 3.6 (Bisoprolol). β-Blockers differently affect several cardiopulmonary functions. Lung diffusion and exercise performance, the former likely due to lower interference with β2-mediated alveolar fluid clearance, were higher in Nebivolol and Bisoprolol. On the other hand, Carvedilol allowed a better ventilation efficiency during exercise, likely via a different chemoreceptor modulation. Results from this study represent the basis for identifying the best match between a specific β-blocker and a specific HF patient. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Pore-scale supercritical CO 2 dissolution and mass transfer under drainage conditions

DOE PAGES

Chang, Chun; Zhou, Quanlin; Oostrom, Mart; ...

2016-12-05

Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO 2 (scCO 2) and a prolonged depletion of residual scCO 2. In this paper, pore-scale scCO 2 dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO 2 into the sandstone-analogue pore network initially saturated by water without dissolved CO 2 (dsCO 2). During the experiments, time-lapse images of dye intensity, reflecting water pH,more » were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO 2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO 2 dissolution and phase equilibrium occurs when scCO 2 bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO 2 dissolution at phase interfaces and diffusion of dsCO 2 at the pore scale (10–100 µm) observed after scCO 2 bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO 2 in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. Finally, this finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO 2 at narrow pore throats.« less

Pore-scale supercritical CO 2 dissolution and mass transfer under drainage conditions

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

Chang, Chun; Zhou, Quanlin; Oostrom, Mart

Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO 2 (scCO 2) and a prolonged depletion of residual scCO 2. In this paper, pore-scale scCO 2 dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO 2 into the sandstone-analogue pore network initially saturated by water without dissolved CO 2 (dsCO 2). During the experiments, time-lapse images of dye intensity, reflecting water pH,more » were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO 2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO 2 dissolution and phase equilibrium occurs when scCO 2 bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO 2 dissolution at phase interfaces and diffusion of dsCO 2 at the pore scale (10–100 µm) observed after scCO 2 bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO 2 in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. Finally, this finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO 2 at narrow pore throats.« less

Pore-scale supercritical CO 2 dissolution and mass transfer under drainage conditions

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

Chang, Chun; Zhou, Quanlin; Oostrom, Mart

Abstract: Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO 2 (scCO 2) and a prolonged depletion of residual scCO 2. In this study, pore-scale scCO 2 dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO 2 into the sandstone-analogue pore network initially saturated by water without dissolved CO 2 (dsCO 2). During the experiments, time-lapse images of dye intensity, reflecting watermore » pH, were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO 2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO 2 dissolution and phase equilibrium occurs when scCO 2 bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO 2 dissolution at phase interfaces and diffusion of dsCO 2 at the pore scale (10-100 µm) observed after scCO 2 bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO 2 in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. This finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO 2 at narrow pore throats.« less

Incorporation of Co into MoS2/graphene nanocomposites: One effective way to enhance the cycling stability of Li/Na storage

NASA Astrophysics Data System (ADS)

Li, Xiaomin; Feng, Zhenxing; Zai, Jiantao; Ma, Zi-Feng; Qian, Xuefeng

2018-01-01

Layered transition metal dichalcogenides are promising as lithium and/or sodium storage materials for lithium and sodium (Li/Na) ion batteries. However they always exhibit limited rate capability and long-term cycling stability, due to the fact that their 2D structures are easily restacking and agglomeration during cycling process and further result poor electrochemical reversibility. Herein, hierarchical Co1/3Mo2/3S2/graphene nanocomposites without CoSx and MoS2 impurities have been synthesized via one-pot solvothermal process. The incorporation of Co into MoS2 at atomic level can not only give rise to thinner and smaller nanosheets in the nanocomposites than MoS2/graphene nanocomposites, but also significantly decrease the size of in-situ formed MoS2/CoSx nanoparticles during electrochemical conversion process, which can greatly promoting the ion diffusion and suppressing the aggregation of active materials. Furthermore, the conductivity of Co1/3Mo2/3S2/graphene nanocomposites can be enhanced from 0.46 S m-1 (MoS2/graphene) to 1.39 S m-1via changing the semiconducting MoS2 to metallic Co1/3Mo2/3S2. The simultaneously optimized electron conductivity and ions diffusion dynamics of Co1/3Mo2/3S2/graphene nanocomposites can effectively improve the reversibility of electrochemical conversion reactions. A capacity of 940 mAh g-1 and 529 mAh g-1 can be maintained at 3200th cycle (2 A g-1) in lithium-ion batteries and 200th cycle (1 A g-1) in sodium-ion batteries, respectively.

Diffusion-based process for carbon dioxide uptake and isoprene emission in gaseous/aqueous two-phase photobioreactors by photosynthetic microorganisms.

PubMed

Bentley, Fiona K; Melis, Anastasios

2012-01-01

Photosynthesis for the generation of fuels and chemicals from cyanobacteria and microalgae offers the promise of a single host organism acting both as photocatalyst and processor, performing sunlight absorption and utilization, as well as CO(2) assimilation and conversion into product. However, there is a need to develop methods for generating, sequestering, and trapping such bio-products in an efficient and cost-effective manner that is suitable for industrial scale-up and exploitation. A sealed gaseous/aqueous two-phase photobioreactor was designed and applied for the photosynthetic generation of volatile isoprene (C(5)H(8)) hydrocarbons, which operates on the principle of spontaneous diffusion of CO(2) from the gaseous headspace into the microalgal or cyanobacterial-containing aqueous phase, followed by photosynthetic CO(2) assimilation and isoprene production by the transgenic microorganisms. Volatile isoprene hydrocarbons were emitted from the aqueous phase and were sequestered into the gaseous headspace. Periodic replacement (flushing) of the isoprene (C(5)H(8)) and oxygen (O(2)) content of the gaseous headspace with CO(2) allowed for the simultaneous harvesting of the photoproducts and replenishment of the CO(2) supply in the gaseous headspace. Reduction in practice of the gaseous/aqueous two-phase photobioreactor is offered in this work with a fed-batch and a semi-continuous culturing system using Synechocystis sp. PCC 6803 heterologously expressing the Pueraria montana (kudzu) isoprene synthase (IspS) gene. Constitutive isoprene production was observed over 192 h of experimentation, coupled with cyanobacterial biomass accumulation. The diffusion-based process in gaseous/aqueous two-phase photobioreactors has the potential to be applied to other high-value photosynthetically derived volatile molecules, emanating from a variety of photosynthetic microorganisms. Copyright © 2011 Wiley Periodicals, Inc.

Understanding of the Elemental Diffusion Behavior in Concentrated Solid Solution Alloys

DOE PAGES

Zhang, Chuan; Zhang, Fan; Jin, Ke; ...

2017-07-13

As one of the core effects on the high-temperature structural stability, the so-called “sluggish diffusion effect” in high-entropy alloy (HEA) has attracted much attention. Experimental investigations on the diffusion kinetics have been carried out in a few HEA systems, such as Al-Co-Cr-Fe-Ni and Co-Cr-Fe-Mn-Ni. However, the mechanisms behind this effect remain unclear. To better understand the diffusion kinetics of the HEAs, a combined computational/experimental approach is employed in the current study. In the present work, a self-consistent atomic mobility database is developed for the face-centered cubic (fcc) phase of the Co-Cr-Fe-Mn-Ni quinary system. The simulated diffusion coefficients and concentration profilesmore » using this database can well describe the experimental data both from this work and the literatures. The validated mobility database is then used to calculate the tracer diffusion coefficients of Ni in the subsystems of the Co-Cr-Fe-Mn-Ni system with equiatomic ratios. The comparisons of these calculated diffusion coefficients reveal that the diffusion of Ni is not inevitably more sluggish with increasing number of components in the subsystem even with homologous temperature. Taking advantage of computational thermodynamics, the diffusivities of alloying elements with composition and/or temperature are also calculated. Furthermore, these calculations provide us an overall picture of the diffusion kinetics within the Co-Cr-Fe-Mn-Ni system.« less

Effect of water vapor on evolution of a thick Pt-layer modified oxide on the NiCoCrAl alloy at high temperature

NASA Astrophysics Data System (ADS)

Song, Peng; He, Xuan; Xiong, Xiping; Ma, Hongqing; Song, Qunling; Lü, Jianguo; Lu, Jiansheng

2018-03-01

To investigate the effect of water vapor on the novel Pt-containing oxide growth behavior, Pt-addition within the oxide layer on the surface of NiCoCrAl coating and furnace cycle tests were carried out at 1050 °C in air and air plus water vapor. The thick Pt-containing oxide layer on NiCoCrAl exhibits a different oxidation growth behavior compared to the conventional Pt-diffusion metallic coatings. The Pt-containing oxide after oxidation in air plus water vapor showed a much thicker oxide layer compare to the ones without Pt addition, and also presented a much better coating adhesion. During the oxidation process in air, Pt promotes the spinel (NiCr2O4) formation. However, the Cr2O3 formed in air with water vapor and fixed Pt within the complex oxide layer. The water vapor promoted the Ni and Co outer-diffusion, and combined with Pt to form CoPt compounds on the surface of the NiCoCrAl coating system.

In vivo free-breathing DTI and IVIM of the whole human heart using a real-time slice-followed SE-EPI navigator-based sequence: A reproducibility study in healthy volunteers.

PubMed

Moulin, Kevin; Croisille, Pierre; Feiweier, Thorsten; Delattre, Benedicte M A; Wei, Hongjiang; Robert, Benjamin; Beuf, Olivier; Viallon, Magalie

2016-07-01

In this study, we proposed an efficient free-breathing strategy for rapid and improved cardiac diffusion-weighted imaging (DWI) acquisition using a single-shot spin-echo echo planar imaging (SE-EPI) sequence. A real-time slice-following technique during free-breathing was combined with a sliding acquisition-window strategy prior Principal Component Analysis temporal Maximum Intensity Projection (PCAtMIP) postprocessing of in-plane co-registered diffusion-weighted images. This methodology was applied to 10 volunteers to quantify the performance of the motion correction technique and the reproducibility of diffusion parameters. The slice-following technique offers a powerful head-foot respiratory motion management solution for SE-EPI cDWI with the advantage of a 100% duty cycle scanning efficiency. The level of co-registration was further improved using nonrigid motion corrections and was evaluated with a co-registration index. Vascular fraction f and the diffusion coefficients D and D* were determined to be 0.122 ± 0.013, 1.41 ± 0.09 × 10(-3) mm(2) /s and 43.6 ± 9.2 × 10(-3) mm(2) /s, respectively. From the multidirectional dataset, the measured mean diffusivity was 1.72 ± 0.09 × 10(-3) mm(2) /s and the fractional anisotropy was 0.36 ± 0.02. The slice-following DWI SE-EPI sequence is a promising solution for clinical implementation, offering a robust improved workflow for further evaluation of DWI in cardiology. Magn Reson Med 76:70-82, 2016. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

CCL21 and IP-10 as blood biomarkers for pulmonary involvement in systemic lupus erythematosus patients.

PubMed

Odler, B; Bikov, A; Streizig, J; Balogh, C; Kiss, E; Vincze, K; Barta, I; Horváth, I; Müller, V

2017-05-01

Biomarkers for pulmonary manifestations in systemic lupus erythematosus (SLE) are missing. Plasma samples of nine SLE patients with known pulmonary involvement (SLE pulm ) and nine SLE patients without pulmonary involvement (SLE) were tested by multiplex microarray analysis for various cyto- and chemokines. Significantly decreased lung function paramters for forced vital capacity (FVC), total lung capacity (TLC), diffusion capacity for carbon monoxide (DL CO ) and diffusion of CO corrected on lung volume (KL CO ) were observed in SLE pulm as compared to SLE patients. CC chemokine ligand 21 (CCL21) and interferon gamma-induced protein 10 (IP-10) levels were significantly higher in SLE pulm , than in patients without pulmonary manifestations. CCL21 correlated negatively with DL CO ( r = -0.73; p < 0.01) and KL CO ( r = -0.62; p < 0.01), while IP-10 with FVC and forced expiratory volume one second. Receiver Operating Characteristics (ROC) analysis confirmed high sensitivity and specificity for the separation of SLE patients with and without pulmonary involvement for the chemokines CCL21 (Area Under Curve (AUC): 0.85; sensitivity%: 88.90; specificity%: 75.00; p < 0.01) and IP-10 (AUC: 0.82; sensitivity%: 66.67, specificity%: 100; p < 0.01). Pleuropulmonary manifestations in SLE patients associated with lung functional and DL CO /KL CO changes and were associated with significant increase in CCL21 and IP-10. These chemokines might serve as potential biomarkers of lung involvement in SLE patients.

Measurements of carbon monoxide and nitrogen dioxide in British homes using unflued heating or cooking appliances.

PubMed

Stevenson, K J

1985-08-01

Measurements of Carbon Monoxide (CO) and Nitrogen Dioxide (NO2) were made in three kitchens, two with gas cookers and one all electric, and two living rooms, one heated by a portable butane heater and the other by a paraffin stove. The measurements were taken whilst the homes were in normal use and the occupants kept a diary of when specific appliances were used. Measurements of NO2 were made simultaneously by chemiluminescence and by diffusion tubes. The accuracy of the diffusion tube measurements relative to the chemiluminescent standard was estimated as +/- 10% and the precision less than or equal to 300 ppb. hr. Results from diffusion tubes were used to indicate the distribution of NO2 throughout other rooms in the house. At the all electric house the CO and NO2 concentrations were very similar to the expected outdoor levels. In all the other houses NO2 levels exceeded typical outdoor concentrations measured in Central London and in the paraffin heated house and one gas cooking house median CO concentrations exceeded these measured at the curbside of a very busy road in Central London. The living room concentrations of NO2 where the paraffin heater was in use were elevated for long periods. Analysis of the decay of pollutant concentration in one kitchen yielded an effective deposition velocity for NO2 of 3 X 10(-5) m s-1. The magnitude of the CO and NO2 concentrations measured in this survey confirms that indoor air pollution should be taken into account when assessing overall public exposure to air pollution.

Comparison of Bone Preserving and Radical Surgical Treatment in 32 Cases of Calcaneal Osteomyelitis.

PubMed

Babiak, Ireneusz; Pędzisz, Piotr; Kulig, Mateusz; Janowicz, Jakub; Małdyk, Paweł

2016-01-01

Introduction. Radical procedures like calcanectomy and amputation performed for calcaneal osteomyelitis are regarded as effective in eradication of infection even though potentially functionally disabling. Bone sparing procedures offer better functional result at the expense of potentially worse infection control. The aim of the study has been to assess the influence of the surgical radicalism as much as the extent of bone infection on the final outcome in the surgical therapy of chronic calcaneal osteomyelitis (CO). Material and method. 32 patients with chronic CO have comprised the group under study: 8 with superficial type, 12 localised type and 12 with diffuse type according to Cierny-Mader classification. The aim of the treatment was to heal infection, preserve the heel shape and achieve good skin coverage over the calcaneus. The therapy consisted of 9 debridement surgeries with or without flaps, 8 drilling-operations of the calcaneus with application of collagen-gentamicin-sponge in bore holes, 15 partial and 2 total calcanectomies, and 4 below-the knee amputations. Results. The healing of infection and wound has been achieved after 7 of 9 debridements, 6 of 8 drilling-operations, 13 of 15 partial and all total calcanectomies. Conclusion. Bone preserving operations in chronic calcaneal osteomyelitis provided inferior infection control (76,47% vs 88,24%) and worse patient satisfaction (88,24% vs 100%) and almost camparable ambulation (100% vs 93,33%). Drilling of the calcaneus with application of collagen sponge containing gentamicin performed in chronic diffuse calcaneal osteomyelitis seems to offer a viable alternative to partial or radical calcanectomy. V.

Comparison of Bone Preserving and Radical Surgical Treatment in 32 Cases of Calcaneal Osteomyelitis

PubMed Central

Babiak, Ireneusz; Pędzisz, Piotr; Kulig, Mateusz; Janowicz, Jakub; Małdyk, Paweł

2016-01-01

Introduction. Radical procedures like calcanectomy and amputation performed for calcaneal osteomyelitis are regarded as effective in eradication of infection even though potentially functionally disabling. Bone sparing procedures offer better functional result at the expense of potentially worse infection control. The aim of the study has been to assess the influence of the surgical radicalism as much as the extent of bone infection on the final outcome in the surgical therapy of chronic calcaneal osteomyelitis (CO). Material and method. 32 patients with chronic CO have comprised the group under study: 8 with superficial type, 12 localised type and 12 with diffuse type according to Cierny-Mader classification. The aim of the treatment was to heal infection, preserve the heel shape and achieve good skin coverage over the calcaneus. The therapy consisted of 9 debridement surgeries with or without flaps, 8 drilling-operations of the calcaneus with application of collagen-gentamicin-sponge in bore holes, 15 partial and 2 total calcanectomies, and 4 below-the knee amputations. Results. The healing of infection and wound has been achieved after 7 of 9 debridements, 6 of 8 drilling-operations, 13 of 15 partial and all total calcanectomies. Conclusion. Bone preserving operations in chronic calcaneal osteomyelitis provided inferior infection control (76,47% vs 88,24%) and worse patient satisfaction (88,24% vs 100%) and almost camparable ambulation (100% vs 93,33%). Drilling of the calcaneus with application of collagen sponge containing gentamicin performed in chronic diffuse calcaneal osteomyelitis seems to offer a viable alternative to partial or radical calcanectomy. Level of evidence: V. PMID:28529846

Tunneling-Magnetoresistance Ratio Comparison of MgO-Based Perpendicular-Magnetic-Tunneling-Junction Spin Valve Between Top and Bottom Co2Fe6B2 Free Layer Structure.

PubMed

Lee, Du-Yeong; Lee, Seung-Eun; Shim, Tae-Hun; Park, Jea-Gun

2016-12-01

For the perpendicular-magnetic-tunneling-junction (p-MTJ) spin valve with a nanoscale-thick bottom Co2Fe6B2 free layer ex situ annealed at 400 °C, which has been used as a common p-MTJ structure, the Pt atoms of the Pt buffer layer diffused into the MgO tunneling barrier. This transformed the MgO tunneling barrier from a body-centered cubic (b.c.c) crystallized layer into a mixture of b.c.c, face-centered cubic, and amorphous layers and rapidly decreased the tunneling-magnetoresistance (TMR) ratio. The p-MTJ spin valve with a nanoscale-thick top Co2Fe6B2 free layer could prevent the Pt atoms diffusing into the MgO tunneling barrier during ex situ annealing at 400 °C because of non-necessity of a Pt buffer layer, demonstrating the TMR ratio of ~143 %.

Carbon dioxide and helium emissions from a reservoir of magmatic gas beneath Mammoth Mountain, California

USGS Publications Warehouse

Sorey, M.L.; Evans, William C.; Kennedy, B.M.; Farrar, C.D.; Hainsworth, L.J.; Hausback, B.

1998-01-01

Carbon dioxide and helium with isotopic compositions indicative of a magmatic source (??13C = -4.5 to -5???, 3He/4He = 4.5 to 6.7 RA) are discharging at anomalous rates from Mammoth Mountain, on the southwestern rim of the Long Valley caldera in eastern California. The gas is released mainly as diffuse emissions from normal-temperature soils, but some gas issues from steam vents or leaves the mountain dissolved in cold groundwater. The rate of gas discharge increased significantly in 1989 following a 6-month period of persistent earthquake swarms and associated strain and ground deformation that has been attributed to dike emplacement beneath the mountain. An increase in the magmatic component of helium discharging in a steam vent on the north side of Mammoth Mountain, which also began in 1989, has persisted until the present time. Anomalous CO2 discharge from soils first occurred during the winter of 1990 and was followed by observations of several areas of tree kill and/or heavier than normal needlecast the following summer. Subsequent measurements have confirmed that the tree kills are associated with CO2 concentrations of 30-90% in soil gas and gas flow rates of up to 31,000 g m-2 d-1 at the soil surface. Each of the tree-kill areas and one area of CO2 discharge above tree line occurs in close proximity to one or more normal faults, which may provide conduits for gas flow from depth. We estimate that the total diffuse CO2 flux from the mountain is approximately 520 t/d, and that 30-50 t/d of CO2 are dissolved in cold groundwater flowing off the flanks of the mountain. Isotopic and chemical analyses of soil and fumarolic gas demonstrate a remarkable homogeneity in composition, suggesting that the CO2 and associated helium and excess nitrogen may be derived from a common gas reservoir whose source is associated with some combination of magmatic degassing and thermal metamorphism of metasedimentary rocks. Furthermore, N2/Ar ratios and nitrogen isotopic values indicate that the Mammoth Mountain gases are derived from sources separate from those that supply gas to the hydrothermal system within the Long Valley caldera. Various data suggest that the Mammoth Mountain gas reservoir is a large, low-temperature cap over an isolated hydrothermal system, that it predates the 1989 intrusion, and that it could remain a source of gas discharge for some time.

Bursts of CO2 released during freezing offer a new perspective on avoidance of winter embolism in trees.

PubMed

Lintunen, A; Lindfors, L; Kolari, P; Juurola, E; Nikinmaa, E; Hölttä, T

2014-12-01

Woody plants can suffer from winter embolism as gas bubbles are formed in the water-conducting conduits when freezing occurs: gases are not soluble in ice, and the bubbles may expand and fill the conduits with air during thawing. A major assumption usually made in studies of winter embolism formation is that all of the gas dissolved in the xylem sap is trapped within the conduits and forms bubbles during freezing. The current study tested whether this assumption is actually valid, or whether efflux of gases from the stem during freezing reduces the occurrence of embolism. CO2 efflux measurements were conducted during freezing experiments for saplings of three Scots pine (Pinus sylvestris) and three Norway spruce (Picea abies) trees under laboratory conditions, and the magnitudes of the freezing-related bursts of CO2 released from the stems were analysed using a previously published mechanistic model of CO2 production, storage, diffusion and efflux from a tree stem. The freezing-related bursts of CO2 released from a mature Scots pine tree growing in field conditions were also measured and analysed. Substantial freezing-related bursts of CO2 released from the stem were found to occur during both the laboratory experiments and under field conditions. In the laboratory, the fraction of CO2 released from the stem ranged between 27 and 96 % of the total CO2 content within the stem. All gases dissolved in the xylem sap are not trapped within the ice in the stem during freezing, as has previously been assumed, thus adding a new dimension to the understanding of winter embolism formation. The conduit water volume not only determines the volume of bubbles formed during freezing, but also the efficiency of gas efflux out of the conduit during the freezing process. © The Author 2014. Published by Oxford University Press on behalf of the Annals of Botany Company.

Alteration of bentonite when contacted with supercritical CO2

NASA Astrophysics Data System (ADS)

Jinseok, K.; Jo, H. Y.; Yun, S. T.

2014-12-01

Deep saline formations overlaid by impermeable caprocks with a high sealing capacity are attractive CO2 storage reservoirs. Shales, which consist of mainly clay minerals, are potential caprocks for the CO2 storage reservoirs. The properties of clay minerals in shales may affect the sealing capacity of shales. In this study, changes in clay minerals' properties when contacted with supercritical (SC) CO2 at various conditions were investigated. Bentonite, whichis composed of primarily montmorillonite, was used as the clay material in this study. Batch reactor tests on wet bentonite samples in the presence of SC CO2 with or without aqueous phases were conducted at high pressure (12 MPa) and moderate temperature (50 oC) conditions for a week. Results show that the bentonite samples obtained from the tests with SC CO2 had less change in porosity than those obtained from the tests without SC CO2 (vacuum-drying) at a given reaction time, indicating that the bentonite samples dried in the presence of SC CO2 maintained their structure. These results suggest that CO2 molecules can diffuse into interlayer of montmorillonite, which is a primary mineral of bentonite, and form a single CO2 molecule layer or double CO2 molecule layers. The CO2 molecules can displace water molecules in the interlayer, resulting in maintaining the interlayer spacing when dehydration occurs. Noticeable changes in reacted bentonite samples obtained from the tests with an aqueous phase (NaCl, CaCl2, or sea water) are decreases in the fraction of plagioclase and pyrite and formation of carbonate minerals (i.e., calcite and dolomite) and halite. In addition, no significant exchanges of Na or Ca on the exchangeable complex of the montmorillonite in the presence of SC CO2 occurred, resulting in no significant changes in the swelling capacity of bentonite samples after reacting with SC CO2 in the presence of aqueous phases. These results might be attributed by the CO2 molecule layer, which prevents diffusion of ions into the interlayer.

Designing High Capacity, Stable Lithium-Manganese Oxide Insertion Electrodes with First Principles Computations

NASA Astrophysics Data System (ADS)

Reed, John; van der Ven, Anton; Ceder, Gerbrand

2001-03-01

The viability of rechargeable lithium batteries in many applications hinges on finding electrode materials with high capacity, excellent chemical and phase stability, and low cost. LiCoO_2, the intercalation oxide currently used is too expensive and unsafe for large-scale batteries. Manganese oxides are a possible low cost alternative, but spinel LiMn_2O _4, the common form of the material, has too low a capacity and some stability problems. Recently, layered LiMnO _2, isostructural to LiCoO _2, has been synthesized. After a few battery cycles this material irreversibly transforms to a spinel structure, with loss of battery capacity. In this work we use Density Functional Theory to investigate why LiMnO2 transforms so rapidly to spinel but LiCoO 2 does not, even though both are known to be thermodynamically unstable towards this transformation. We find that the difference between the two compound is due to remarkably rapid diffusion of Mn ^3+. Diffusion of Mn^3+ occurs by disproportionation into Mn ^2+ an Mn ^4+ which gives the system a remarkable flexibility in its hybridization with the oxygen ions, even at the saddle point for diffusion. This knowledge has now been used to suggest compositional modifications of LiMnO 2 which slow down or even prevent the transformation to a spinel.

Dynamics of Functionalized Surface Molecular Monolayers Studied with Ultrafast Infrared Vibrational Spectroscopy

PubMed Central

Rosenfeld, Daniel E.; Nishida, Jun; Yan, Chang; Gengeliczki, Zsolt; Smith, Brian J.; Fayer, Michael D.

2012-01-01

The structural dynamics of thin films consisting of tricarbonyl (1,10-phenanthroline)rhenium chloride (RePhen(CO)3Cl) linked to an alkyl silane monolayer through a triazole linker synthesized on silica-on-calcium-fluoride substrates are investigated using ultrafast infrared (IR) techniques. Ultrafast 2D IR vibrational echo experiments and polarization selective heterodyne detected transient grating (HDTG) measurements, as well as polarization dependent FT-IR and AFM experiments are employed to study the samples. The vibrational echo experiments measure spectral diffusion, while the HDTG experiments measure the vibrational excited state population relaxation and investigate the vibrational transition dipole orientational anisotropy decay. To investigate the anticipated impact of vibrational excitation transfer, which can be caused by the high concentration of RePhen(CO)3Cl in the monolayer, a concentration dependence of the spectral diffusion is measured. To generate a range of concentrations, mixed monolayers consisting of both hydrogen terminated and triazole/RePhen(CO)3Cl terminated alkyl silanes are synthesized. It is found that the measured rate of spectral diffusion is independent of concentration, with all samples showing spectral diffusion of 37 ± 6 ps. To definitively test for vibrational excitation transfer, polarization selective HDTG experiments are conducted. Excitation transfer will cause anisotropy decay. Polarization resolved heterodyne detected transient grating spectroscopy is sensitive to anisotropy decay (depolarization) caused by excitation transfer and molecular reorientation. The HDTG experiments show no evidence of anisotropy decay on the appropriate time scale, demonstrating the absence of excitation transfer the RePhen(CO)3Cl. Therefore the influence of excitation transfer on spectral diffusion is inconsequential in these samples, and the vibrational echo measurements of spectral diffusion report solely on structural dynamics. A small amount of very fast (~2 ps time scale) anisotropy decay is observed. The decay is concentration independent, and is assigned to wobbling-in-a-cone orientational motions of the RePhen(CO)3Cl. Theoretical calculations reported previously for experiments on a single concentration of the same type of sample suggested the presence of some vibrational excitation transfer and excitation transfer induced spectral diffusion. Possible reasons for the experimentally observed lack of excitation transfer in these high concentration samples are discussed. PMID:23259027

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.

Influence of the manganese and cobalt content on the electrochemical performance of P2-Na0.67MnxCo1-xO2 cathodes for sodium-ion batteries.

PubMed

Hemalatha, K; Jayakumar, M; Prakash, A S

2018-01-23

The resurgence of sodium-ion batteries in recent years is due to their potential ability to form intercalation compounds possessing a high specific capacity and energy density comparable to existing lithium systems. To comprehend the role of cobalt substitution in the structure and electrochemical performance of Na 0.67 MnO 2 , the solid solutions of P2-Na 0.67 Mn x Co 1-x O 2 (x = 0.25, 0.5, 0.75) are synthesized and characterized. The XRD-Rietveld analysis revealed that the Co-substitution in Na 0.67 MnO 2 decreases lattice parameters 'a' and 'c' resulting in the contraction of MO 6 octahedra and the enlargement of inter-layer 'd' spacing. XPS indicates that the isovalent cobalt substitution in Na 0.67 MnO 2 results in the partial/complete replacement of Jahn-Teller active trivalent manganese to form low-spin complexes of better structural stability. The Na-ion diffusion coefficient, D Na + , derived from cyclic voltammetry and impedance spectroscopy, confirmed the enhanced mass transport in Co-rich phases compared to Mn-rich phases. Furthermore, higher diffusion coefficient values are observed for Co 3+ /Co 4+ than for their Mn 3+ /Mn 4+ redox processes. In addition, Co-rich phases exhibit a high structural stability and superior capacity retention, whereas Mn-rich phases discharge higher capacities.

Effects of melamine formaldehyde resin and CaCO3 diffuser-loaded encapsulation on correlated color temperature uniformity of phosphor-converted LEDs.

PubMed

Yang, Liang; Lv, Zhicheng; Jiaojiao, Yuan; Liu, Sheng

2013-08-01

Phosphor-free dispensing is the most widely used LED packaging method, but this method results in poor quality in angular CCT uniformity. This study proposes a diffuser-loaded encapsulation to solve the problem; the effects of melamine formaldehyde (MF) resin and CaCO3 loaded encapsulation on correlated color temperature (CCT) uniformity and luminous efficiency reduction of the phosphor-converted LEDs are investigated. Results reveal that MF resin loaded encapsulation has better light diffusion performance compared to MF resin loaded encapsulation at the same diffuser concentration, but CaCO3 loaded encapsulation has better luminous efficiency maintenance. The improvements in angular color uniformity for the LEDs emitting with MF resin and CaCO3 loaded encapsulation can be explained by the increase in photon scattering. The utility of this low cost and controllable mineral diffuser packaging method provides a practical approach for enhancing the angular color uniformity of LEDs. The diffuser mass ratio of 1% MF resin or 10% CaCO3 is the optimum condition to obtain low angular CCT variance and high luminous efficiency.

Fabrication of Graded Porous and Skin-Core Structure RDX-Based Propellants via Supercritical CO2 Concentration Profile

NASA Astrophysics Data System (ADS)

Yang, Weitao; Li, Yuxiang; Ying, Sanjiu

2015-04-01

A fabrication process to produce graded porous and skin-core structure propellants via supercritical CO2 concentration profile is reported in this article. It utilizes a partial gas saturation technique to obtain nonequilibrium gas concentration profiles in propellants. Once foamed, the propellant obtains a graded porous or skin-pore structure. This fabrication method was studied with RDX(Hexogen)-based propellant under an SC-CO2 saturation condition. The principle was analyzed and the one-dimensional diffusion model was employed to estimate the gas diffusion coefficient and to predict the gas concentration profiles inside the propellant. Scanning electron microscopy images were used to analyze the effects of partial saturation on the inner structure. The results also suggested that the sorption time and desorption time played an important role in gas profile generation and controlled the inner structure of propellants.

Infrared Study of CO2 Sorption over ?Molecular Basket? Sorbent Consisting of Polyethylenimine-Modified Mesoporous Molecular Sieve

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

Overbury, Steven; Wang, Xiaoxing; Clark, Jason

2009-01-01

An infrared study has been conducted on CO{sub 2} sorption into nanoporous CO{sub 2} 'molecular basket' sorbents prepared by loading polyethylenimine (PEI) into mesoporous molecular sieve SBA-15. IR results from DRIFTS showed that a part of loaded PEI is anchored on the surface of SBA-15 through the interaction between amine groups and isolated surface silanol groups. Raising the temperature from 25 to 75 C increased the molecular flexibility of PEI loaded in the mesopore channels, which may partly contribute to the increase of CO{sub 2} sorption capacity at higher temperatures. CO{sub 2} sorption/desorption behavior studied by in situ transmission FTIRmore » showed that CO{sub 2} is sorbed on amine sites through the formation of alkylammonium carbamates and absorbed into the multiple layers of PEI located in mesopores of SBA-15. A new observation by in situ IR is that two broad IR bands emerged at 2450 and 2160 cm{sup -1} with CO{sub 2} flowing over PEI(50)/SBA-15, which could be attributed to chemically sorbed CO{sub 2} species on PEI molecules inside the mesopores of SBA-15. The intensities of these two bands also increased with increasing CO{sub 2} exposure time and with raising CO{sub 2} sorption temperature. By comparison of the CO{sub 2} sorption rate at 25 and 75 C in terms of differential IR intensities, it was found that CO{sub 2} sorption over molecular basket sorbent includes two rate regimes which suggest two distinct steps: rapid sorption on exposed outer surface layers of PEI (controlled by sorption affinity or thermodynamics) and the diffusion and sorption inside the bulk of multiple layers of PEI (controlled by diffusion). The sorption of CO{sub 2} is reversible at 75 C. Comparative IR examination of the CO{sub 2} sorption/desorption spectra on dry and prewetted PEI/SBA-15 sorbent revealed that presorbed water does not significantly affect the CO{sub 2}-amine interaction patterns.« less

Influence of compositional complexity on interdiffusion in Ni-containing concentrated solid-solution alloys

DOE PAGES

Jin, Ke; Zhang, Chuan; Zhang, Fan; ...

2018-03-07

To investigate the compositional effects on thermal-diffusion kinetics in concentrated solid-solution alloys, interdiffusion in seven diffusion couples with alloys from binary to quinary is systematically studied. The alloys with higher compositional complexity exhibit in general lower diffusion coefficients against homologous temperature, however, an exception is found that diffusion in NiCoFeCrPd is faster than in NiCoFeCr and NiCoCr. While the derived diffusion parameters suggest that diffusion in medium and high entropy alloys is overall more retarded than in pure metals and binary alloys, they strongly depend on specific constituents. The comparative features are captured by computational thermodynamics approaches using a self-consistentmore » database.« less

On the enhancement of Er{sup 3+} diffusion in LiNbO{sub 3} crystals by Er{sup 3+}/Ti{sup 4+} co-diffusion

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

Almeida, José Manuel Marques Martins de, E-mail: jmmma@utad.pt; Department of Physics, School of Science and Technology, University of Trás-os-Montes e Alto Douro, PO. Box 1013, 5001-801 Vila Real; Sada, Cinzia

2016-02-15

Highlights: • Enhancement of the diffusion of erbium ions (Er{sup 3+}) in lithium niobate crystals. • Incoherence on published results lead to need for systematic revision of literature. • Further insight into the topic of co-diffusion of Er{sup 3+}/Ti{sup 4+} ions into LiNbO{sub 3}. - Abstract: After carrying out a revision of the literature on the enhancement of Er{sup 3+} diffusion in LiNbO{sub 3} crystals by Er{sup 3+}/Ti{sup 4+} co-diffusion and analyzing our own experimental results, we conclude that no reproducible results were reported, meaning that further research on this subject is necessary.

Synthesis, characterization, microstructure, optical and magnetic properties of strontium cobalt carbonate precursor and Sr2Co2O5 oxide material

NASA Astrophysics Data System (ADS)

Agilandeswari, K.; Ruban Kumar, A.

2014-04-01

Sr2Co2O5 ceramic synthesized by the coprecipitation of strontium cobalt carbonate method. XRD analysis shows the single phase strontianite precursor and decomposed oxide product as orthorhombic structure of Sr2Co2O5. Thermal analysis proves the Sr2Co2O5 phase formation temperature of 800 °C. SEM image indicates crystalline rod shaped carbonate precursor transformed to oxide as porous diffused sphere shape particles. Optical band gap it reveals the strontium cobalt carbonate precursor as insulating material and the Sr2Co2O5 as semiconducting nature. The room temperature magnetic study indicates the carbonate precursor as paramagnetic but its oxide Sr2Co2O5 as superparamagnetic behavior.

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.