Stomatal Conductance, Plant Species Distribution, and an Exploration of Rhizosphere Microbes and Mycorrhizae at a Deliberately Leakimg Experimental Carbon Sequestration Field (ZERT)

NASA Astrophysics Data System (ADS)

Sharma, B.; Apple, M. E.; Morales, S.; Zhou, X.; Holben, B.; Olson, J.; Prince, J.; Dobeck, L.; Cunningham, A. B.; Spangler, L.

2010-12-01

One measure to reduce atmospheric CO2 is to sequester it in deep geological formations. Rapid surface detection of any CO2 leakage is crucial. CO2 leakage rapidly affects vegetation above sequestration fields. Plant responses to high CO2 are valuable tools in surface detection of leaking CO2. The Zero Emission Research Technology (ZERT) site in Bozeman, MT is an experimental field for surface detection of CO2 where 0.15 ton/day of CO2 was released (7/19- 8/15/2010) from a 100m horizontal injection well, HIW, 1.5 m underground with deliberate leaks of CO2 at intervals, and from a vertical injector, VI, (6/3-6/24/2010). The vegetation includes Taraxacum officinale (Dandelion), Dactylis glomerata (Orchard Grass), and other herbaceous plants. We collected soil and roots 1, 3 and 5 m from the VI to determine the responses of mycorrhizal fungi and rhizosphere microbes to high CO2. Mycorrhizal fungi obtain C from root exudates, increase N and P availability, and reduce desiccation, while prokaryotic rhizosphere microbes fix atmospheric N and will be examined for abundance and expression of carbon and nitrogen cycling genes. We are quantifying mycorrhizal colonization and the proportion of spores, hyphae, and arbuscules in vesicular-arbuscular mycorrhizae (VAM) in cleared and stained roots. Stomatal conductance is an important measure of CO2 uptake and water loss via transpiration. We used a porometer (5-40°C, 0-90% RH, Decagon) to measure stomatal conductivity in dandelion and orchard grass at 1, 3, and 5 m from the VI and along a transect perpendicular to the HIW. Dandelion conductance was highest close to the VI and almost consistently higher close to hot spots (circular regions with maximum CO2 and leaf dieback) at the HIW, with 23.2 mmol/m2/s proximal to the hot spot, and 10.8 mmol/m2/s distally. Average conductance in grass (50.3 mmol/m2/s) was higher than in dandelion, but grass did not have high conductance near hot spots. Stomata generally close at elevated CO2. Dandelion leaves near hot spots undergo rapid color change from green to red before senescing to a desiccated brown, while xeromorphic grass leaves do not. Species-specific differences in leaf survival following exposure to CO2 may be linked to species-specific differences in stomatal conductance, and to rhizosphere and mycorrhizal responses. Initial survey results of plant species distribution suggest a shift from a dandelion-grass to a grass-dominated community over hot spots. Sudden and long-term shifts in species composition have important ecological implications and may provide a means of surface detection of upwelling CO2.

Surface restructuring behavior of various types of poly(dimethylsiloxane) in water detected by SFG.

PubMed

Chen, Chunyan; Wang, Jie; Chen, Zhan

2004-11-09

Surface structures of several different poly(dimethylsiloxane) (PDMS) materials, tetraethoxysilane-cured hydroxy-terminated PDMS (TEOS-PDMS), platinum-cured vinyl-terminated PDMS (Pt-PDMS), platinum-cured vinyl-terminated poly(diphenylsiloxane)-co-poly(dimethylsiloxane) (PDPS-co-PDMS), and PDMS-co-polystyrene (PDMS-co-PS) copolymer in air and water have been investigated by sum frequency generation (SFG) vibrational spectroscopy. The SFG spectra collected from all PDMS surfaces in both air and water are dominated by methyl group stretches, indicating that all the surfaces are mainly covered by methyl groups. Other than surface-dominating methyl groups, some -Si-CH2-CH2- moieties on the Pt-PDMS surface have also been detected in air, which are present at cross-linking points. Information about the average orientation angle and angle distribution of the methyl groups on the PDMS surface has been evaluated. Surface restructuring of the methyl groups has been observed for all PDMS surfaces in water. Upon contacting water, the methyl groups on all PDMS surfaces tilt more toward the surface. The detailed restructuring behaviors of several PDMS surfaces in water and the effects of molecular weight on restructuring behaviors have been investigated. For comparison, in addition to air and water, surface structures of PDMS materials mentioned above in a nonpolar solvent, FC-75, have also been studied. By comparing the different response of phenyl groups to water on both PDPS-co-PDMS and PS-co-PDMS surfaces, we have demonstrated how the restructuring behaviors of surface phenyl groups are affected by the structural flexibility of the molecular chains where they are attached.

Nature, formation, and distribution of carbonates on Ceres.

PubMed

Carrozzo, Filippo Giacomo; De Sanctis, Maria Cristina; Raponi, Andrea; Ammannito, Eleonora; Castillo-Rogez, Julie; Ehlmann, Bethany L; Marchi, Simone; Stein, Nathaniel; Ciarniello, Mauro; Tosi, Federico; Capaccioni, Fabrizio; Capria, Maria Teresa; Fonte, Sergio; Formisano, Michelangelo; Frigeri, Alessandro; Giardino, Marco; Longobardo, Andrea; Magni, Gianfranco; Palomba, Ernesto; Zambon, Francesca; Raymond, Carol A; Russell, Christopher T

2018-03-01

Different carbonates have been detected on Ceres, and their abundance and spatial distribution have been mapped using a visible and infrared mapping spectrometer (VIR), the Dawn imaging spectrometer. Carbonates are abundant and ubiquitous across the surface, but variations in the strength and position of infrared spectral absorptions indicate variations in the composition and amount of these minerals. Mg-Ca carbonates are detected all over the surface, but localized areas show Na carbonates, such as natrite (Na 2 CO 3 ) and hydrated Na carbonates (for example, Na 2 CO 3 ·H 2 O). Their geological settings and accessory NH 4 -bearing phases suggest the upwelling, excavation, and exposure of salts formed from Na-CO 3 -NH 4 -Cl brine solutions at multiple locations across the planet. The presence of the hydrated carbonates indicates that their formation/exposure on Ceres' surface is geologically recent and dehydration to the anhydrous form (Na 2 CO 3 ) is ongoing, implying a still-evolving body.

Likelihood of Brine and CO 2 Leak Detection using Magnetotellurics and Electrical Resistivity Tomography Methods

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

Yang, X.; Buscheck, T. A.; Mansoor, K.

The US DOE National Risk Assessment Partnership (NRAP), funded through the Office of Fossil Energy and NETL, is developing methods to evaluate the effectiveness of monitoring techniques to detect brine and CO 2 leakage from legacy wells into underground sources of drinking water (USDW) overlying a CO 2 storage reservoir. As part of the NRAP Strategic Monitoring group, we have generated 140 simulations of aquifer impact data based on the Kimberlina site in California’s southern San Joaquin Basin, Kimberlina Rev. 1.1. CO 2 buoyancy allows some of the stored CO 2 to reach shallower permeable zones and is detectable withmore » surface geophysical sensors. We are using this simulated data set to evaluate effectiveness of electrical resistivity tomography (ERT) and magnetotellurics (MT) for leak detection. The evaluation of additional monitoring methods such as pressure, seismic and gravity is underway through a multi-lab collaboration.« less

The effects of colorimetric detection of heavy metal ions based on Au nanoparticles (NPs): size and shape—a case of Co2+

NASA Astrophysics Data System (ADS)

Leng, Yumin; He, Junbao; Li, Bo; Xing, Xiaojing; Guo, Yongming; Ye, Liqun; Lu, Zhiwen

2017-09-01

The different sized and shaped Au NPs have intrigued considerable attention, because they possess different surface plasma resonance (SPR) absorption bands and thus result in many colorimetric Au NP-based detection applications. In this article, four different sized and shaped Au NPs of nanodots/rods were prepared and characterized. The as-prepared Au NPs were modified by the negatively charged anions of [SCH2CO2]2- to investigate both the size and shape effects of modified Au NPs on colorimetric detection of Co2+ and the corresponding SPR absorption properties. The different-shaped Au NPs possess different SPR absorption properties. The Au nanorods appeared to be colorimetric sensitive for Co2+ sensing.

Molecular beam scattering from C-13 enriched Kapton and correlation with the EOIM-3 carousel experiment

NASA Technical Reports Server (NTRS)

Minton, Timothy K.; Moore, Teresa A.

1995-01-01

Mass spectra of products emerging from identical samples of a C-13-enriched polyimide polymer (chemically equivalent to Kapton) under atomic oxygen bombardment in space and in the laboratory were collected. Reaction products unambiguously detected in space were CO-13, NO, (12)CO2, and (13)CO2. These reaction products and two others, H2O and CO-12, were detected in the laboratory, along with inelastically scattered atomic and molecular oxygen. Qualitative agreement was seen in the mass spectra taken in space and in the laboratory; the agreement may be improved by reducing the fraction of O2 in the laboratory molecular beam. Both laboratory and space data indicated that CO and CO2 products come preferentially from reaction with the imide component of the polymer chain, raising the possibility that the either component may degrade in part by the 'evaporation' of higher molecular weight fragments. Laboratory time-of-flight distributions showed: (1) incomplete energy accommodation of impinging O and O2 species that do not react with the surface; and (2) both hyperthermal and thermal CO and CO2 products, suggesting two distinct reaction mechanisms with the surface.

Methods and apparatus for measuring small leaks from carbon dioxide sequestration facilities

DOEpatents

Nelson, Jr., David D.; Herndon, Scott C.

2018-01-02

In one embodiment, a CO.sub.2 leak detection instrument detects leaks from a site (e.g., a CO.sub.2 sequestration facility) using rapid concentration measurements of CO.sub.2, O.sub.2 and optionally water concentration that are achieved, for example, using laser spectroscopy (e.g. direct absorption laser spectroscopy). Water vapor in the sample gas may not be removed, or only partially removed. The sample gas may be collected using a multiplexed inlet assembly from a plurality of locations. CO.sub.2 and O.sub.2 concentrations may be corrected based on the water concentration. A resulting dataset of the CO.sub.2 and O.sub.2 concentrations is analyzed over time intervals to detect any changes in CO.sub.2 concentration that are not anti-correlated with O.sub.2 concentration, and to identify a potential CO.sub.2 leak in response thereto. The analysis may include determining eddy covariance flux measurements of sub-surface potential carbon.

Laboratory IR Detection of H2O, CO2 in Ion-Irradiated Ices Relevant to Europa

NASA Technical Reports Server (NTRS)

Moore, Marla H.; Hudson, R. L.

1999-01-01

Hydrogen peroxide has been identified on Europa (Carlson et al. 1999) based in part on the 3.50 micron absorption feature observed in Galileo NIMS spectra. The observed feature was fitted with laboratory reflectance spectra of H2O + H2O2. Since condensed phase molecules on Europa (H2O, CO2, SO2, and H2O2) are bombarded with a significant flux of energetic particles (H(+), O(n+), S(n+) and e-), we examined the proton irradiation of H2O at 80 K and the conditions for the IR detection of H2O2 near 3.5 microns. Contrary to expectations, H2O2 was not detected if pure H2O ice was irradiated at 80 K. This was an unexpected result since, H2O2 was detected if pure H2O was irradiated at 18 K. We find, however, that if H2O ice contains either O2 or CO2 then H2O2 is detected after irradiation at 80 K (Moore and Hudson, 1999). The source of O2 for the H2O ice on Europa could come from surface interactions with the tenuous oxygen atmosphere, or from the bombardment of the surface by O(n+).

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.

Feasibility study of a space-based high pulse energy 2  μm CO2 IPDA lidar.

PubMed

Singh, Upendra N; Refaat, Tamer F; Ismail, Syed; Davis, Kenneth J; Kawa, Stephan R; Menzies, Robert T; Petros, Mulugeta

2017-08-10

Sustained high-quality column carbon dioxide (CO 2 ) atmospheric measurements from space are required to improve estimates of regional and continental-scale sources and sinks of CO 2 . Modeling of a space-based 2 μm, high pulse energy, triple-pulse, direct detection integrated path differential absorption (IPDA) lidar was conducted to demonstrate CO 2 measurement capability and to evaluate random and systematic errors. Parameters based on recent technology developments in the 2 μm laser and state-of-the-art HgCdTe (MCT) electron-initiated avalanche photodiode (e-APD) detection system were incorporated in this model. Strong absorption features of CO 2 in the 2 μm region, which allows optimum lower tropospheric and near surface measurements, were used to project simultaneous measurements using two independent altitude-dependent weighting functions with the triple-pulse IPDA. Analysis of measurements over a variety of atmospheric and aerosol models using a variety of Earth's surface target and aerosol loading conditions were conducted. Water vapor (H 2 O) influences on CO 2 measurements were assessed, including molecular interference, dry-air estimate, and line broadening. Projected performance shows a <0.35  ppm precision and a <0.3  ppm bias in low-tropospheric weighted measurements related to column CO 2 optical depth for the space-based IPDA using 10 s signal averaging over the Railroad Valley (RRV) reference surface under clear and thin cloud conditions.

Using the Bongwana natural CO2 release to understand leakage processes and develop monitoring

NASA Astrophysics Data System (ADS)

Jones, David; Johnson, Gareth; Hicks, Nigel; Bond, Clare; Gilfillan, Stuart; Kremer, Yannick; Lister, Bob; Nkwane, Mzikayise; Maupa, Thulani; Munyangane, Portia; Robey, Kate; Saunders, Ian; Shipton, Zoe; Pearce, Jonathan; Haszeldine, Stuart

2016-04-01

Natural CO2 leakage along the Bongwana Fault in South Africa is being studied to help understand processes of CO2 leakage and develop monitoring protocols. The Bongwana Fault crops out over approximately 80 km in KwaZulu-Natal province, South Africa. In outcrop the fault is expressed as a broad fracture corridor in Dwyka Tillite, with fractures oriented approximately N-S. Natural emissions of CO2 occur at various points along the fault, manifest as travertine cones and terraces, bubbling in the rivers and as gas fluxes through soil. Exposed rock outcrop shows evidence for Fe-staining around fractures and is locally extensively kaolinitised. The gas has also been released through a shallow water well, and was exploited commercially in the past. Preliminary studies have been carried out to better document the surface emissions using near surface gas monitoring, understand the origin of the gas through major gas composition and stable and noble gas isotopes and improve understanding of the structural controls on gas leakage through mapping. In addition the impact of the leaking CO2 on local water sources (surface and ground) is being investigated, along with the seismic activity of the fault. The investigation will help to build technical capacity in South Africa and to develop monitoring techniques and plans for a future CO2 storage pilot there. Early results suggest that CO2 leakage is confined to a relatively small number of spatially-restricted locations along the weakly seismically active fault. Fracture permeability appears to be the main method by which the CO2 migrates to the surface. The bulk of the CO2 is of deep origin with a minor contribution from near surface biogenic processes as determined by major gas composition. Water chemistry, including pH, DO and TDS is notably different between CO2-rich and CO2-poor sites. Soil gas content and flux effectively delineates the fault trace in active leakage sites. The fault provides an effective testing ground for field-based monitoring with results to date indicating the methods and technologies tested successfully detect leaking CO2. Further work will investigate the source of the CO2 and attempt to quantify CO2 flux rates and detection thresholds.

Rapid detection and characterization of surface CO2 leakage through the real-time measurement of δ13C signatures in CO2 flux from the ground

NASA Astrophysics Data System (ADS)

Krevor, Samuel; Benson, Sally; Rella, Chris; Perrin, Jean-Christophe; Esposito, Ariel; Crosson, Eric

2010-05-01

The surface monitoring of CO2 over geologic sequestration sites will be an essential tool in the monitoring and verification of sequestration projects. Surface monitoring is the only tool that currently provides the opportunity to detect and quantify leakages on the order of 1000 tons/year CO2. Near-surface detection and quantification can be made complicated, however, due to large temporal and spatial variations in natural background CO2 fluxes from biological processes. In addition, current surface monitoring technologies, such as the use of IR spectroscopy in eddy covariance towers and aerial surveys, radioactive or noble gas isotopic tracers, and flux chamber gas measurements can generally accomplish one or two of the necessary tasks of leak detection, identification, and quantification, at both large spatial scales and high spatial resolution. It would be useful, however, to combine the utility of these technologies so that a much simplified surface monitoring program can be deployed. Carbon isotopes of CO2 provide an opportunity to distinguish between natural biogenic CO2 fluxes from the ground and CO2 leaking from a sequestration reservoir that has ultimate origins in a process giving it a distinct isotopic signature such as natural gas processing. Until recently, measuring isotopic compositions of gases was a time-consuming and expensive process utilizing mass-spectrometry, not practical for deployment in a high-resolution survey of a potential leakage site at the surface. Recent developments in commercially available instruments utilizing wavelength scanned cavity ringdown spectroscopy (WS-CRDS) and Fourier transform infrared spectroscopy (FT-IR) have made it possible to rapidly measure the isotopic composition of gases including the 13C and 12C isotopic composition of CO2 in a field setting. A portable stable carbon isotope ratio analyzer for carbon dioxide, based on wavelength scanned cavity ringdown spectroscopy, has been used to rapidly detect and characterize an intentional leakage of CO2 from an underground pipeline at the ZERT experimental facility in Bozeman, Montana. Rapid ( 1 hour) walking surveys of the entire 100m x 100m site were collected using this mobile, real-time instrument. The resulting concentration and 13C isotopic abundance maps were processed using simple yet powerful analysis techniques, permitting not only the identification of specific leakage locations, but providing the ability to distinguish petrogenic sources of CO2 from biogenic sources. At the site an approximately 100-meter horizontal well has been drilled below an alfalfa field at a depth between 1-3 meters below the surface. The well has perforations along the central 70 meters of the well. The overlying strata are highly permeable sand, silt, and topsoil. For 30 days starting July 15, 2009, CO2 was injected at a rate of 0.2 tonnes per day. The injection rate is designed to simulate leakage from a mature storage reservoir at an annual rate of between .001 and .01%. The isotopic composition of the gas from the tank is at δ13C signature of approximately -52 parts per thousand (per mil), far more negative than either atmospheric (approx. -8 per mil) or CO2 from soil respiration (approx. -26 per mil) at the site. The CO2 isotopic and concentration measurements were taken with a Picarro WS-CRDS analyzer with 1/8' tubing connected to a sampling inlet. Simultaneous with CO2 concentrations (including 13C), position data was logged using a GPS receiver. Datapoints are taken around every second. The analyzer was powered using batteries and housed in a mobile cart. The surveys consisted of traverses of the site along the length of the pipeline and extending out 100 meters on either side of the pipeline with the end of the gas inlet tube approximate 9 cm above the ground at a speed of 1-2m/sec. This simulates the type of survey that could be easily performed if the actual or potential site of a leak was known to within an area on the order of 100 square kilometers or less, the scale of expected industrial CO2 sequestration operations. The surveys were performed both during the day and during the evening when CO2 flux due to respiration from the soil is markedly different. Keeling plots were used to characterize the spatially varying 13C composition of ground source CO2 across the site. A map constructed from this data shows that CO2 flux from sources of leakage was characterized by a δ13C of -40 per mil or less whereas locations away from the leakage spots had much higher δ13C signatures, -25 per mil or higher. The distinct isotopic signature allows for a clear discernment between leakage of petrogenic CO2 and that of natural CO2 fluxes from soil respiration. This is particularly valuable in the circumstance where the leak is slow enough that it could not be identified from CO2 concentration or flux changes above the natural background signal alone. Moreover, this detection took place both rapidly and at high spatial resolution. Samples collected from a mobile platform moving at the rate and with the sampling frequency used in this study could provide a 1000 km of survey traverses over an area of 100 km2 within 2-3 weeks. This provides a powerful tool for surface monitoring, combining the utilities of leak detection, characterization, and source identification with rapid deployment across large spatial scales and high spatial resolutions.

Synthesis and processing of ELISA polymer substitute: The influence of surface chemistry and morphology on detection sensitivity

NASA Astrophysics Data System (ADS)

Hosseini, Samira; Ibrahim, Fatimah; Djordjevic, Ivan; Rothan, Hussin A.; Yusof, Rohana; van der Marel, Cees; Koole, Leo H.

2014-10-01

Despite the known drawbacks of enzyme-linked immunosorbent assay (ELISA), one of the deficiencies that have relatively been ignored is the performance of ELISA substrate itself. Polystyrene (PS), as the cost effective material of choice for mass production of ELISA well-plates, has shown obvious lacks of suitable physical and chemical properties for protein attachment. The general concept of this work was to develop a potential substrate that can be suggested as a material of choice for production of a new generation of ELISA analytical kits. Spin-coated thin films of polymethyl methacrylate-co-methacrylic acid (PMMA-co-MAA) on silicon surfaces were designed and processed for detection of dengue virus. Coated surfaces of different molar ratios have been investigated as carboxyl-functionalized layers for obtaining platform for biomolecule immobilization with high level of protein activity. To improve the sensitivity of detection, we have used amine functional "spacers", hexamethylenediamine (HMDA) and polyethyleneimine (PEI), which were covalently bonded to the surfaces of PMMA-co-MAA coatings. Results demonstrate that the variation of surface concentration of carboxyl groups of PMMA-co-MAA can be used to control the amine surface concentration after carbodiimide coupling with HMDA and PEI spacers. The presence of amine spacers increases hydrophilicity of the coatings and significantly impacts the polymer surface morphology. In particular, protein immobilization via amine-bearing spacers has been achieved in two effective steps: (1) carbodiimide bonding between amine spacer molecules and PMMA-co-MAA polymer coatings; and (2) covalent immobilization of antibody via glutaraldehyde reaction with amine groups from amine-treated surfaces. The application of PEI spacer in comparison to HMDA has shown much higher intensity of detection signal in ELISA experiment, indicating better immobilization efficiency and preservation of antibody activity upon attachment to the polymer surface.

Synthesis, characterization and magnetic behavior of Co/MCM-41 nano-composites

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

Cuello, N.; Elías, V.; CONICET

2013-09-15

Synthesis, structure and magnetic properties of Co/MCM-41 as magnetic nano-composites have been investigated. Mesoporous materials with different degrees of metal loading were prepared by wet impregnation and characterized by ICP, XRD, N{sub 2} adsorption, UV–vis DRS, TPR and EPMA-EDS. Cobalt oxide clusters and Co{sub 3}O{sub 4} nano-particles could be confined inside the mesopores of MCM-41, being this fact favored by the Co loading increasing. In addition, larger crystals of Co{sub 3}O{sub 4} detectable by XRD also grow on the surface when the Co loading is enhanced. The magnetic characterization was performed in a SQUID magnetometer using a maximum magnetic appliedmore » field µ{sub 0}Ha=1 T. While the samples with the higher Co loadings showed a behavior typically paramagnetic, a superparamagnetic contribution is more notorious for lower loadings, suggesting high Co species dispersion. - Graphical abstract: Room temperature hysteresis loops as a function of the Co content. Display Omitted - Highlights: • Co species as isolated Co{sup 2+}, oxide clusters and Co{sub 3}O{sub 4} nano-particles were detected. • For higher Co loads were detected, by XRD, Co{sub 3}O{sub 4} particles on the external surface. • The confining of Co species inside the mesopores was achieved by increasing Co load. • Paramagnetism from oxide clusters/nano-particles becomes dominant for higher Co loads. • Superparamagnetism can be assigned to Co species of small size and finely dispersed.« less

In Situ X-Ray Photoelectron Spectroscopy of Model Catalysts: At the Edge of the Gap

NASA Astrophysics Data System (ADS)

Blomberg, S.; Hoffmann, M. J.; Gustafson, J.; Martin, N. M.; Fernandes, V. R.; Borg, A.; Liu, Z.; Chang, R.; Matera, S.; Reuter, K.; Lundgren, E.

2013-03-01

We present high-pressure x-ray photoelectron spectroscopy (HP-XPS) and first-principles kinetic Monte Carlo study addressing the nature of the active surface in CO oxidation over Pd(100). Simultaneously measuring the chemical composition at the surface and in the near-surface gas phase, we reveal both O-covered pristine Pd(100) and a surface oxide as stable, highly active phases in the near-ambient regime accessible to HP-XPS. Surprisingly, no adsorbed CO can be detected during high CO2 production rates, which can be explained by a combination of a remarkably short residence time of the CO molecule on the surface and mass-transfer limitations in the present setup.

Hierarchical Co(OH)2 nanostructures/glassy carbon electrode derived from Co(BTC) metal-organic frameworks for glucose sensing

NASA Astrophysics Data System (ADS)

He, Juan; Lu, Xingping; Yu, Jie; Wang, Li; Song, Yonghai

2016-07-01

A novel Co(OH)2/glassy carbon electrode (GCE) has been fabricated via metal-organic framework (MOF)-directed method. In the strategy, the Co(BTC, 1,3,5-benzentricarboxylic acid) MOFs/GCE was firstly prepared by alternately immersing GCE in Co2+ and BTC solution based on a layer-by-layer method. And then, the Co(OH)2 with hierarchical flake nanostructure/GCE was constructed by immersing Co(BTC) MOFs/GCE into 0.1 M NaOH solution at room temperature. Such strategy improves the distribution of hierarchical Co(OH)2 nanostructures on electrode surface greatly, enhances the stability of nanomaterials on the electrode surface, and increases the use efficiency of the Co(OH)2 nanostructures. Scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray powder diffraction, energy dispersive spectroscopy, Fourier transform infrared spectroscopy, and Raman spectra were used to characterize the Co(BTC) MOFs/GCE and Co(OH)2/GCE. Based on the hierarchical Co(OH)2 nanostructures/GCE, a novel and sensitive nonenzymatic glucose sensor was developed. The good performance of the resulted sensor toward the detection of glucose was ascribed to hierarchical flake nanostructures, good mechanical stability, excellent distribution, and large specific surface area of Co(OH)2 nanostructures. The proposed preparation method is simple, efficient, and cheap .

Detecting regional patterns of changing CO2 flux in Alaska

PubMed Central

Parazoo, Nicholas C.; Wofsy, Steven C.; Koven, Charles D.; Sweeney, Colm; Lawrence, David M.; Lindaas, Jakob; Chang, Rachel Y.-W.; Miller, Charles E.

2016-01-01

With rapid changes in climate and the seasonal amplitude of carbon dioxide (CO2) in the Arctic, it is critical that we detect and quantify the underlying processes controlling the changing amplitude of CO2 to better predict carbon cycle feedbacks in the Arctic climate system. We use satellite and airborne observations of atmospheric CO2 with climatically forced CO2 flux simulations to assess the detectability of Alaskan carbon cycle signals as future warming evolves. We find that current satellite remote sensing technologies can detect changing uptake accurately during the growing season but lack sufficient cold season coverage and near-surface sensitivity to constrain annual carbon balance changes at regional scale. Airborne strategies that target regular vertical profile measurements within continental interiors are more sensitive to regional flux deeper into the cold season but currently lack sufficient spatial coverage throughout the entire cold season. Thus, the current CO2 observing network is unlikely to detect potentially large CO2 sources associated with deep permafrost thaw and cold season respiration expected over the next 50 y. Although continuity of current observations is vital, strategies and technologies focused on cold season measurements (active remote sensing, aircraft, and tall towers) and systematic sampling of vertical profiles across continental interiors over the full annual cycle are required to detect the onset of carbon release from thawing permafrost. PMID:27354511

Detecting regional patterns of changing CO 2 flux in Alaska

DOE PAGES

Parazoo, Nicholas C.; Commane, Roisin; Wofsy, Steven C.; ...

2016-06-27

With rapid changes in climate and the seasonal amplitude of carbon dioxide (CO 2) in the Arctic, it is critical that we detect and quantify the underlying processes controlling the changing amplitude of CO 2 to better predict carbon cycle feedbacks in the Arctic climate system. We use satellite and airborne observations of atmospheric CO 2 with climatically forced CO 2 flux simulations to assess the detectability of Alaskan carbon cycle signals as future warming evolves. We find that current satellite remote sensing technologies can detect changing uptake accurately during the growing season but lack sufficient cold season coverage andmore » near-surface sensitivity to constrain annual carbon balance changes at regional scale. Airborne strategies that target regular vertical profile measurements within continental interiors are more sensitive to regional flux deeper into the cold season but currently lack sufficient spatial coverage throughout the entire cold season. Thus, the current CO 2 observing network is unlikely to detect potentially large CO 2 sources associated with deep permafrost thaw and cold season respiration expected over the next 50 y. In conclusion, although continuity of current observations is vital, strategies and technologies focused on cold season measurements (active remote sensing, aircraft, and tall towers) and systematic sampling of vertical profiles across continental interiors over the full annual cycle are required to detect the onset of carbon release from thawing permafrost.« less

Constraining the processes modifying the surfaces of the classical Uranian satellites

NASA Astrophysics Data System (ADS)

Cartwright, Richard J.; Emery, Joshua P.

2016-10-01

Near-infrared (NIR) observations of the classical Uranian moons have detected relatively weak H2O ice bands, mixed with a spectrally red, low albedo constituent on the surfaces of their southern hemispheres (sub-observer lat. ~10 - 75°S). The H2O bands and the degree of spectral reddening are greatest on the leading hemispheres of these moons. CO2 ice bands have been detected in spectra collected over their trailing hemispheres, with stronger CO2 bands on the moons closest to Uranus. Our preferred hypotheses to explain the distribution of CO2, H2O, and dark material are: bombardment by magnetospherically-embedded charged particles, primarily on the trailing hemispheres of these moons, and bombardment by micrometeorites, primarily on their leading hemispheres.To test these complementary hypotheses, we are constraining the distribution and spectral characteristics of surface constituents on the currently observable northern hemispheres (sub-observer lat. ~20 - 35°N) to compare with existing southern hemisphere data. Analysis of northern hemisphere data shows that CO2 is present on their trailing hemispheres, and H2O bands and the degree of spectral reddening are strongest on their leading hemispheres, in agreement with the southern hemisphere data. This longitudinal distribution of constituents supports our preferred hypotheses.However, tantalizing mysteries regarding the distribution of constituents remain. There has been no detection of CO2 on Miranda, and H2O bands are stronger on its trailing hemisphere. NIR slope measurements indicate that the northern hemisphere of Titania is redder than Oberon, unlike the spectral colors of their southern hemispheres. There are latitudinal variations in H2O band strengths on these moons, with stronger H2O bands at northern latitudes compared to southern latitudes on Umbriel and Titania. Several Miranda and Ariel spectra potentially include weak and unconfirmed NH3-hydrate bands, which could be tracers of cryovolcanic emplacement. We will present work related to our goals of constraining the processes modifying the surfaces of the classical Uranian moons.

Sensitivity Studies for Space-based Measurements of Atmospheric Total Column Carbon Dioxide Using Reflected Sunlight

NASA Technical Reports Server (NTRS)

Mao, Jianping; Kawa, S. Randolph

2003-01-01

A series of sensitivity studies is carried out to explore the feasibility of space-based global carbon dioxide (CO2) measurements for global and regional carbon cycle studies. The detection method uses absorption of reflected sunlight in the CO2 vibration-rotation band at 1.58 micron. The sensitivities of the detected radiances are calculated using the line-by-line model (LBLRTM), implemented with the DISORT (Discrete Ordinates Radiative Transfer) model to include atmospheric scattering in this band. The results indicate that (a) the small (approx.1%) changes in CO2 near the Earth's surface are detectable in this CO2 band provided adequate sensor signal-to-noise ratio and spectral resolution are achievable; (b) the effects of other interfering constituents, such as water vapor, aerosols and cirrus clouds, on the radiance are significant but the overall effects of the modification of light path length on total back-to-space radiance sensitivity to CO2 change are minor for general cases, which means that generally the total column CO2 can be derived in high precision from the ratio of the on-line center to off-line radiances; (c) together with CO2 gas absorption aerosol/cirrus cloud layer has differential scattering which may result in the modification of on-line to off-line radiance ratio which could lead a large bias in the total column CO2 retrieval. Approaches to correct such bias need further investigation. (d) CO2 retrieval requires good knowledge of the atmospheric temperature profile, e.g. approximately 1K RMS error in layer temperature, which is achievable from new atmospheric sounders in the near future; (e) the atmospheric path length, over which the CO2 absorption occurs, should be known in order to correctly interpret horizontal gradients of CO2 from the total column CO2 measurement; thus an additional sensor for surface pressure measurement needs to be attached for a complete measurement package.

FutureGen 2.0 Monitoring Program: An Overview of the Monitoring Approach and Technologies Selected for Implementation

DOE PAGES

Vermeul, Vince R.; Strickland, Chris E.; Thorne, Paul D.; ...

2014-12-31

The FutureGen 2.0 Project will design and build a first-of-its-kind, near-zero emissions coal-fueled power plant with carbon capture and storage (CCS). To assess storage site performance and meet the regulatory requirements of the Class VI Underground Injection Control (UIC) Program for CO2 Geologic Sequestration, the FutureGen 2.0 project will implement a suite of monitoring technologies designed to 1) evaluate CO2 mass balance and 2) detect any unforeseen loss in CO2 containment. The monitoring program will include direct monitoring of the injection stream and reservoir, and early-leak-detection monitoring directly above the primary confining zone. It will also implement an adaptive monitoringmore » strategy whereby monitoring results are continually evaluated and the monitoring network is modified as required, including the option to drill additional wells in out-years. Wells will be monitored for changes in CO2 concentration and formation pressure, and other geochemical/isotopic signatures that provide indication of CO2 or brine leakage. Indirect geophysical monitoring technologies that were selected for implementation include passive seismic, integrated surface deformation, time-lapse gravity, and pulsed neutron capture logging. Near-surface monitoring approaches that have been initiated include surficial aquifer and surface- water monitoring, soil-gas monitoring, atmospheric monitoring, and hyperspectral data acquisition for assessment of vegetation conditions. Initially, only the collection of baseline data sets is planned; the need for additional near- surface monitoring will be continually evaluated throughout the design and operational phases of the project, and selected approaches may be reinstituted if conditions warrant. Given the current conceptual understanding of the subsurface environment, early and appreciable impacts to near-surface environments are not expected.« less

Field Tests of Real-time In-situ Dissolved CO2 Monitoring for CO2 Leakage Detection in Groundwater

NASA Astrophysics Data System (ADS)

Yang, C.; Zou, Y.; Delgado, J.; Guzman, N.; Pinedo, J.

2016-12-01

Groundwater monitoring for detecting CO2 leakage relies on groundwater sampling from water wells drilled into aquifers. Usually groundwater samples are required be collected periodically in field and analyzed in the laboratory. Obviously groundwater sampling is labor and cost-intensive for long-term monitoring of large areas. Potential damage and contamination of water samples during the sampling process can degrade accuracy, and intermittent monitoring may miss changes in the geochemical parameters of groundwater, and therefore signs of CO2 leakage. Real-time in-situ monitoring of geochemical parameters with chemical sensors may play an important role for CO2 leakage detection in groundwater at a geological carbon sequestration site. This study presents field demonstration of a real-time in situ monitoring system capable of covering large areas for detection of low levels of dissolved CO2 in groundwater and reliably differentiating natural variations of dissolved CO2 concentration from small changes resulting from leakage. The sand-alone system includes fully distributed fiber optic sensors for carbon dioxide detection with a unique sensor technology developed by Intelligent Optical Systems. The systems were deployed to the two research sites: the Brackenridge Field Laboratory where the aquifer is shallow at depths of 10-20 ft below surface and the Devine site where the aquifer is much deeper at depths of 140 to 150 ft. Groundwater samples were periodically collected from the water wells which were installed with the chemical sensors and further compared to the measurements of the chemical sensors. Our study shows that geochemical monitoring of dissolved CO2 with fiber optic sensors could provide reliable CO2 leakage signal detection in groundwater as long as CO2 leakage signals are stronger than background noises at the monitoring locations.

Atmospheric and soil-gas monitoring for surface leakage at the San Juan Basin CO{sub 2} pilot test site at Pump Canyon New Mexico, using perfluorocarbon tracers, CO{sub 2} soil-gas flux and soil-gas hydrocarbons

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

Wells, Arthur W; Diehl, J Rodney; Strazisar, Brian R

2012-05-01

Near-surface monitoring and subsurface characterization activities were undertaken in collaboration with the Southwest Regional Carbon Sequestration Partnership on their San Juan Basin coal-bed methane pilot test site near Navajo City, New Mexico. Nearly 18,407 short tons (1.670 × 107 kg) of CO{sub 2} were injected into 3 seams of the Fruitland coal between July 2008 and April 2009. Between September 18 and October 30, 2008, two additions of approximately 20 L each of perfluorocarbon (PFC) tracers were mixed with the CO{sub 2} at the injection wellhead. PFC tracers in soil-gas and in the atmosphere were monitored over a period ofmore » 2 years using a rectangular array of permanent installations. Additional monitors were placed near existing well bores and at other locations of potential leakage identified during the pre-injection site survey. Monitoring was conducted using sorbent containing tubes to collect any released PFC tracer from soil-gas or the atmosphere. Near-surface monitoring activities also included CO{sub 2} surface flux and carbon isotopes, soil-gas hydrocarbon levels, and electrical conductivity in the soil. The value of the PFC tracers was demonstrated when a significant leakage event was detected near an offset production well. Subsurface characterization activities, including 3D seismic interpretation and attribute analysis, were conducted to evaluate reservoir integrity and the potential that leakage of injected CO{sub 2} might occur. Leakage from the injection reservoir was not detected. PFC tracers made breakthroughs at 2 of 3 offset wells which were not otherwise directly observable in produced gases containing 20–30% CO{sub 2}. These results have aided reservoir geophysical and simulation investigations to track the underground movement of CO{sub 2}. 3D seismic analysis provided a possible interpretation for the order of appearance of tracers at production wells.« less

An In-Situ Root-Imaging System in the Context of Surface Detection of CO2

NASA Astrophysics Data System (ADS)

Apple, M. E.; Prince, J. B.; Bradley, A. R.; Zhou, X.; Lakkaraju, V. R.; Male, E. J.; Pickles, W.; Thordsen, J. J.; Dobeck, L.; Cunningham, A.; Spangler, L.

2009-12-01

Carbon sequestration is a valuable method of spatially confining CO2 belowground. The Zero Emissions Research Technology, (ZERT), site is an experimental facility in a former agricultural field on the Montana State University campus in Bozeman, Montana, where CO2 was experimentally released at a rate of 200kg/day in 2009 into a 100 meter underground injection well running parallel to the ground surface. This injection well, or pipe, has deliberate leaks at intervals, and CO2 travels from these leaks upward to the surface of the ground. The ZERT site is a model system designed with the purpose of testing methods of surface detection of CO2. One important aspect of surface detection is the determination of the effects of CO2 on the above and belowground portions of plants growing above sequestration fields. At ZERT, these plants consist of a pre-existing mixture of herbaceous species present at the agricultural field. Species growing at the ZERT site include several grasses, Dactylis glomerata (Orchard Grass), Poa pratensis (Kentucky Bluegrass), and Bromus japonicus (Japanese Brome); the nitrogen-fixing legumes Medicago sativa, (Alfalfa), and Lotus corniculatus, (Birdsfoot trefoil); and an abundance of Taraxacum officinale, (Dandelion). Although the aboveground parts of the plants at high CO2 are stressed, as indicated by changes in hyperspectral plant signatures, leaf fluorescence and leaf chlorophyll content, we are interested in determining whether the roots are also stressed. To do so, we are combining measurements of soil conductivity and soil moisture with root imaging. We are using an in-situ root-imaging system manufactured by CID, Inc. (Camas, WA), along with image analysis software (Image-J) to analyze morphometric parameters in the images and to determine what effects, if any, the presence of leaking and subsequently upwelling CO2 has on the phenology of root growth, growth and turnover of individual fine and coarse roots, branching patterns, and root density and depth in the soil. We drilled three holes for the plexiglass root-imaging tubes in December 2008 and installed the tubes post-thaw in May 2009, with the initial set of images taken in July 2009 on the day preceding the 4-week long CO2 injection. We collected images weekly thereafter until late August 2009 by inserted a rotating camera into the tube and photographing at 10 cm intervals from the surface to a depth of 75-80 cm. By August 2009, roots were visible at 80 cm below ground. The root-imaging tubes will remain in place so that we can track the roots through the upcoming years at the ZERT site. Each year, we anticipate gathering images in the fall, winter, before the beginning of root growth in the spring, as well as during the summer injections of CO2. The information gained from these images will be useful in linking above and belowground responses of plants to CO2.

Estimating lake-atmosphere CO2 exchange

USGS Publications Warehouse

Anderson, D.E.; Striegl, Robert G.; Stannard, D.I.; Michmerhuizen, C.M.; McConnaughey, T.A.; LaBaugh, J.W.

1999-01-01

Lake-atmosphere CO2 flux was directly measured above a small, woodland lake using the eddy covariance technique and compared with fluxes deduced from changes in measured lake-water CO2 storage and with flux predictions from boundary-layer and surface-renewal models. Over a 3-yr period, lake-atmosphere exchanges of CO2 were measured over 5 weeks in spring, summer, and fall. Observed springtime CO2 efflux was large (2.3-2.7 ??mol m-2 s-1) immediately after lake-thaw. That efflux decreased exponentially with time to less than 0.2 ??mol m-2 s-1 within 2 weeks. Substantial interannual variability was found in the magnitudes of springtime efflux, surface water CO2 concentrations, lake CO2 storage, and meteorological conditions. Summertime measurements show a weak diurnal trend with a small average downward flux (-0.17 ??mol m-2 s-1) to the lake's surface, while late fall flux was trendless and smaller (-0.0021 ??mol m-2 s-1). Large springtime efflux afforded an opportunity to make direct measurement of lake-atmosphere fluxes well above the detection limits of eddy covariance instruments, facilitating the testing of different gas flux methodologies and air-water gas-transfer models. Although there was an overall agreement in fluxes determined by eddy covariance and those calculated from lake-water storage change in CO2, agreement was inconsistent between eddy covariance flux measurements and fluxes predicted by boundary-layer and surface-renewal models. Comparison of measured and modeled transfer velocities for CO2, along with measured and modeled cumulative CO2 flux, indicates that in most instances the surface-renewal model underpredicts actual flux. Greater underestimates were found with comparisons involving homogeneous boundary-layer models. No physical mechanism responsible for the inconsistencies was identified by analyzing coincidentally measured environmental variables.

Hydrochemical variations in selected geothermal groundwater and carbonated springs in Korea: a baseline study for early detection of CO2 leakage.

PubMed

Choi, Hanna; Piao, Jize; Woo, Nam C; Cho, Heuynam

2017-02-01

A baseline hydrochemistry of the above zone aquifer was examined for the potential of CO 2 early detection monitoring. Among the major ionic components and stable isotope ratios of oxygen, hydrogen, and carbon, components with a relative standard deviation (RSD) of <10 % for the seasonal variation were selected as relatively stable. These components were tested for sensitivity to the introduction of 0.1 mol/L CO 2 (g) using the PHREEQC simulation results. If the relatively stable components were sensitive to the introduction of CO 2 , then they could be used as indicators of CO 2 leakage into the above zone. As an analog to the zone above CO 2 storage formation, we sampled deep groundwater, including geothermal groundwater from well depths of 400-700 m below the ground surface (bgs) and carbonated springs with a high CO 2 content in Korea. Under the natural conditions of inland geothermal groundwater, pH, electrical conductivity (EC), bicarbonate (HCO 3 ), δ 18 O, δ 2 H, and δ 13 C were relatively stable as well as sensitive to the introduction of CO 2 (g), thus showing good potential as monitoring parameters for early detection of CO 2 leakage. In carbonated springs, the parameters identified were pH, δ 18 O, and δ 2 H. Baseline hydrochemistry monitoring could provide information on parameters useful for detecting anomalies caused by CO 2 leakage as measures for early warning.

Monitoring CO2 Intrusion in shallow aquifer using complex electrical methods and a novel CO2 sensitive Lidar-based sensor

NASA Astrophysics Data System (ADS)

Leger, E.; Dafflon, B.; Thorpe, M.; Kreitinger, A.; Laura, D.; Haivala, J.; Peterson, J.; Spangler, L.; Hubbard, S. S.

2016-12-01

While subsurface storage of CO2 in geological formations offers significant potential to mitigate atmospheric greenhouse gasses, approaches are needed to monitor the efficacy of the strategy as well as possible negative consequences, such as leakage of CO2 or brine into groundwater or release of fugitive gaseous CO2. Groundwater leakages can cause subsequent reactions that may also be deleterious. For example, a release of dissolved CO2 into shallow groundwatersystems can decrease groundwater pH which can potentiallymobilize naturally occurring trace metals and ions. In this perspective, detecting and assessing potential leak requires development of novel monitoring techniques.We present the results of using surface electrical resistivity tomography (ERT) and a novel CO2 sensitive Lidar-based sensor to monitor a controlled CO2 release at the ZeroEmission Research and Technology Center (Bozeman, Montana). Soil temperature and moisture sensors, wellbore water quality measurements as well as chamber-based CO2 flux measurements were used in addition to the ERT and a novel Lidar-based sensor to detect and assess potential leakage into groundwater, vadose zone and atmosphere. The three-week release wascarried out in the vadose and the saturated zones. Well sampling of pH and conductivity and surface CO2 fluxes and concentrations measurements were acquired during the release and are compared with complex electricalresistivity time-lapse measurements. The novel Lidar-based image of the CO2 plume were compared to chamber-based CO2 flux and concentration measurements. While a continuous increase in subsurface ERT and above ground CO2 was documented, joint analysis of the above and below ground data revealed distinct transport behavior in the vadose and saturated zones. Two type of transport were observed, one in the vadoze zone, monitored by CO2 flux chamber and ERT, and the other one in the saturated zone, were ERT and wellsampling were carried. The experiment suggests how a range of geophysical, remote sensing, hydrological and geochemical measurement approaches can be optimally configured to detect the distribution and explore behavior of possible CO2 leakages in distinct compartments, including groundwater, vadose zone, and atmosphere.

Reaction Mechanisms for the Electrochemical Reduction of CO 2 to CO and Formate on the Cu(100) Surface at 298 K from Quantum Mechanics Free Energy Calculations with Explicit Water

DOE PAGES

Cheng, Tao; Xiao, Hai; Goddard, William A.

2016-10-11

Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions is not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or to carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). We carry out QM calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO 2 reduction reaction conditions) to examine the initial reaction pathways to form CO and formatemore » (HCOO –) from CO 2 through free energy calculations at 298 K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ-), with a free energy barrier of ΔG ‡ = 0.43 eV, the rate-determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 and 0.30 eV, respectively. HCOO– formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO – formation occurs in the first electron-transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Therefore, to alter the product distribution, we need to control this first step of CO 2 binding, which might involve controlling pH, alloying, or changing the structure at the nanoscale.« less

Reaction Mechanisms for the Electrochemical Reduction of CO2 to CO and Formate on the Cu(100) Surface at 298K from Quantum Mechanics Free Energy Calculations with Explicit Water.

PubMed

Cheng, Tao; Xiao, Hai; Goddard, William A

2016-10-11

Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions are not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). Here, we carry out Quantum Mechanics (QM) calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO2RR conditions) to examine the initial reaction pathways to form CO and formate (HCOO - ) from CO 2 through free energy calculations at 298K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ- ), with a free energy barrier of ΔG ‡ =0.43 eV, the rate determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 eV and 0.30 eV, respectively. HCOO - formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO - formation occurs in the first electron transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Thus, to alter the product distribution we need to control this first step of CO 2 binding, which might involve alloying or changing the structure at the nanoscale.

Comparison of CO 2 Detection Methods Tested in Shallow Groundwater Monitoring Wells at a Geological Sequestration Site

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

Edenborn, Harry M.; Jain, Jinesh N.

The geological storage of anthropogenic carbon dioxide (CO 2) is one method of reducing the amount of CO 2 released into the atmosphere. Monitoring programs typically determine baseline conditions in surface and near-surface environments before, during, and after CO 2 injection to evaluate if impacts related to injection have occurred. Because CO 2 concentrations in groundwater fluctuate naturally due to complex geochemical and geomicrobiologicalinteractions, a clear understanding of the baseline behavior of CO 2 in groundwater near injection sites is important. Numerous ways of measuring aqueous CO 2 in the field and lab are currently used, but most methods havemore » significant shortcomings (e.g., are tedious, lengthy, have interferences, or have significant lag time before a result is determined). In this study, we examined the effectiveness of two novel CO 2 detection methods and their ability to rapidly detect CO2in shallow groundwater monitoring wells associated with the Illinois Basin –Decatur Project geological sequestration site. The CarboQC beverage carbonation meter was used to measure the concentration of CO 2 in water by monitoring temperature and pressure changes and calculating the PCO 2 from the ideal gas law. Additionally, a non-dispersive infrared (NDIR) CO< sub>2sensor enclosed in a gas-permeable, water-impermeable membrane measured CO2by determining an equilibrium concentration. Results showed that the CarboQC method provided rapid (< 3 min) and repeatable results under field conditions within a measured concentration range of 15 –125 mg/L CO 2. The NDIR sensor results correlated well (r 2= 0.93) with the CarboQC data, but CO 2 equilibration required at least 15 minutes, making the method somewhat less desirable under field conditions. In contrast, NDIR-based sensors have a greater potential for long-term deployment. Both systems are adaptable to in-line groundwater sampling methods. Other specific advantages and disadvantages associated with the two approaches, and anomalies associated with specific samples, are discussed in greater detail in this poster.« less

The potential of near-surface geophysical methods in a hierarchical monitoring approach for the detection of shallow CO2 seeps at geological storage sites

NASA Astrophysics Data System (ADS)

Sauer, U.; Schuetze, C.; Dietrich, P.

2013-12-01

The MONACO project (Monitoring approach for geological CO2 storage sites using a hierarchic observation concept) aims to find reliable monitoring tools that work on different spatial and temporal scales at geological CO2 storage sites. This integrative hierarchical monitoring approach based on different levels of coverage and resolutions is proposed as a means of reliably detecting CO2 degassing areas at ground surface level and for identifying CO2 leakages from storage formations into the shallow subsurface, as well as CO2 releases into the atmosphere. As part of this integrative hierarchical monitoring concept, several methods and technologies from ground-based remote sensing (Open-path Fourier-transform infrared (OP-FTIR) spectroscopy), regional measurements (near-surface geophysics, chamber-based soil CO2 flux measurement) and local in-situ measurements (using shallow boreholes) will either be combined or used complementary to one another. The proposed combination is a suitable concept for investigating CO2 release sites. This also presents the possibility of adopting a modular monitoring concept whereby our monitoring approach can be expanded to incorporate other methods in various coverage scales at any temporal resolution. The link between information obtained from large-scale surveys and local in-situ monitoring can be realized by sufficient geophysical techniques for meso-scale monitoring, such as geoelectrical and self-potential (SP) surveys. These methods are useful for characterizing fluid flow and transport processes in permeable near-surface sedimentary layers and can yield important information concerning CO2-affected subsurface structures. Results of measurements carried out a natural analogue site in the Czech Republic indicate that the hierarchical monitoring approach represents a successful multidisciplinary modular concept that can be used to monitor both physical and chemical processes taking place during CO2 migration and seepage. The application of FTIR spectroscopy in combination with soil gas surveys and geophysical investigations results in a comprehensive site characterization, including atmospheric and near-surface CO2 distribution, as well as subsurface structural features. We observed a correlation of higher CO2 concentration and flux rates at the meso-scale that coincides with distinct geophysical anomalies. Here, we found prominent SP anomalies and zones of lower resistivity in the geoelectrical images compared to undisturbed regions nearby. This presentation will discuss the results we obtained and illustrate the influence of CO2 on electrical parameters measured under field conditions in relation to environmental parameters.

Reactivity of formic acid (HCOOD and DCOOH) at uranium and UO 2.0 surfaces

NASA Astrophysics Data System (ADS)

Manner, William L.; Lloyd, Jane A.; Paffett, Mark T.

1999-10-01

Interactions of DCOOH and HCOOD with uranium and UO 2.0 surfaces have been examined using surface-specific techniques of thermal desorption mass spectroscopy (TDMS), X-ray photoelectron spectroscopy (XPS), and static secondary ion mass spectroscopy (SSIMS). On the clean uranium surface, formate is the predominant product following formic acid adsorption at 100 K. A wide range of products is observed after annealing to 200 K, including formate, hydroxyl, O ads, and H ads (D ads) groups. Adsorbed formate decomposes by 300 K increasing the concentration of the remaining surface products. Surface-adsorbed carbon following TDMS measurements remains as the carbide, as indicated from XPS and SSIMS measurements. The only gaseous species created in high yields from the clean surface upon annealing are H 2, HD, and D 2. On the oxide surface (UO 2.0), adsorbed formate groups are more stable toward dissociation in comparison with the clean uranium surface. Between 100 and 300 K the predominant species on the UO 2.0 surface are surface formate and hydroxyl groups. Hydroxyl groups react between 300 and 350 K to release water from the surface. Adsorbed formate groups decompose between 400 and 500 K to release CO and H 2CO (D 2CO) groups from the oxide surface. Carbon was not detected on the oxide surface by XPS or SSIMS after annealing to 500 K, indicating that all carbon-containing species either desorb in the form of CO-containing products or migrate into the surface.

Amine–mixed oxide hybrid materials for carbon dioxide adsorption from CO2/H2 mixture

NASA Astrophysics Data System (ADS)

Ravi, Navin; Aishah Anuar, Siti; Yusuf, Nur Yusra Mt; Isahak, Wan Nor Roslam Wan; Shahbudin Masdar, Mohd

2018-05-01

Bio-hydrogen mainly contains hydrogen and high level of carbon dioxide (CO2). High concentration of CO2 lead to a limitation especially in fuel cell application. In this study, the amine-mixed oxide hybrid materials for CO2 separation from bio-hydrogen model (50% CO2:50% H2) have been studied. Fourier-transform infrared spectroscopy (FTIR) and x-ray diffraction (XRD) characterizations showed that the amine–mixed oxide hybrid materials successfully adsorbed CO2 physically with no chemical adsorption evidence. The dry gas of CO2/H2 mixture adsorbed physically on amine–CuO–MgO hybrid material. No carbonates were detected after several times of adsorption, which indicated the good recyclability of adsorbents. The adsorbent system of diethanolamine (DEA)/15% CuO–75% MgO showed the highest CO2 adsorption capacity of 21.2 wt% due to the presence of polar substance on MgO surface, which can adsorb CO2 at ambient condition. The alcohol group of DEA can enhance the CO2 solubility on the adsorbent surface. In the 20% CuO–50% MgO adsorbent system, DEA as amine type showed a high CO2 adsorption of 19.4 wt%. The 10% amine loading system showed that the DEA adsorption system provided high CO2 adsorption. The BET analysis confirmed that a high amine loading contributed to the decrease in CO2 adsorption due to the low surface area of the adsorbent system.

Skating on thin ice: surface chemistry under interstellar conditions

NASA Astrophysics Data System (ADS)

Fraser, H.; van Dishoeck, E.; Tielens, X.

Solid CO2 has been observed towards both active star forming regions and quiescent clouds (Gerakines et. al. (1999)). The high abundance of CO2 in the solid phase, and its low abundance in the gas phase, support the idea that CO2 is almost exclusively formed in the solid state. Several possible formation mechanisms have been postulated (Ruffle &Herbst (2001): Charnley &Kaufman (2000)), and the detection of CO2 towards quiescent sources such as Elias 16 (Whittet et. al. (1998)) clearly suggests that CO2 can be produced in the absence of UV or electron mediated processes. The most likely route is via the surface reactions between O atoms, or OH radicals, and CO. The tools of modern surface- science offer us the potential to determine many of the physical and chemical attributes of icy interstellar grain mantles under highly controlled conditions, that closely mimic interstellar environments. The Leiden Surface Reaction Simulation Device ( urfreside) combines UHV (UltraS High Vacuum) surface science techniques with an atomic beam to study chemical reactions occurring on the SURFACE and in the BULK of interstellar ice grain mimics. By simultaneously combining two or more surface analysis techniques, the chemical kinetics, reaction mechanisms and activation energies can be determined directly. The experiment is aimed at identifying the key barrierless reactions and desorption pathways on and in H2 O and CO ices under interstellar conditions. The results from traditional HV (high vacuum) and UHV studies of the CO + O and CO + OH reactions will be presented in this paper. Charnley, S.B., & Kaufman, M.J., 2000, ApJ, 529, L111 Gerakines, P.A., 1999, ApJ, 522, 357 Ruffle, D.P., & Herbst, E., 2001, MNRAS, 324, 1054 Whittet, D.C.B., et.al., 1998, ApJ, 498, L159

Evidence for speckle effects on pulsed CO2 lidar signal returns from remote targets

NASA Technical Reports Server (NTRS)

Menzies, R. T.; Kavaya, M. J.; Flamant, P. H.

1984-01-01

A pulsed CO2 lidar was used to study statistical properties of signal returns from various rough surfaces at distances near 2 km. These included natural in situ topographic materials as well as man-made hard targets. Three lidar configurations were used: heterodyne detection with single temporal mode transmitter pulses, and direct detection with single and multiple temporal mode pulses. The significant differences in signal return statistics, due largely to speckle effects, are discussed.

Characterizing near-surface CO2 conditions before injection - Perspectives from a CCS project in the Illinois Basin, USA

USGS Publications Warehouse

Locke, R.A.; Krapac, I.G.; Lewicki, J.L.; Curtis-Robinson, E.

2011-01-01

The Midwest Geological Sequestration Consortium is conducting a large-scale carbon capture and storage (CCS) project in Decatur, Illinois, USA to demonstrate the ability of a deep saline formation to store one million tonnes of carbon dioxide (CO2) from an ethanol facility. Beginning in early 2011, CO2 will be injected at a rate of 1,000 tonnes/day for three years into the Mount Simon Sandstone at a depth of approximately 2,100 meters. An extensive Monitoring, Verification, and Accounting (MVA) program has been undertaken for the Illinois Basin Decatur Project (IBDP) and is focused on the 0.65 km2 project site. Goals include establishing baseline conditions to evaluate potential impacts from CO2 injection, demonstrating that project activities are protective of human health and the environment, and providing an accurate accounting of stored CO2. MVA efforts are being conducted pre-, during, and post- CO2 injection. Soil and net CO2 flux monitoring has been conducted for more than one year to characterize near-surface CO2 conditions. More than 2,200 soil CO2 flux measurements have been manually collected from a network of 118 soil rings since June 2009. Three ring types have been evaluated to determine which type may be the most effective in detecting potential CO 2 leakage. Bare soil, shallow-depth rings were driven 8 cm into the ground and were prepared to minimize surface vegetation in and near the rings. Bare soil, deep-depth rings were prepared similarly, but were driven 46 cm. Natural-vegetation, shallow-depth rings were driven 8 cm and are most representative of typical vegetation conditions. Bare-soil, shallow-depth rings had the smallest observed mean flux (1.78 ??mol m-2 s-1) versus natural-vegetation, shallow-depth rings (3.38 ??mol m-2 s-1). Current data suggest bare ring types would be more sensitive to small CO2 leak signatures than natural ring types because of higher signal to noise ratios. An eddy covariance (EC) system has been in use since June 2009. Baseline data from EC monitoring is being used to characterize pre-injection conditions, and may then be used to detect changes in net exchange CO2 fluxes (Fc) that could be the result of CO2 leakage into the near-surface environment during or following injection. When injection at IBDP begins, soil and net CO2 monitoring efforts will have established a baseline of near-surface conditions that will be important to help demonstrate the effectiveness of storage activities. ?? 2011 Published by Elsevier Ltd.

Can we detect national-scale under-reporting of CO2 emissions using OCO-2 XCO2 observations in a carbon-weather data assimilation system?

NASA Astrophysics Data System (ADS)

Wuerth, S. M.; Fung, I. Y.; Anderson, J. L.; Raeder, K.

2016-12-01

A long-standing challenge in carbon cycle science is the inference of surface fluxes from atmospheric CO2 observations. Here we present initial results from our carbon-weather data assimilation system coupled to a mass-balance inversion . Our system combines the Community Atmosphere Model (CAM 5FV) with state-of-the-art ensemble data assimilation techniques from the Data Assimilation Research Testbed (DART), and assimilates OCO-2 XCO2 observations together with raw meteorological observations. The system uses a mass balance of the optimized atmospheric state to calculate CO2 sources and sinks throughout the globe. We present results from observing system simulation experiments (OSSE) aimed at comparing two different mass-balance approaches' abilities to detect under-reporting of national-scale CO2 emissions. In both experiments, we define a true state as the atmospheric state resulting from running CAM with a prognostic carbon cycle and CO2 emissions from CarbonTracker CT2015. Meteorological and OCO-2-like observations are harvested from this true state for assimilation. We create a hypothetical scenario in which fossil fuel CO2 emissions of a large emitter are scaled to half of their true values. Surface fluxes are then estimated using one of two approaches. The first approach computes, at every 6-hourly assimilation window, surface fluxes as the residual in the mass balance equation after divergence has been accounted for. The updated surface fluxes are then used as forcing in the ensuing CAM forecast. The second approach uses the initial false emissions for two weeks of model integration, then computes improved emissions by adding the time-averaged analysis increment in near-surface CO2 mixing ratio to the initial false emissions. The two weeks are re-run with these updated fluxes, and the process is then repeated for further refinement of fluxes. The advantages and disadvantages of the two approaches are discussed, and the system's ability to recover the true fluxes is assessed.

Saturn's satellites: Predictions for Cassini

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Hibbitts, C. A.

2004-11-01

Saturn's satellites are subjected to a variety of energy inputs (from photons, magnetospheric and solar ions and electrons) which will affect their surface composition. The Saturn magnetosphere contains an assortment of ions, including O+ and H+ from sputtering of water ice on the inner satellites and N+ from sputtering of Titan's atmosphere. Implantation of these ions onto the surfaces of the satellites may produce compounds possibly detectable by Cassini instruments. The satellites contain water ice and carbon dioxide ice (and possibly organics, on Phoebe). In Delitsky and Lane (2002), chemistry resulting from nitrogen ion implantation into water ice and carbon dioxide ice was outlined. From deposition of N+ ions into H2O/CO2, a complicated C-H-N-O chemistry may result, including formation of isocyanates, nitriles, nitrogen oxides and amino acids. Upon irradiation, H2O/CO2 mixtures will yield esters, ketones, alcohols, carboxylic acids and other interesting compounds. Cassini's infrared instruments CIRS and VIMS have spectral ranges that can detect many bands of these compounds. VIMS spectral range is 0.35 - 5.1 microns; CIRS covers the spectral range 7 - 100 microns, although its Mid-IR interferometer portion (7 -16 microns) is where organic materials are particularly spectrally active. Weak features are present in the short IR for NO (1.91 microns), NO2 (1.95), NH3 (2.00, 2.24), CH3OH (2.27, 2.34), and CO2 (1.965, 2.01) [Quirico et al.,1999]. Some molecules have stronger absorption features at these wavelengths: [CO2: 4.25 - 4.27 microns; NH3: 3 microns and 9.2 microns (important because the 3 micron band can be masked by water); H2CO3: 3.88 microns (weak); HCOOH: 8.2 microns; O2: 9.7 microns]. These molecules may exist as ices, or as molecules trapped in the surface. CH- and CN-containing molecules absorb at 3.2 - 3.4 microns, and 4.6 microns, respectively. H2O2, detected on Europa by its 3.5 micron band, may exist in the icy surfaces of the Saturn satellites as well.

Newly designed silver coated-magnetic, monodisperse polymeric microbeads as SERS substrate for low-level detection of amoxicillin

NASA Astrophysics Data System (ADS)

Kibar, Güneş; Topal, Ahmet Emin; Dana, Aykutlu; Tuncel, Ali

2016-09-01

We report the preparation of silver-coated magnetic polymethacrylate core-shell nanoparticles for use in surface-enhanced Raman scattering based drug detection. Monodisperse porous poly (mono-2-(methacryloyloxy)ethyl succinate-co-glycerol dimethacrylate), poly (MMES-co-GDMA) microbeads of ca. 5 μm diameter were first synthesized through a multistage microsuspension polymerization technique to serve as a carboxyl-bearing core region. Microspheres were subsequently magnetized by the co-precipitation of ferric ions, aminated through the surface hydroxyl groups and decorated with Au nanoparticles via electrostatic attraction. An Ag shell was then formed on top of the Au layer through a seed-mediated growth process, resulting in micron-sized monodisperse microbeads that exhibit Raman enhancement effects due to the roughness of the Ag surface layer. The core-shell microspheres were used as a new substrate for the detection of amoxicillin at trace concentrations up to 10-8 M by SERS. The proposed SERS platform can be evaluated as a useful tool for the follow-up amoxicillin pollution and low-level detection of amoxicillin in aqueous media.

Saturn's satellites: Potential for organic chemistry

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Lane, A. L.; Henry-Riyad, H.; Tidwell, T. T.

2003-05-01

The surfaces of the Saturnian satellites are subjected to irradiation from solar wind ions, photons, and magnetospheric ions and electrons. This bombardment will transform the chemical nature of the surfaces. At present, only water ice has been detected on their surfaces. Further studies by the Cassini spacecraft may reveal other molecules. If CO2 ice is found there, a whole panoply of new species may be detected. As nitrogen ions in the magnetosphere are thought to be an important species bombarding the satellites, Delitsky and Lane (2002) outlined the nitrogen oxides chemistry that may result from implantation of N+ into the water ice surfaces. Sittler et al (2002) showed that N+ ions originating from Titan will be enriched in the magnetospheric ion population as they move inwards towards Saturn, making the nitrogen oxides chemistry more likely. If CO2 is present, a complicated C-H-N-O chemistry may result from deposition of the N+ into a H2O/CO2 mixed ice, including nitriles, isocyanates, polymers, and amino acids. The combination of H2O/CO2 upon irradiation may also yield a complex mixture of hydrocarbons, esters, alcohols, organic acids and ketones. Possible chemical pathways and computations of their energetics will be presented. -Ref:- 1. Delitsky and Lane, Saturn's inner satellites: Ice chemistry and magnetosphere effects, JGR (Planets), Nov 2002, 3-1;; 2. Sittler et al., Energetic nitrogen ions within the inner magnetosphere of Saturn, Fall AGU meeting, Dec 2002, abstracts, pg F858, P21B-0379

In-lake carbon dioxide concentration patterns in four distinct phases in relation to ice cover dynamics

NASA Astrophysics Data System (ADS)

Denfeld, B. A.; Wallin, M.; Sahlee, E.; Sobek, S.; Kokic, J.; Chmiel, H.; Weyhenmeyer, G. A.

2014-12-01

Global carbon dioxide (CO2) emission estimates from inland waters include emissions at ice melt that are based on simple assumptions rather than evidence. To account for CO2 accumulation below ice and potential emissions into the atmosphere at ice melt we combined continuous CO2 concentrations with spatial CO2 sampling in an ice-covered small boreal lake. From early ice cover to ice melt, our continuous surface water CO2 concentration measurements at 2 m depth showed a temporal development in four distinct phases: In early winter, CO2 accumulated continuously below ice, most likely due to biological in-lake and catchment inputs. Thereafter, in late winter, CO2 concentrations remained rather constant below ice, as catchment inputs were minimized and vertical mixing of hypolimnetic water was cut off. As ice melt began, surface water CO2 concentrations were rapidly changing, showing two distinct peaks, the first one reflecting horizontal mixing of CO2 from surface and catchment waters, the second one reflecting deep water mixing. We detected that 83% of the CO2 accumulated in the water during ice cover left the lake at ice melt which corresponded to one third of the total CO2 storage. Our results imply that CO2 emissions at ice melt must be accurately integrated into annual CO2 emission estimates from inland waters. If up-scaling approaches assume that CO2 accumulates linearly under ice and at ice melt all CO2 accumulated during ice cover period leaves the lake again, present estimates may overestimate CO2 emissions from small ice covered lakes. Likewise, neglecting CO2 spring outbursts will result in an underestimation of CO2 emissions from small ice covered lakes.

Surface analysis of Fe-Co-Mo electrolytic coatings

NASA Astrophysics Data System (ADS)

Yar-Mukhamedova, G. Sh; Sakhnenko, N. D.; Ved', M. V.; Yermolenko, I. Yu; Zyubanova, S. I.

2017-06-01

Coatings Fe-Co-Mo with a composition of 47 at.% iron, 28 at.% Cobalt and 25 at.% Molybdenum were deposited from citrate electrolyte using pulse electrolysis mode. Scanning electron and atomic force microscopy have established the surface morphology and topography. It was identified the parts with a globular structure which have an average size of 0.2-0.5μm and singly located sharp grains. Within the same scan area sites with developed surface were detected the topography of which is identical to the crystal structure of cobalt with the crystallites size of 0.2-1.75μm. The parameters Ra and Rq for parts with different morphology as well as average characteristics of coatings demonstrated the low roughness of the surface. It is found that the coercive force of Fe-Co-Mo films is 7-10 Oe, which allow us to classify the Fe-Co-Mo coatings as soft magnetic materials.

Functionalized graphene oxide quantum dot-PVA hydrogel: a colorimetric sensor for Fe2+, Co2+ and Cu2+ ions

NASA Astrophysics Data System (ADS)

Baruah, Upama; Chowdhury, Devasish

2016-04-01

Functionalized graphene oxide quantum dots (GOQDs)-poly(vinyl alcohol) (PVA) hybrid hydrogels were prepared using a simple, facile and cost-effective strategy. GOQDs bearing different surface functional groups were introduced as the cross-linking agent into the PVA matrix thereby resulting in gelation. The four different types of hybrid hydrogels were prepared using graphene oxide, reduced graphene oxide, ester functionalized graphene oxide and amine functionalized GOQDs as cross-linking agents. It was observed that the hybrid hydrogel prepared with amine functionalized GOQDs was the most stable. The potential applicability of using this solid sensing platform has been subsequently explored in an easy, simple, effective and sensitive method for optical detection of M2+ (Fe2+, Co2+ and Cu2+) in aqueous media involving colorimetric detection. Amine functionalized GOQDs-PVA hybrid hydrogel when put into the corresponding solution of Fe2+, Co2+ and Cu2+ renders brown, orange and blue coloration respectively of the solution detecting the presence of Fe2+, Co2+ and Cu2+ ions in the solution. The minimum detection limit observed was 1 × 10-7 M using UV-visible spectroscopy. Further, the applicability of the sensing material was also tested for a mixture of co-existing ions in solution to demonstrate the practical applicability of the system. Insight into the probable mechanistic pathway involved in the detection process is also being discussed.

COI oxidation on a single Pd atom supported on magnesia.

PubMed

Abbet, S; Heiz, U; Häkkinen, H; Landman, U

2001-06-25

The oxidation of CO on single Pd atoms anchored to MgO(100) surface oxygen vacancies is studied with temperature-programmed-reaction mass spectrometry and infrared spectroscopy. In one-heating-cycle experiments, CO(2), formed from O(2) and CO preadsorbed at 90 K, is detected at 260 and 500 K. Ab-initio simulations suggest two reaction routes, with Pd(CO)(2)O(2) and PdCO(3)CO found as precursors for the low and high temperature channels, respectively. Both reactions result in annealing of the vacancy and induce migration and coalescence of the remaining Pd-CO to form larger clusters.

Relationship between soil cobalt and vitamin B12 levels in the liver of livestock in Saudi Arabia: role of competing elements in soils.

PubMed

Huwait, Etimad A; Kumosani, Taha A; Moselhy, Said S; Mosaoa, Rami M; Yaghmoor, Soonham S

2015-09-01

This study aimed to analyze the agricultural soils from different regions in Saudi Arabia for cobalt and related metals as Cu(2+), Ni(2+), Cr(3+), Zn(2+) and Pb(2+). Liver and muscle tissues of livestock grazing on the selected areas were analyzed for the content of Co and vitamin B12. Our results indicated that the levels of Co in surface soil (0-15 cm) were higher than in sub-surface soil (>15 cm-45 cm). In contrast, Pb and Zn were higher in sub-surface soil than in surface soil. A significant positive correlation existed between the levels of Co and vitamin B12 in the liver of livestock. However, Co was not detected in muscle tissues while vitamin B12 was present at very low levels in comparison with the levels found in the liver. The results indicated that Zn(2+), Pb(2+) compete with Co in soil, which eventually affected the levels of vitamin B12 in liver. It was recommended that survey of heavy metals in grazing fields of cattle should consider inclusion of multiple elements that compete with the bioavailability of essential elements in plants and animals for the prevention of deficiency of essential elements such as Co.

Biomolecule detection using wheatstone bridge giant magnetoresistance (GMR) sensors based on CoFeB spin-valve thin film

NASA Astrophysics Data System (ADS)

Elda Swastika, P.; Antarnusa, G.; Suharyadi, E.; Kato, T.; Iwata, S.

2018-04-01

A potential wheatstone bridge giant magnetoresistance (GMR) biosensor have been successfully developed for biomolecule detection. [IrMn(10 nm)/CoFe(3 nm)/Cu(2.2 nm)/CoFeB(10 nm)] spin-valve structure has been chosen as the magnetic sensing surface, showing a magnetoresistance (MR) of 6% fabricated by DC magnetron sputtering method. The Fe3O4 magnetic nanoparticles used as biomolecular labels (nanotags) was synthesized by co-precipitation method, exhibiting soft magnetic behavior with saturation magnetization (Ms), remanent magnetization (Mr) and coercivity (Hc) is 77.2 emu/g, 7.8 emu/g and 51 Oe, respectively. The X-ray diffraction (XRD) patterns and transmission electron microscopy (TEM) images showed that Fe3O4 was well crystallized and grew in their inverse spinel structure, highly uniform morphology with an average grain size was about 20 nm. Fe3O4 was coated with polyethylene-glycol (PEG)-4000 for surface functionalization. Detection of biomolecule such as formalin, gelatin from bovine-skin and porcine-skin were dispersed in ethanol at room temperature. Induction would cause a shift in output voltage with a minimum delta output voltage (ΔV) 4.937 mV (10%) for formalin detection, 2.268 mV (7%) for bovine-skin gelatin and 2.943 mV (7%) for porcine-skin gelatin detection. The ΔV of the wheatstone bridge in real-time measurement decrease by increase in biomolecules concentration. The change of ΔV with various concentration of biomolecule indicates that the spin-valve thin film with wheatstone-bridge circuit is potential as a biosensor.

Following the south polar cap recession as viewed by OMEGA/MEX using automatic detection of H2O and CO2 ices.

NASA Astrophysics Data System (ADS)

Schmidt, F.; Doute, S.; Schmitt, B.

In order to understand Mars' current climate it is necessary to detect, characterize and monitor CO2 and H2O at the surface (permanent and seasonal icy deposits) and in the atmosphere (vapor and clouds). Here we will focus on the South Seasonal Polar Cap (SSPC) whose recession was previously observed with different techniques : from earth in the visible range with HST [James 1996], or from MGS spacecraft with MOC images [Benson 2005], in the thermal IR range by the TES [Kieffer 2000], in the near infrared by OMEGA/MEX [Langevin submitted]. The time and space evolutions of the SSPC is a major annual climatic signal both at the global and the regional scales. In particular the measurement of the temporal and spatial distributions of CO2 constrains exchange processes between both surface and atmosphere. This exchange may involve preponderant species : H2O, CO2 and dust. In this work we will apply a new detection technique : "wavanglet" in order to follow the recession of the SSPC thanks to OMEGA/MEX observations. This method was especially developed in the goal to classify a huge dataset, such OMEGA ones. We propose to use "wavanglet" as a supervised automatic classification method that identifies spectral features and classifies the image in spectrally homogeneous units. Additionally we will evaluate quantitative detection limits of "wavanglet" based on synthetic dataset simulating OMEGA spectra in typical situation of the SSPC. This detection limit will be discussed in terms of abundance for H2O and CO2 ices in order to improve the interpretation of the classification. Finally we will present the recession of the SSPC using "wavanglet" and we will compare the results with those of earlier investigation. An interpretation of the similarities and disagreements between those maps will be done.

New advances in non-dispersive IR technology for CO2 detection

NASA Technical Reports Server (NTRS)

Small, John W.; Odegard, Wayne L.

1988-01-01

This paper discusses new technology developments in CO2 detection using Non-Dispersive Infrared (NDIR) techniques. The method described has successfully been used in various applications and environments. It has exhibited extremely reliable long-term stability without the need of routine calibration. The analysis employs a dual wavelength, differential detection approach with compensating circuitry for component aging and dirt accumulation on optical surfaces. The instrument fails 'safe' and provides the operator with a 'fault' alarm in the event of a system failure. The NDIR analyzer described has been adapted to NASA Space Station requirements.

The role of optimality in characterizing CO2 seepage from geological carbon sequestration sites

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

Cortis, Andrea; Oldenburg, Curtis M.; Benson, Sally M.

Storage of large amounts of carbon dioxide (CO{sub 2}) in deep geological formations for greenhouse gas mitigation is gaining momentum and moving from its conceptual and testing stages towards widespread application. In this work we explore various optimization strategies for characterizing surface leakage (seepage) using near-surface measurement approaches such as accumulation chambers and eddy covariance towers. Seepage characterization objectives and limitations need to be defined carefully from the outset especially in light of large natural background variations that can mask seepage. The cost and sensitivity of seepage detection are related to four critical length scales pertaining to the size ofmore » the: (1) region that needs to be monitored; (2) footprint of the measurement approach, and (3) main seepage zone; and (4) region in which concentrations or fluxes are influenced by seepage. Seepage characterization objectives may include one or all of the tasks of detecting, locating, and quantifying seepage. Each of these tasks has its own optimal strategy. Detecting and locating seepage in a region in which there is no expected or preferred location for seepage nor existing evidence for seepage requires monitoring on a fixed grid, e.g., using eddy covariance towers. The fixed-grid approaches needed to detect seepage are expected to require large numbers of eddy covariance towers for large-scale geologic CO{sub 2} storage. Once seepage has been detected and roughly located, seepage zones and features can be optimally pinpointed through a dynamic search strategy, e.g., employing accumulation chambers and/or soil-gas sampling. Quantification of seepage rates can be done through measurements on a localized fixed grid once the seepage is pinpointed. Background measurements are essential for seepage detection in natural ecosystems. Artificial neural networks are considered as regression models useful for distinguishing natural system behavior from anomalous behavior suggestive of CO{sub 2} seepage without need for detailed understanding of natural system processes. Because of the local extrema in CO{sub 2} fluxes and concentrations in natural systems, simple steepest-descent algorithms are not effective and evolutionary computation algorithms are proposed as a paradigm for dynamic monitoring networks to pinpoint CO{sub 2} seepage areas.« less

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

Cheng, Tao; Xiao, Hai; Goddard, William A.

Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions is not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or to carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). We carry out QM calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO 2 reduction reaction conditions) to examine the initial reaction pathways to form CO and formatemore » (HCOO –) from CO 2 through free energy calculations at 298 K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ-), with a free energy barrier of ΔG ‡ = 0.43 eV, the rate-determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 and 0.30 eV, respectively. HCOO– formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO – formation occurs in the first electron-transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Therefore, to alter the product distribution, we need to control this first step of CO 2 binding, which might involve controlling pH, alloying, or changing the structure at the nanoscale.« less

Rapid Surface Detection of CO2 Leaks from Geologic Sequestration Sites

NASA Astrophysics Data System (ADS)

Moriarty, D. M.; Krevor, S. C.; Benson, S. M.

2013-12-01

Carbon sequestration is becoming a viable option for global CO2 mitigation but effective monitoring methods are needed assure the carbon dioxide stays underground. Above surface monitoring using a mobile gas analyzer is one such method (e.g. Krevor et al., 2010). The Picarro gas analyzer uses wavelength-scanned cavity ring down spectroscopy to accurately identify concentrations of various atmospheric gases including their isotopic composition. These measurements can then be used for anomaly (leak) detection and source attribution. Leaks are detected by anomalous absolute concentration of CO2 and anomalous δ13C values. Source attribution is determined by the isotopic concentrations of the identified leaking gas. To distinguish between noise from ambient signals and leaks, a method based on mixing ratios has been developed. A newly acquired data set presented here has been collected from a 3.7km2 area with naturally occurring CO2 springs near Green River, Utah. All of the areas of known leakage were readily detected using this method along with several other areas that showed significant signs of leakage. In addition, testing on the Stanford campus has shown that this method is sensitive enough to distinguish between open fields and roadways. Another data set is being collected at Montana State University at the ZERT monitoring test site where an artificial leak has been created for the purpose of testing leak detection and quantification methods. Data collected from this site are being used for (1) assessing of detection levels and how they depend on environmental parameters such as wind speed, and acquisition variables such as sample rate and traverse speed, (2) optimizing acquisition parameters to increase detection levels and increase confidence in leak detection, (3) evaluating the potential for quantifying the magnitude of the leak and (4) spatial data analysis to identify the most probable leak locations.

Comparative study on CO2 and CO sensing performance of LaOCl-coated ZnO nanowires.

PubMed

Van Hieu, Nguyen; Khoang, Nguyen Duc; Trung, Do Dang; Toan, Le Duc; Van Duy, Nguyen; Hoa, Nguyen Duc

2013-01-15

Carbon dioxide (CO(2)) and carbon monoxide (CO) emissions from industries and combustion fuels such as coal, oil, hydrocarbon, and natural gases are increasing, thus causing environmental pollution and climate change. The selective detection of CO(2) and CO gases is important for environmental monitoring and industrial safety applications. In this work, LaOCl-coated ZnO nanowires (NWs) sensors are fabricated and characterized for the detection of CO(2) (250-4000 ppm) and CO (10-200 ppm) gases at different operating temperatures. The effects of the LaCl(3) coating concentration and calcination temperature of the sensors are studied. They are found to have a strong influence on the sensing performance to CO(2) gas, but a relatively slight influence on that to CO. The LaOCl coating enhances the response and shortens the response and recovery times to CO(2) compared with those to CO. The enhanced response of the LaOCl-coated ZnO NW sensors is attributed to the extension of the electron depletion layer due to the formation of p-LaOCl/n-ZnO junctions on the surfaces of the ZnO NWs. Copyright © 2012 Elsevier B.V. All rights reserved.

Hyperspectral detection of a subsurface CO2 leak in the presence of water stressed vegetation.

PubMed

Bellante, Gabriel J; Powell, Scott L; Lawrence, Rick L; Repasky, Kevin S; Dougher, Tracy

2014-01-01

Remote sensing of vegetation stress has been posed as a possible large area monitoring tool for surface CO2 leakage from geologic carbon sequestration (GCS) sites since vegetation is adversely affected by elevated CO2 levels in soil. However, the extent to which remote sensing could be used for CO2 leak detection depends on the spectral separability of the plant stress signal caused by various factors, including elevated soil CO2 and water stress. This distinction is crucial to determining the seasonality and appropriateness of remote GCS site monitoring. A greenhouse experiment tested the degree to which plants stressed by elevated soil CO2 could be distinguished from plants that were water stressed. A randomized block design assigned Alfalfa plants (Medicago sativa) to one of four possible treatment groups: 1) a CO2 injection group; 2) a water stress group; 3) an interaction group that was subjected to both water stress and CO2 injection; or 4) a group that received adequate water and no CO2 injection. Single date classification trees were developed to identify individual spectral bands that were significant in distinguishing between CO2 and water stress agents, in addition to a random forest classifier that was used to further understand and validate predictive accuracies. Overall peak classification accuracy was 90% (Kappa of 0.87) for the classification tree analysis and 83% (Kappa of 0.77) for the random forest classifier, demonstrating that vegetation stressed from an underground CO2 leak could be accurately discerned from healthy vegetation and areas of co-occurring water stressed vegetation at certain times. Plants appear to hit a stress threshold, however, that would render detection of a CO2 leak unlikely during severe drought conditions. Our findings suggest that early detection of a CO2 leak with an aerial or ground-based hyperspectral imaging system is possible and could be an important GCS monitoring tool.

Hyperspectral Detection of a Subsurface CO2 Leak in the Presence of Water Stressed Vegetation

PubMed Central

Bellante, Gabriel J.; Powell, Scott L.; Lawrence, Rick L.; Repasky, Kevin S.; Dougher, Tracy

2014-01-01

Remote sensing of vegetation stress has been posed as a possible large area monitoring tool for surface CO2 leakage from geologic carbon sequestration (GCS) sites since vegetation is adversely affected by elevated CO2 levels in soil. However, the extent to which remote sensing could be used for CO2 leak detection depends on the spectral separability of the plant stress signal caused by various factors, including elevated soil CO2 and water stress. This distinction is crucial to determining the seasonality and appropriateness of remote GCS site monitoring. A greenhouse experiment tested the degree to which plants stressed by elevated soil CO2 could be distinguished from plants that were water stressed. A randomized block design assigned Alfalfa plants (Medicago sativa) to one of four possible treatment groups: 1) a CO2 injection group; 2) a water stress group; 3) an interaction group that was subjected to both water stress and CO2 injection; or 4) a group that received adequate water and no CO2 injection. Single date classification trees were developed to identify individual spectral bands that were significant in distinguishing between CO2 and water stress agents, in addition to a random forest classifier that was used to further understand and validate predictive accuracies. Overall peak classification accuracy was 90% (Kappa of 0.87) for the classification tree analysis and 83% (Kappa of 0.77) for the random forest classifier, demonstrating that vegetation stressed from an underground CO2 leak could be accurately discerned from healthy vegetation and areas of co-occurring water stressed vegetation at certain times. Plants appear to hit a stress threshold, however, that would render detection of a CO2 leak unlikely during severe drought conditions. Our findings suggest that early detection of a CO2 leak with an aerial or ground-based hyperspectral imaging system is possible and could be an important GCS monitoring tool. PMID:25330232

Cassini finds an oxygen-carbon dioxide atmosphere at Saturn's icy moon Rhea.

PubMed

Teolis, B D; Jones, G H; Miles, P F; Tokar, R L; Magee, B A; Waite, J H; Roussos, E; Young, D T; Crary, F J; Coates, A J; Johnson, R E; Tseng, W-L; Baragiola, R A

2010-12-24

The flyby measurements of the Cassini spacecraft at Saturn's moon Rhea reveal a tenuous oxygen (O(2))-carbon dioxide (CO(2)) atmosphere. The atmosphere appears to be sustained by chemical decomposition of the surface water ice under irradiation from Saturn's magnetospheric plasma. This in situ detection of an oxidizing atmosphere is consistent with remote observations of other icy bodies, such as Jupiter's moons Europa and Ganymede, and suggestive of a reservoir of radiolytic O(2) locked within Rhea's ice. The presence of CO(2) suggests radiolysis reactions between surface oxidants and organics or sputtering and/or outgassing of CO(2) endogenic to Rhea's ice. Observations of outflowing positive and negative ions give evidence for pickup ionization as a major atmospheric loss mechanism.

The concurrent use of novel soil surface microclimate measurements to evaluate CO2 pulses in biocrusted interspaces in a cool desert ecosystem

USGS Publications Warehouse

Tucker, Colin; McHugh, Theresa A.; Howell, Armin; Gill, Richard; Weber, Bettina; Belnap, Jayne; Grote, Ed; Reed, Sasha C.

2017-01-01

Carbon cycling associated with biological soil crusts, which occupy interspaces between vascular plants in drylands globally, may be an important part of the coupled climate-carbon cycle of the Earth system. A major challenge to understanding CO2 fluxes in these systems is that much of the biotic and biogeochemical activity occurs in the upper few mm of the soil surface layer (i.e., the ‘mantle of fertility’), which exhibits highly dynamic and difficult to measure temperature and moisture fluctuations. Here, we report a multi-sensor approach to simultaneously measuring temperature and moisture of this biocrust surface layer (0–2 mm), and the deeper soil profile, concurrent with automated measurement of surface soil CO2effluxes. Our results illuminate robust relationships between biocrust water content and field CO2 pulses that have previously been difficult to detect and explain. All observed CO2 pulses over the measurement period corresponded to surface wetting events, including when the wetting events did not penetrate into the soil below the biocrust layer (0–2 mm). The variability of temperature and moisture of the biocrust surface layer was much greater than even in the 0–5 cm layer of the soil beneath the biocrust, or deeper in the soil profile. We therefore suggest that coupling surface measurements of biocrust moisture and temperature to automated CO2flux measurements may greatly improve our understanding of the climatic sensitivity of carbon cycling in biocrusted interspaces in our study region, and that this method may be globally relevant and applicable.

Exploring the influence of surface waves in the carbon dioxide transfer velocity between the ocean and atmosphere in the coastal region

NASA Astrophysics Data System (ADS)

Ocampo-Torres, Francisco Javier; Francisco Herrera, Carlos; Gutiérrez-Loza, Lucía; Osuna, Pedro

2016-04-01

Field measurements have been carried out in order to better understand the possible influence of ocean surface waves in the transfer of carbon dioxide between the ocean and atmosphere in the coastal zone. The CO2 fluxes are being analysed and results are shown in a contribution by Gutiérrez-Loza et al., in this session. Here we try to highlight the findings regarding the transfer velocity (kCO2) once we have incorporated direct measurements of carbon dioxide concentration in the water side. In this study direct measurements of CO2 fluxes were obtained with an eddy covariance tower located in the shoreline equipped with an infrared open-path gas analyzer (LI-7500, LI-COR) and a sonic anemometer (R3-100 Professional Anemometer, Gill Instruments), both at about 13 m above the mean sea level, and sampling at 20 Hz. For some period of time simultaneous information of waves was recorded with a sampling rate of 2 Hz using an Acoustic Doppler Current Profiler (Workhorse Sentinel, Teledyne RD Instruments) at 10 m depth and 350 m away from the tower. Besides, recently the concentration of CO2 in water has also been recorded making use of a SAMI-CO2 instrument. A subtle effect of the wave field is detected in the estimated kCO2. Looking into details of the surface currents being detected very near the air-sea interface through an ADPC, a certain association can be found with the gas transfer velocity. Furthermore, some of the possible effects of breaking wave induced turbulence in the coastal zone is to be addressed. This work represents a RugDiSMar Project (CONACYT 155793) contribution. The support from CB-2011-01-168173 CONACYT project is greatly acknowledged.

Remote-Raman and Micro-Raman Studies of Solid CO2, CH4, Gas Hydrates and Ice

NASA Technical Reports Server (NTRS)

Sharma, S. K.; Misra, A. K.; Lucey, P. G.; Exarhos, G. J.; Windisch, C. F., Jr.

2004-01-01

It is well known that on Mars CO2 is the principal constituent of the thin atmosphere and on a seasonal basis CO2 snow and frost coats the polar caps. Also over 25% of the Martian atmosphere freezes out and sublimes again each year. The Mars Odyssey Emission Imaging system (THEMIS) has discovered water ice exposed near the edge of Mars southern perennials cap. In recent years, it has been suggested that in Martian subsurface CO2 may exist as gas hydrate (8CO2 + 44 H2O) with melting temperature of 10C. Since the crust of Mars has been stable for enough time there is also a possibility that methane formed by magmatic processes and/or as a byproduct of anaerobic deep biosphere activity to have raised toward the planet s surface. This methane would have been captured and stored as methane hydrate, which concentrates methane and water. Determination of abundance and distribution of these ices on the surface and in the near surface are of fundamental importance for understanding Martian atmosphere, and for future exploration of Mars. In this work, we have evaluated feasibility of using remote Raman and micro-Raman spectroscopy as potential nondestructive and non-contact techniques for detecting solid CO2, CH4 gas, and gas hydrates as well as water-ice on planetary surfaces.

Numerical modeling of time-lapse monitoring of CO2 sequestration in a layered basalt reservoir

USGS Publications Warehouse

Khatiwada, M.; Van Wijk, K.; Clement, W.P.; Haney, M.

2008-01-01

As part of preparations in plans by The Big Sky Carbon Sequestration Partnership (BSCSP) to inject CO2 in layered basalt, we numerically investigate seismic methods as a noninvasive monitoring technique. Basalt seems to have geochemical advantages as a reservoir for CO2 storage (CO2 mineralizes quite rapidly while exposed to basalt), but poses a considerable challenge in term of seismic monitoring: strong scattering from the layering of the basalt complicates surface seismic imaging. We perform numerical tests using the Spectral Element Method (SEM) to identify possibilities and limitations of seismic monitoring of CO2 sequestration in a basalt reservoir. While surface seismic is unlikely to detect small physical changes in the reservoir due to the injection of CO2, the results from Vertical Seismic Profiling (VSP) simulations are encouraging. As a perturbation, we make a 5%; change in wave velocity, which produces significant changes in VSP images of pre-injection and post-injection conditions. Finally, we perform an analysis using Coda Wave Interferometry (CWI), to quantify these changes in the reservoir properties due to CO2 injection.

Combining Theory and Experiment for Multitechnique Characterization of Activated CO 2 on Transition Metal Carbide (001) Surfaces

DOE PAGES

Kunkel, Christian; Viñes, Francesc; Ramírez, Pedro J.; ...

2018-01-15

Early transition metal carbides (TMC; TM = Ti, Zr, Hf, V, Nb, Ta, Mo) with face-centered cubic crystallographic structure have emerged as promising materials for CO 2 capture and activation. Density functional theory (DFT) calculations using the Perdew–Burke–Ernzerhof exchange–correlation functional evidence charge transfer from the TMC surface to CO 2 on the two possible adsorption sites, namely, MMC and TopC, and the electronic structure and binding strength differences are discussed. Further, the suitability of multiple experimental techniques with respect to (1) adsorbed CO2 recognition and (2) MMC/TopC adsorption distinction is assessed from extensive DFT simulations. Results show that ultraviolet photoemissionmore » spectroscopies (UPS), work function changes, core level X-ray photoemission spectroscopy (XPS), and changes in linear optical properties could well allow for adsorbed CO2 detection. Only infrared (IR) spectra and scanning tunnelling microscopy (STM) seem to additionally allow for MMC/TopC adsorption site distinction. These findings are confirmed with experimental XPS measurements, demonstrating CO 2 binding on single crystal (001) surfaces of TiC, ZrC, and VC. The experiments also help resolving ambiguities for VC, where CO 2 activation was unexpected due to low adsorption energy, but could be related to kinetic trapping involving a desorption barrier. With a wealth of data reported and direct experimental evidence provided, this study aims to motivate further basic surface science experiments on an interesting case of CO 2 activating materials, allowing also for a benchmark of employed theoretical models.« less

Combining Theory and Experiment for Multitechnique Characterization of Activated CO 2 on Transition Metal Carbide (001) Surfaces

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

Kunkel, Christian; Viñes, Francesc; Ramírez, Pedro J.

Early transition metal carbides (TMC; TM = Ti, Zr, Hf, V, Nb, Ta, Mo) with face-centered cubic crystallographic structure have emerged as promising materials for CO 2 capture and activation. Density functional theory (DFT) calculations using the Perdew–Burke–Ernzerhof exchange–correlation functional evidence charge transfer from the TMC surface to CO 2 on the two possible adsorption sites, namely, MMC and TopC, and the electronic structure and binding strength differences are discussed. Further, the suitability of multiple experimental techniques with respect to (1) adsorbed CO2 recognition and (2) MMC/TopC adsorption distinction is assessed from extensive DFT simulations. Results show that ultraviolet photoemissionmore » spectroscopies (UPS), work function changes, core level X-ray photoemission spectroscopy (XPS), and changes in linear optical properties could well allow for adsorbed CO2 detection. Only infrared (IR) spectra and scanning tunnelling microscopy (STM) seem to additionally allow for MMC/TopC adsorption site distinction. These findings are confirmed with experimental XPS measurements, demonstrating CO 2 binding on single crystal (001) surfaces of TiC, ZrC, and VC. The experiments also help resolving ambiguities for VC, where CO 2 activation was unexpected due to low adsorption energy, but could be related to kinetic trapping involving a desorption barrier. With a wealth of data reported and direct experimental evidence provided, this study aims to motivate further basic surface science experiments on an interesting case of CO 2 activating materials, allowing also for a benchmark of employed theoretical models.« less

A high-pressure atomic force microscope for imaging in supercritical carbon dioxide

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

Lea, Alan S.; Higgins, Steven R.; Knauss, Kevin G.

2011-04-26

A high-pressure atomic force microscope (AFM) that enables in-situ, atomic scale measurements of topography of solid surfaces in contact with supercritical CO2 (scCO2) fluids has been developed. This apparatus overcomes the pressure limitations of the hydrothermal AFM and is designed to handle pressures up to 100 atm at temperatures up to ~ 350 K. A standard optically-based cantilever deflection detection system was chosen. When imaging in compressible supercritical fluids such as scCO2, precise control of pressure and temperature in the fluid cell is the primary technical challenge. Noise levels and imaging resolution depend on minimization of fluid density fluctuations thatmore » change the fluid refractive index and hence the laser path. We demonstrate with our apparatus in-situ atomic scale imaging of a calcite (CaCO3) mineral surface in scCO2; both single, monatomic steps and dynamic processes occurring on the (10¯14) surface are presented. This new AFM provides unprecedented in-situ access to interfacial phenomena at solid-fluid interfaces under pressure.« less

Compositional Trends on the Large Moons of Uranus: Evidence for System-Wide Modification

NASA Astrophysics Data System (ADS)

Cartwright, R.; Emery, J. P.

2017-12-01

Previous near-infrared (NIR) observations centered over southern latitudes ( 5 - 30°S) of the classical Uranian moons have detected H2Oww ice bands, mixed with a spectrally neutral and low albedo constituent. The strengths of the detected H2O bands are greater on the leading hemispheres of these moons compared to their trailing hemispheres, with a reduction in leading/trailing H2O band strengths with distance from Uranus. CO2 ice bands have been detected in spectra collected over the trailing hemispheres of the classical Uranian satellites, with stronger CO2 bands on the moons closest to Uranus. Our preferred hypotheses to explain the hemispherical and planetocentric trends in the distribution of CO2 and the strength of detected H2O bands are: bombardment by magnetospherically-embedded charged particles, primarily on the trailing hemispheres of these moons, and bombardment by dust particles, primarily on their leading hemispheres. To test these complementary hypotheses, we are constraining the distribution and spectral characteristics of surface constituents on the currently observable northern hemispheres (sub-observer lat. 20 - 35°N) of these moons with new NIR observations. Analysis of northern hemisphere data shows that CO2 is present on their trailing hemispheres, and H2O bands are strongest on their leading hemispheres, in agreement with the southern hemisphere data. This longitudinal distribution of constituents supports our preferred hypotheses. Tantalizing mysteries regarding the distribution of constituents on these moons remain. There has been no detection of CO2 on Miranda, and H2O bands are subtly stronger on its trailing hemisphere compared to its leading hemisphere, counter to the hemispherical trends displayed on the other classical satellites. Some Uranian satellite spectra display a subtle absorption feature near 2.2 µm, which could result from the presence of NH3-hydrates on these moons. The presence of this volatile constituent could indicate recent cryovolcanic emplacement and/or recent exposure of NH3-hydrates via mass wasting, tectonism, or impact events. We will present work related to our goals of constraining the processes modifying the surfaces of the classical Uranian moons.

Inverse Modeling of Water-Rock-CO2 Batch Experiments: Potential Impacts on Groundwater Resources at Carbon Sequestration Sites.

PubMed

Yang, Changbing; Dai, Zhenxue; Romanak, Katherine D; Hovorka, Susan D; Treviño, Ramón H

2014-01-01

This study developed a multicomponent geochemical model to interpret responses of water chemistry to introduction of CO2 into six water-rock batches with sedimentary samples collected from representative potable aquifers in the Gulf Coast area. The model simulated CO2 dissolution in groundwater, aqueous complexation, mineral reactions (dissolution/precipitation), and surface complexation on clay mineral surfaces. An inverse method was used to estimate mineral surface area, the key parameter for describing kinetic mineral reactions. Modeling results suggested that reductions in groundwater pH were more significant in the carbonate-poor aquifers than in the carbonate-rich aquifers, resulting in potential groundwater acidification. Modeled concentrations of major ions showed overall increasing trends, depending on mineralogy of the sediments, especially carbonate content. The geochemical model confirmed that mobilization of trace metals was caused likely by mineral dissolution and surface complexation on clay mineral surfaces. Although dissolved inorganic carbon and pH may be used as indicative parameters in potable aquifers, selection of geochemical parameters for CO2 leakage detection is site-specific and a stepwise procedure may be followed. A combined study of the geochemical models with the laboratory batch experiments improves our understanding of the mechanisms that dominate responses of water chemistry to CO2 leakage and also provides a frame of reference for designing monitoring strategy in potable aquifers.

Pulsed Airborne Lidar Measurements of Atmospheric CO2 Column Absorption and Line Shapes from 3-13 km Altitudes

NASA Technical Reports Server (NTRS)

Abshire, James; Riris, Haris; Allan, Graham; Weaver, Clark; Mao, Jianping; Sun, Xiaoli; Hasselbrack, William

2010-01-01

We have developed a pulsed lidar technique for measuring the tropospheric CO2 concentrations as a candidate for NASA's planned ASCENDS space mission. Our technique uses two pulsed laser transmitters allowing simultaneous measurement of a CO2 absorption line in the 1570 nm band, O2 extinction in the Oxygen A-band and surface height and backscatter. The lidar measures the energy and time of flight of the laser echoes reflected from the atmosphere and surface. The lasers are rapidly and precisely stepped in wavelength across the CO2 line and an O2 line region during the measurement. The direct detection receiver uses a telescope and photon counting detectors, and measures the background light and energies of the laser echoes from the surface along with scattering from any aerosols in the path. The gas extinction and column densities for the CO2 and O2 gases are estimated from the ratio of the on- and off- line signals via the DIAL technique. Time gating is used to isolate the laser echo signals from the surface, and to reject laser photons scattered in the atmosphere. The time of flight of the laser pulses are also used to estimate the height of the scattering surface and to identify cases of mixed cloud and ground scattering. We have developed an airborne lidar to demonstrate the CO2 measurement from the NASA Glenn Lear-25 aircraft. The airborne lidar steps the pulsed laser's wavelength across the selected CO2 line with 20 steps per scan. The line scan rate is 450 Hz, the laser pulse widths are 1 usec, and laser pulse energy is 24 uJ. The time resolved laser backscatter is collected by a 20 cm telescope, detected by a photomultiplier and is recorded by a photon counting system. We made initial airborne measurements on flights during fall 2008. Laser backscatter and absorption measurements were made over a variety of land and water surfaces and through thin clouds. The atmospheric CO2 column measurements using the 1572.33 nm CO2 lines. Two flights were made above the US Department of Energy's (DOE) SGP ARM site at altitudes from 3-8 km. These flights were coordinated with DOE investigators who flew an in-situ CO2 sensor on a Cessna aircraft under the path. The increasing CO2 line absorptions with altitudes were evident and comparison with in-situ measurements showed agreements to 6 ppm. In spring 2009 we improved the aircraft's nadir window and during July and August we made 9 additional 2 hour long flights and measured the atmospheric CO2 absorption and line shapes using the 1572.33 nm CO2 line. Measurements were made at stepped altitudes from 3-13 km over a variety of surface types in Nebraska, Illinois, the SGP ARM site, and near and over the Chesapeake Bay in North Carolina and eastern Virginia. Strong laser signals and clear CO2 line shapes were observed at all altitudes, and some measurements were made through thin clouds. The flights over the ARM site were underflown with in-situ measurements made from the DOE Cessna. Analysis shows that the average signal levels follow predicted values, the altimetry measurements had an uncertainty of about 4 m, and that the average optical line depths follow the number density calculated from in-situ sensor readings. The Oklahoma and east coast flights were coordinated with a LaRC/ITT CO2 lidar on the LaRC UC-12 aircraft, a LaRC in-situ CO2 sensor, and the Oklahoma flights also included a JPL CO2 lidar on a Twin Otter aircraft. More details of the flights, measurements, analysis and scaling to space will be described in the presentation.

Porous NiCo2O4 nanoarray-integrated binder-free 3D open electrode offers a highly efficient sensing platform for enzyme-free glucose detection.

PubMed

Luo, X; Huang, M; He, D; Wang, M; Zhang, Y; Jiang, P

2018-05-29

High electrical conductivity and the exposure to more active sites are crucial to boost the performance of a glucose sensor. A porous binary metal oxide nanoarray integrated on a binder-free 3D electrode is expected to offer a highly sensitive sensing platform. As a model, porous NiCo2O4 nanowire arrays supported on carbon cloth (NiCo2O4 NWA/CC) have been prepared and used for enzyme-free glucose sensing. NiCo2O4 NWA/CC shows larger effective surface area, superior electronic conductivity, and higher catalytic activity towards enzyme-free glucose sensing, with a linear range from 1 μM to 0.63 mM, a sensitivity of 4.12 mA mM-1 cm-2, and low detection limit of 0.5 μM. Moreover, NiCo2O4 NWA/CC also displays good selectivity and stability and thus, it can be reliable for glucose detection in human serum samples. These findings inspire the fabrication of a high-performance electrochemical sensing platform by preparing porous binary metal oxide nanoarrays supported on a 3D conductive substrate.

The Surface Compositions of Triton, Pluto, and Charon

NASA Technical Reports Server (NTRS)

Cruikshank, Dale P.; Roush, Ted L.; Owen, Tobias C.; Quirico, Eric; DeBergh, Catherine

1995-01-01

Neptune's satellite Triton, and the planet-satellite binary Pluto and Charon, are the most distant planetary bodies on which ices have been directly detected. Triton and Pluto have very similar dimensions and mean densities, suggesting a similar or common origin. Through earth-based spectroscopic observations in the near-infrared, solid N2, CH4, and CO have been found on both bodies, with the additional molecule C02 on Triton. N2 dominates both surfaces, although the coverage is not spatially uniform. On Triton, the CH4 and CO are mostly or entirely frozen in the N2 matrix, while CO2 may be spatially segregated. On Pluto, some CH4 and the CO are frozen in the N2 matrix, but there is evidence for additional CH4 in a pure state, perhaps lying as a lag deposit on a subsurface layer of N2. Despite their compositional and dimensional similarities, Pluto and Triton are quite different from one another in detail. Additional hydrocarbons and other volatile ices have been sought spectroscopically but not yet have been detected. The only molecule identified on Pluto's satellite Charon is solid H2O, but the spectroscopic data are of low precision and admit the presence of other ices such as CH4.

CO2 migration in the vadose zone: experimental and numerical modelling of controlled gas injection

NASA Astrophysics Data System (ADS)

gasparini, andrea; credoz, anthony; grandia, fidel; garcia, david angel; bruno, jordi

2014-05-01

The mobility of CO2 in the vadose zone and its subsequent transfer to the atmosphere is a matter of concern in the risk assessment of the geological storage of CO2. In this study the experimental and modelling results of controlled CO2 injection are reported to better understanding of the physical processes affecting CO2 and transport in the vadose zone. CO2 was injected through 16 micro-injectors during 49 days of experiments in a 35 m3 experimental unit filled with sandy material, in the PISCO2 facilities at the ES.CO2 centre in Ponferrada (North Spain). Surface CO2 flux were monitored and mapped periodically to assess the evolution of CO2 migration through the soil and to the atmosphere. Numerical simulations were run to reproduce the experimental results, using TOUGH2 code with EOS7CA research module considering two phases (gas and liquid) and three components (H2O, CO2, air). Five numerical models were developed following step by step the injection procedure done at PISCO2. The reference case (Model A) simulates the injection into a homogeneous soil(homogeneous distribution of permeability and porosity in the near-surface area, 0.8 to 0.3 m deep from the atmosphere). In another model (Model B), four additional soil layers with four specific permeabilities and porosities were included to predict the effect of differential compaction on soil. To account for the effect of higher soil temperature, an isothermal simulation called Model C was also performed. Finally, the assessment of the rainfall effects (soil water saturation) on CO2 emission on surface was performed in models called Model D and E. The combined experimental and modelling approach shows that CO2 leakage in the vadose zone quickly comes out through preferential migration pathways and spots with the ranges of fluxes in the ground/surface interface from 2.5 to 600 g·m-2·day-1. This gas channelling is mainly related to soil compaction and climatic perturbation. This has significant implications to design adapted detection and monitoring strategies of early leakage in commercial CO2 storage. The presence of soils with different compactions at surface influences the CO2 dispersion. The inclusion of soils with different permeability, porosity and liquid saturation results in preferential pathways. The formation of preferential pathways in the soil and hot spots on the surface has commonly been observed in natural systems where deep CO2 fluxes interact with shallow aquifers. Increase of ambient temperature increases CO2 fluxes intensity whereas rainfall decreases CO2 emission in gas phase and trap it as aqueous species in the porous media of the soil. A good accuracy has been obtained for surface CO2 fluxes location and intensity between experimental and modelling results taking into account the selected equation of state, the soil characteristics and the operational conditions. Phenomena of compaction and preferential pathways located only in the first centimetres of the soil can explain the heterogeneity of CO2 fluxes in the 16 m2 surface area of PISCO2 experimental platform.

Eastern equatorial pacific productivity and related-CO2 changes since the last glacial period.

PubMed

Calvo, Eva; Pelejero, Carles; Pena, Leopoldo D; Cacho, Isabel; Logan, Graham A

2011-04-05

Understanding oceanic processes, both physical and biological, that control atmospheric CO(2) is vital for predicting their influence during the past and into the future. The Eastern Equatorial Pacific (EEP) is thought to have exerted a strong control over glacial/interglacial CO(2) variations through its link to circulation and nutrient-related changes in the Southern Ocean, the primary region of the world oceans where CO(2)-enriched deep water is upwelled to the surface ocean and comes into contact with the atmosphere. Here we present a multiproxy record of surface ocean productivity, dust inputs, and thermocline conditions for the EEP over the last 40,000 y. This allows us to detect changes in phytoplankton productivity and composition associated with increases in equatorial upwelling intensity and influence of Si-rich waters of sub-Antarctic origin. Our evidence indicates that diatoms outcompeted coccolithophores at times when the influence of Si-rich Southern Ocean intermediate waters was greatest. This shift from calcareous to noncalcareous phytoplankton would cause a lowering in atmospheric CO(2) through a reduced carbonate pump, as hypothesized by the Silicic Acid Leakage Hypothesis. However, this change does not seem to have been crucial in controlling atmospheric CO(2), as it took place during the deglaciation, when atmospheric CO(2) concentrations had already started to rise. Instead, the concomitant intensification of Antarctic upwelling brought large quantities of deep CO(2)-rich waters to the ocean surface. This process very likely dominated any biologically mediated CO(2) sequestration and probably accounts for most of the deglacial rise in atmospheric CO(2).

The Evolution of Silica Nanoparticle-polyester Coatings on Surfaces Exposed to Sunlight.

PubMed

Truong, Vi Khanh; Stefanovic, Miljan; Maclaughlin, Shane; Tobin, Mark; Vongsvivut, Jitraporn; Al Kobaisi, Mohammad; Crawford, Russell J; Ivanova, Elena P

2016-10-11

Corrosion of metallic surfaces is prevalent in the environment and is of great concern in many areas, including the military, transport, aviation, building and food industries, amongst others. Polyester and coatings containing both polyester and silica nanoparticles (SiO2NPs) have been widely used to protect steel substrata from corrosion. In this study, we utilized X-ray photoelectron spectroscopy, attenuated total reflection infrared micro-spectroscopy, water contact angle measurements, optical profiling and atomic force microscopy to provide an insight into how exposure to sunlight can cause changes in the micro- and nanoscale integrity of the coatings. No significant change in surface micro-topography was detected using optical profilometry, however, statistically significant nanoscale changes to the surface were detected using atomic force microscopy. Analysis of the X-ray photoelectron spectroscopy and attenuated total reflection infrared micro-spectroscopy data revealed that degradation of the ester groups had occurred through exposure to ultraviolet light to form COO·, -H2C·, -O·, -CO· radicals. During the degradation process, CO and CO2 were also produced.

Cassini CAPS Identification of Pickup Ion Compositions at Rhea

NASA Astrophysics Data System (ADS)

Desai, R. T.; Taylor, S. A.; Regoli, L. H.; Coates, A. J.; Nordheim, T. A.; Cordiner, M. A.; Teolis, B. D.; Thomsen, M. F.; Johnson, R. E.; Jones, G. H.; Cowee, M. M.; Waite, J. H.

2018-02-01

Saturn's largest icy moon, Rhea, hosts a tenuous surface-sputtered exosphere composed primarily of molecular oxygen and carbon dioxide. In this Letter, we examine Cassini Plasma Spectrometer velocity space distributions near Rhea and confirm that Cassini detected nongyrotropic fluxes of outflowing CO2+ during both the R1 and R1.5 encounters. Accounting for this nongyrotropy, we show that these possess comparable along-track densities of ˜2 × 10-3 cm-3. Negatively charged pickup ions, also detected during R1, are surprisingly shown as consistent with mass 26 ± 3 u which we suggest are carbon-based compounds, such as CN-, C2H-, C2-, or HCO-, sputtered from carbonaceous material on the moon's surface. The negative ions are calculated to possess along-track densities of ˜5 × 10-4 cm-3 and are suggested to derive from exogenic compounds, a finding consistent with the existence of Rhea's dynamic CO2 exosphere and surprisingly low O2 sputtering yields. These pickup ions provide important context for understanding the exospheric and surface ice composition of Rhea and of other icy moons which exhibit similar characteristics.

Depth and Distribution of CO2 Snow on Mars

NASA Technical Reports Server (NTRS)

Aharonson, Oded; Zuber, Maria T.; Smith, David E.; Neumann, Gregory A.

2003-01-01

The dynamic role of volatiles on the surface of Mars has been a subject of longstanding interest. In the pre-Viking era, much of the debate was necessarily addressed by theoretical considerations. A particularly influential treatment by Leighton and Murray put forth a simple model relying on solar energy balance, and led to the conclusion that the most prominent volatile exchanging with the atmosphere over seasonal cycles is carbon dioxide. Their model suggested that due to this exchange, atmospheric CO2 partial pressure is regulated by polar ice. While current thinking attributes a larger role to H2O ice than did the occasional thin polar coating this model predicted, the CO2 cycle appears to be essentially correct. There are a number of observational constraints on the seasonal exchange of surface volatiles with the atmosphere. The growth and retreat of polar CO2 frost is visible from Earth-based telescopes and from spacecraft in Mars orbit, both at visible wavelengths and in thermal IR properties of the surface. Recently, variations in Gamma ray and neutron fluxes have also been used to infer integrated changes in CO2 mass on the surface. Measurements made by Viking's Mars Atmospheric Water Detector experiment were sensitive to atmospheric H2O vapor abundance. Surface condensates and their transient nature were detected by the Viking landers. The study here is motivated by recent data collected by the Mars Global Surveyor, affording the opportunity to not only detect the lateral distribution of volatiles, but also to constrain the variable volumes of the reservoirs. We elaborate on a technique first employed by Smith et al. By examining averages of a large number of topographic measurements collected by the Mars Orbiter Laser Altimeter (MOLA), that study showed that the zonal pattern of deposition and sublimation of CO2 can be determined. In their first approach, reference surfaces were fit to all measurements in narrow latitude annuli, and the time dependent variations about those mean surfaces were examined. In their second approach, height measurements from pairs of tracks that cross on the surface were interpolated and differenced, forming a set of crossover residuals. These residuals were then examined as a function of time and latitude. The initial studies averaged over longitude to maximize signal and minimize noise in order to isolate the expected small signal. In this follow-up study we now attempt to extract the elevation change pattern also as a function of longitude, and we focus on the crossover approach.

Using radiocarbon to investigate soil respiration impacts on atmospheric CO2

NASA Astrophysics Data System (ADS)

Phillips, C. L.; LaFranchi, B. W.; McFarlane, K. J.; Desai, A. R.

2013-12-01

While soil respiration is believed to represent the largest single source of CO2 emissions on a global scale, there are few tools available to measure soil emissions at large spatial scales. We investigated whether radiocarbon (14C) abundance in CO2 could be used to detect and characterize soil emissions in the atmosphere, taking advantage of the fact that 14C abundance in soil carbon is elevated compared to the background atmosphere, a result of thermonuclear weapons testing during the mid-20th Century (i.e. bomb-C). Working in a temperate hardwood forest in Northern Wisconsin during 2011-12, we made semi-high-frequency measurements of CO2 at nested spatial scales from the soil subsurface to 150 m above ground level. These measurements were used to investigate seasonal patterns in respired C sources, and to evaluate whether variability in soil-respired Δ14C could also be detected in atmospheric measurements. In our ground-level measurements we found large seasonal variation in soil-respired 14CO2 that correlated with soil moisture, which was likely related to root activity. Atmospheric measurements of 14CO2 in the forest canopy (2 to 30m) were used to construct Keeling plots, and these provided larger spatial-scale estimates of respired 14CO2 that largely agreed with the soil-level measurements. In collaboration with the NOAA we also examined temporal patterns of 14CO2 at the Park Falls tall-tower (150m), and found elevated 14CO2 levels during summer months that likely resulted from increased respiration from heterotrophic sources. These results demonstrate that a fingerprint from soil-respired CO2 can be detected in the seasonal patterns of atmospheric 14CO2, even at a regionally-integrating spatial scale far from the soil surface.

Electrochemical primer extension based on polyoxometalate electroactive labels for multiplexed detection of single nucleotide polymorphisms.

PubMed

Chahin, Nassif; Uribe, Laura A; Debela, Ahmed M; Thorimbert, Serge; Hasenknopf, Bernold; Ortiz, Mayreli; Katakis, Ioannis; O'Sullivan, Ciara K

2018-06-07

Polyoxymetalates (POMs) ([SiW 11 O 39 {Sn(CH 2 ) 2 CO)}] 4- and [P 2 W 17 O 61 {Sn(CH 2 ) 2 CO)}] 6- ) were used to modify dideoxynucleotides (ddNTPs) through amide bond formation, and applied to the multiplexed detection of single nucleotide polymorphisms (SNPs) in an electrochemical primer extension reaction. Each gold electrode of an array was functionalised with a short single stranded thiolated DNA probe, specifically designed to extend with the POM-ddNTP at the SNP site to be interrogated. The system was applied to the simultaneous detection of 4 SNPs within a single stranded 103-mer model target generated using asymmetric PCR, highlighting the potential of POM-ddNTPs for targeted, multiplexed SNP detection. The four DNA bases were successfully labelled with both ([SiW 11 O 39 {Sn(CH 2 ) 2 CO)}] 4- and [P 2 W 17 O 61 {Sn(CH 2 ) 2 CO)}] 6- ), and [SiW 11 O 39 {Sn(CH 2 ) 2 CO)}] 4- demonstrated to be the more suitable due to its single oxidation peak, which provides an unequivocal signal. The POM-ddNTP enzymatically incorporated to the DNA anchored to the surface was visualised by AFM using gold coated mica. The developed assay has been demonstrated to be highly reproducible, simple to carry out and with very low non-specific background signals. Future work will focus on applying the developed platform to the detection of SNPs associated with rifampicin resistance in real samples from patients suffering from tuberculosis. Copyright © 2018. Published by Elsevier B.V.

The Role of Optimality in Characterizing CO2 Seepage from Geological Carbon Sequestration Sites

NASA Astrophysics Data System (ADS)

Cortis, A.; Oldenburg, C. M.; Benson, S. M.

2007-12-01

Storage of large amounts of carbon dioxide (CO2) in deep geological formations for greenhouse-gas mitigation is gaining momentum and moving from its conceptual and testing stages towards widespread application. In this talk we explore various optimization strategies for characterizing surface leakage (seepage) using near-surface measurement approaches such as accumulation chambers and eddy covariance towers. Seepage characterization objectives and limitations need to be defined carefully from the outset especially in light of large natural background variations that can mask seepage. The cost and sensitivity of seepage detection are related to four critical length scales pertaining to the size of the: (1) region that needs to be monitored; (2) footprint of the measurement approach; (3) main seepage zone; and (4) region in which concentrations or fluxes are influenced by seepage. Seepage characterization objectives may include one or all of the tasks of detecting, locating, and quantifying seepage. Each of these tasks has its own optimal strategy. Detecting and locating seepage in a region in which there is no expected or preferred location for seepage nor existing evidence for seepage requires monitoring on a fixed grid, e.g., using eddy covariance towers. The fixed-grid approaches needed to detect seepage are expected to require large numbers of eddy covariance towers for large-scale geologic CO2 storage. Once seepage has been detected and roughly located, seepage zones and features can be optimally pinpointed through a dynamic search strategy, e.g., employing accumulation chambers and/or soil-gas sampling. Quantification of seepage rates can be done through measurements on a localized fixed grid once the seepage is pinpointed. Background measurements are essential for seepage detection in natural ecosystems. Artificial neural networks are considered as regression models useful for distinguishing natural system behavior from anomalous behavior suggestive of CO2 seepage without need for detailed understanding of natural system processes. Because of the local extrema in CO2 fluxes and concentrations in natural systems, simple steepest-descent algorithms are not effective and evolutionary computation algorithms are proposed as a paradigm for dynamic monitoring networks to pinpoint CO2 seepage areas. This work was carried out within the ZERT project, funded by the Assistant Secretary for Fossil Energy, Office of Sequestration, Hydrogen, and Clean Coal Fuels, National Energy Technology Laboratory, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

CO dissociation and CO hydrogenation on smooth and ion-bombarded Pd(1 1 1): SFG and XPS spectroscopy at mbar pressures

NASA Astrophysics Data System (ADS)

Rupprechter, G.; Kaichev, V. V.; Unterhalt, H.; Morkel, M.; Bukhtiyarov, V. I.

2004-07-01

The CO dissociation probability on transition metals is often invoked to explain the product distribution (selectivity) of catalytic CO hydrogenation. Along these lines, we have investigated CO adsorption and dissociation on smooth and ion-bombarded Pd(1 1 1) at pressures up to 1 mbar using vibrational sum frequency generation (SFG) and X-ray photoelectron spectroscopy (XPS). Under high pressure, CO adsorbate structures were observed that were identical to high-coverage structures in UHV. On ion-bombarded surfaces an additional species was detected which was attributed to CO bridge bonded to defect (low-coordinated) sites. On both surfaces, no indications of CO dissociation were found even after hours of 0.1 mbar CO exposure. However, exposing CO/H 2 mixtures to ion-bombarded Pd(1 1 1) produced carbonaceous deposits suggesting CH xO species as precursors for CO bond cleavage and that the formation of CH xO is facilitated by surface defects. The relevance of the observations for CO hydrogenation on Pd catalysts is discussed.

Synthesis of Co3O4/TiO2 composite by pyrolyzing ZIF-67 for detection of xylene

NASA Astrophysics Data System (ADS)

Bai, Shouli; Tian, Ke; Tian, Ye; Guo, Jun; Feng, Yongjun; Luo, Ruixian; Li, Dianqing; Chen, Aifan; Liu, Chung Chiun

2018-03-01

Co3O4/TiO2 composites with p-n heterojunction have been successfully prepared by pyrolyzing sacrificial template of Ti ion loaded Co-based Zeolitic imidazolate framework (ZIF-67). The structure and morphology of composite have been characterized by means of the analysis of XRD, FESEM, HRTEM and XPS spectra. The composite with a Co/Ti molar ratio of 4:1 exhibits the maximum sensing response of 6.17-50 ppm xylene, which is 5 times higher than pristine Co3O4. Moreover, Co3O4/TiO2 composite also shows good selectivity, long-term stability and rapid response and recovery. Such excellent sensing performances are attributed to material porous structure, high specific surface and the formation of abundant p-n heterojunction that permits the gas adsorption, diffusion and surface reaction and then improve the gas sensing performance. This work develops a promising synthesized approach of metal oxide composites for broader MOFs application in gas sensor field.

[Experimental liver and kidney surgery with CO2, CO, holmium, and neodym lasers. Cutting effect, hemostasis, histopathology, and healing (author's transl)].

PubMed

Karbe, E; Königsmann, G; Beck, R

1980-01-01

Various laser devices (CO2, CO, Nd: YAG, and holmium: YAG lasers) have been used on pig livers and on dog kidneys for comparison with conventional surgical instruments (electroscalpel, cryoscalpel, and scalpel). CO2 and CO lasers caused the least tissue damage, followed by the holmium laser; severe damage was caused by the Nd: YAG laser. The order was reverse for coagulative effect. The conventional reference instruments showed a weaker hemostatic effect. Surfaces cut by laser healed in four to eight weeks without complications. Remnants of charred tissue in various quantities could still be detected after eight weeks in all cases where CO2, CO, and Nd: YAG lasers had been used. This obviously did not affect scar formation.

Measurements of soil, surface water, and groundwater CO2 concentration variability within Earth's critical zone: low-cost, long-term, high-temporal resolution monitoring

NASA Astrophysics Data System (ADS)

Blackstock, J. M.; Covington, M. D.; Williams, S. G. W.; Myre, J. M.; Rodriguez, J.

2017-12-01

Variability in CO2 fluxes within Earth's Critical zone occurs over a wide range of timescales. Resolving this and its drivers requires high-temporal resolution monitoring of CO2 both in the soil and aquatic environments. High-cost (> 1,000 USD) gas analyzers and data loggers present cost-barriers for investigations with limited budgets, particularly if high spatial resolution is desired. To overcome high-costs, we developed an Arduino based CO2 measuring platform (i.e. gas analyzer and data logger). The platform was deployed at multiple sites within the Critical Zone overlying the Springfield Plateau aquifer in Northwest Arkansas, USA. The CO2 gas analyzer used in this study was a relatively low-cost SenseAir K30. The analyzer's optical housing was covered by a PTFE semi-permeable membrane allowing for gas exchange between the analyzer and environment. Total approximate cost of the monitoring platform was 200 USD (2% detection limit) to 300 USD (10% detection limit) depending on the K30 model used. For testing purposes, we deployed the Arduino based platform alongside a commercial monitoring platform. CO2 concentration time series were nearly identical. Notably, CO2 cycles at the surface water site, which operated from January to April 2017, displayed a systematic increase in daily CO2 amplitude. Preliminary interpretation suggests key observation of seasonally increasing stream metabolic function. Other interpretations of observed cyclical and event-based behavior are out of the scope of the study; however, the presented method describes an accurate near-hourly characterization of CO2 variability. The new platform has been shown to be operational for several months, and we infer reliable operation for much longer deployments (> 1 year) given adequate environmental protection and power supply. Considering cost-savings, this platform is an attractive option for continuous, accurate, low-power, and low-cost CO2 monitoring for remote locations, globally.

Optical Interference-Free Surface-Enhanced Raman Scattering CO-Nanotags for Logical Multiplex Detection of Vascular Disease-Related Biomarkers.

PubMed

Gong, Tianxun; Hong, Zi-Yao; Chen, Ching-Hsiang; Tsai, Cheng-Yen; Liao, Lun-De; Kong, Kien Voon

2017-03-28

Matrix metalloproteinases (MMPs), specifically MMP-2, MMP-7, and MMP-9, have been discovered to be linked to many forms of vascular diseases such as stroke, and their detection is crucial to facilitate clinical diagnosis. In this work, we prepared a class of optical interference-free SERS nanotags (CO-nanotags) that can be used for the purpose of multiplex sensing of different MMPs. Multiplex detection with the absence of cross-talk was achieved by using CO-nanotags with individual tunable intrinsic Raman shifts of CO in the 1800-2200 cm -1 region determined by the metal core and ligands of the metal carbonyl complex. Boolean logic was used as well to simultaneously probe for two proteolytic inputs. Such nanotags offer the advantages of convenient detection of target nanotags and high sensitivity as validated in the ischemia rat model.

Ultrathin NiCo2O4 nanowalls supported on a 3D nanoporous gold coated needle for non-enzymatic amperometric sensing of glucose.

PubMed

Li, Weiwei; Qi, Hui; Wang, Baogang; Wang, Qiyu; Wei, Shuting; Zhang, Xiaolin; Wang, Ying; Zhang, Lei; Cui, Xiaoqiang

2018-01-24

A disposable needle-type of hybrid electrode was prepared from a core of stainless steel needle whose surface was modified with a 3D nanoporous gold/NiCo 2 O 4 nanowall hybrid structure for electrochemical non-enzymatic glucose detection. This hybrid electrode, best operated at 0.45 V (vs. SCE) in solutions of pH 13 has a linear response in the 0.01 to 21 mM glucose concentration range, a response time of <1 s, and a 1 μM detection limit (at an S/N ratio of 3). The remarkable enhancement compared to the solid gold/NiCo 2 O 4 and stainless steel/NiCo 2 O 4 hybrid electrodes in electrochemical performance is assumed to originate from the good electrical conductivity and large surface area of the hybrid electrode, which enhance the transport of mass and charge during electrochemical reactions. This biosensor was also applied to real sample analysis with little interferences. The electrode is disposable and considered to be a promising tool for non-enzymatic sensing of glucose in a variety of practical situations. Graphical abstract Ultrathin NiCo 2 O 4 nanowalls supported on nanoporous gold that is coated on a stainless steel needle was fabricated for sensitive non-enzymatic amperometric sensing of glucose.

Modeling Minor Constituents of Europa's Atmosphere

NASA Astrophysics Data System (ADS)

Cassidy, T. A.; Johnson, R. E.

2007-12-01

A spacecraft orbiting Jupiter's moon Europa, of the sort considered by both ESA and NASA, would provide an opportunity to determine the composition and morphology of its tenuous atmosphere. Europa's atmosphere, though tenuous, has been detected by Earth-based telescopes. Its O2 atmosphere was detected from Earth orbit and its much thinner alkali atmosphere was detected by ground-based telescopes. Many other species are expected based on surface reflectance spectra, such as H2O, Sn, SO2, CO2, H2O2. I will discuss the issues involved in the modeling of these as-yet-undetected components. Previous theoretical studies and observations of the atmosphere produced important conclusions about the surface and its interaction with the Jovian magnetosphere. The modeling and detection of minor components could reveal much more. Of particular interest is the detectability of these species with an orbiting mass spectrometer or more distant light spectrometer.

EPR spin trapping evidence of radical intermediates in the photo-reduction of bicarbonate/CO2 in TiO2 aqueous suspensions.

PubMed

Molinari, Alessandra; Samiolo, Luca; Amadelli, Rossano

2015-05-01

Using the EPR spin trapping technique, we prove that simultaneous reactions take place in illuminated suspensions of TiO2 in aqueous carbonate solutions (pH ≈ 7). The adsorbed HCO3(-) is reduced to formate as directly made evident by the detection of formate radicals (˙CO2(-)). In addition, the amount of OH˙ radicals from the photo-oxidation of water shows a linear dependence on the concentration of bicarbonate, indicating that electron scavenging by HCO3(-) increases the lifetime of holes. In a weakly alkaline medium, photo-oxidation of HCO3(-)/CO3(2-) to ˙CO3(-) interferes with the oxidation of water. A comparative analysis of different TiO2 samples shows that formation of ˙CO2(-) is influenced by factors related to the nature of the surface, once expected surface area effects are accounted for. Modification of the TiO2 surface with noble metal nanoparticles does not have unequivocal benefits: the overall activity improves with Pd and Rh but not with Ru, which favours HCO3(-) photo-oxidation even at pH = 7. In general, identification of radical intermediates of oxidation and reduction reactions can provide useful mechanistic information that may be used in the development of photocatalytic systems for the reduction of CO2 also stored in the form of carbonates.

The Mechanism of Low-Temperature Oxidation of Carbon Monoxide by Oxygen over the PdCl2–CuCl2/γ-Al2O3 Nanocatalyst

PubMed Central

Bruk, Lev; Titov, Denis; Ustyugov, Alexander; Chernikova, Valeriya; Tkachenko, Olga; Kustov, Leonid; Murzin, Vadim; Oshanina, Irina; Temkin, Oleg

2018-01-01

The state of palladium and copper on the surface of the PdCl2–CuCl2/γ-Al2O3 nanocatalyst for the low-temperature oxidation of CO by molecular oxygen was studied by various spectroscopic techniques. Using X-ray absorption spectroscopy (XAS), powder X-ray diffraction (XRD), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), freshly prepared samples of the catalyst were studied. The same samples were also evaluated after interaction with CO, O2, and H2O vapor in various combinations. It was shown that copper exists in the form of Cu2Cl(OH)3 (paratacamite) nanophase on the surface of the catalyst. No palladium-containing crystalline phases were identified. Palladium coordination initially is comprised of four chlorine atoms. It was shown by XAS that this catalyst is not capable of oxidizing CO at room temperature in the absence of H2O and O2 over 12 h. Copper(II) and palladium(II) are reduced to Cu(I) and Pd(I,0) species, respectively, in the presence of CO and H2O vapor (without O2). It was found by DRIFTS that both linear (2114 cm−1, 1990 cm−1) and bridging (1928 cm−1) forms of coordinated CO were formed upon adsorption onto the catalyst surface. Moreover, the formation of CO2 was detected upon the interaction of the coordinated CO with oxygen. The kinetics of CO oxidation was studied at 18–38 °C at an atmospheric pressure for CO, O2, N2, and H2O (gas) mixtures in a flow reactor (steady state conditions). PMID:29614029

Modeling and Evaluation of Geophysical Methods for Monitoring and Tracking CO2 Migration

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

Daniels, Jeff

2012-11-30

Geological sequestration has been proposed as a viable option for mitigating the vast amount of CO{sub 2} being released into the atmosphere daily. Test sites for CO{sub 2} injection have been appearing across the world to ascertain the feasibility of capturing and sequestering carbon dioxide. A major concern with full scale implementation is monitoring and verifying the permanence of injected CO{sub 2}. Geophysical methods, an exploration industry standard, are non-invasive imaging techniques that can be implemented to address that concern. Geophysical methods, seismic and electromagnetic, play a crucial role in monitoring the subsurface pre- and post-injection. Seismic techniques have beenmore » the most popular but electromagnetic methods are gaining interest. The primary goal of this project was to develop a new geophysical tool, a software program called GphyzCO2, to investigate the implementation of geophysical monitoring for detecting injected CO{sub 2} at test sites. The GphyzCO2 software consists of interconnected programs that encompass well logging, seismic, and electromagnetic methods. The software enables users to design and execute 3D surface-to-surface (conventional surface seismic) and borehole-to-borehole (cross-hole seismic and electromagnetic methods) numerical modeling surveys. The generalized flow of the program begins with building a complex 3D subsurface geological model, assigning properties to the models that mimic a potential CO{sub 2} injection site, numerically forward model a geophysical survey, and analyze the results. A test site located in Warren County, Ohio was selected as the test site for the full implementation of GphyzCO2. Specific interest was placed on a potential reservoir target, the Mount Simon Sandstone, and cap rock, the Eau Claire Formation. Analysis of the test site included well log data, physical property measurements (porosity), core sample resistivity measurements, calculating electrical permittivity values, seismic data collection, and seismic interpretation. The data was input into GphyzCO2 to demonstrate a full implementation of the software capabilities. Part of the implementation investigated the limits of using geophysical methods to monitor CO{sub 2} injection sites. The results show that cross-hole EM numerical surveys are limited to under 100 meter borehole separation. Those results were utilized in executing numerical EM surveys that contain hypothetical CO{sub 2} injections. The outcome of the forward modeling shows that EM methods can detect the presence of CO{sub 2}.« less

A new signal amplification strategy of photoelectrochemical immunoassay for highly sensitive interleukin-6 detection based on TiO2/CdS/CdSe dual co-sensitized structure.

PubMed

Fan, Gao-Chao; Ren, Xiao-Lin; Zhu, Cheng; Zhang, Jian-Rong; Zhu, Jun-Jie

2014-09-15

Dual co-sensitized structure of TiO2/CdS/CdSe was designed to develop a novel photoelectrochemical immunoassay for highly sensitive detection of human interleukin-6 (IL-6). To construct a sensing electrode, TiO2/CdS hybrid was prepared by successive adsorption and reaction of Cd(2+) and S(2-) ions on the surface of TiO2 and then was employed as matrix for immobilization of anti-IL-6 antibody, whereas CdSe QDs linked to IL-6 were used for signal amplification via the specific antibody-antigen immunoreaction between anti-IL-6 and IL-6-CdSe bioconjugate. Greatly enhanced sensitivity for IL-6 detection was derived from the new co-sensitization signal amplification strategy. First, the TiO2/CdS/CdSe co-sensitized structure extended the absorption range to long wavelength of white light, which adequately utilized the light energy. Second, the TiO2/CdS/CdSe co-sensitized structure possessed stepwise band-edge levels favoring ultrafast transfer of photogenerated electrons and significantly prompted the photoelectrochemical performance. Besides, the introduction of CdSe effectively prevented the recombination of photogenerated electrons in the conduction band of CdS, further causing an enhanced photocurrent. Accordingly, upon the co-sensitization strategy, a novel immunoassay based on the competitive binding of anti-IL-6 antibody with IL-6 antigen and IL-6-CdSe bioconjugate was developed, and it exhibited a wide linear range from 1.0 pg/mL to 100 ng/mL with a low detection limit of 0.38 pg/mL for IL-6 detection. The proposed co-sensitization strategy presented high sensitivity, reproducibility, specificity and stability, and also opened up a new promising platform for detection of other biomarkers. Copyright © 2014 Elsevier B.V. All rights reserved.

In situ detection of microbial respiration in soils and salt flats. [Nevada desert

NASA Technical Reports Server (NTRS)

Tew, R. W.

1973-01-01

Increase in CO2 partial pressures over a desert soil treated with casamino-acids glucose solution correlated with bacterial growth. Few or no increases in numbers of bacteria or CO2 concentrations were noted in similar plots treated with water only or receiving no treatment. Growth in the soil appeared to be severely nutrient limited during the 10 day experiment. Especially rapid growth took place between the third and fifth day, when temperatures ranged from 0 deg. (night) to a maximum of 17.4 deg. (day). Under the conditions of the experiment, intermittent CO2 assay was an insensitive indicator of growth, possibly because of restiction of gas escape by the desert pavement or solution, exchange, or precipitation of carbonate, but more likely because of inefficient sealing of hoods to and below the soil surface. CO2 assay was unable to detect microbial successions. The unpredictable course of these successions, plus unpredictable relative retentions mitigates against assay of organic gases as reliable in situ detection of microbial activity, except perhaps in very alkaline environments such as Owens Lake salts.

Metal Carbonation of Forsterite in Supercritical CO2 and H2O Using Solid State 29Si, 13C NMR Spectroscop

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

Kwak, Ja Hun; Hu, Jian Z.; Hoyt, David W.

2010-03-11

Ex situ solid state NMR was used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration (GCS) using a model silicate mineral forsterite (Mg2SiO4)+supercriticalCO2 with and without H2O. Run conditions were 80 C and 96 atm. 29Si NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce dissolved Mg2+, and mono- and oligomeric hydroxylated silica species. Surface hydrolysis products contain only Q0 (Si(OH)4) and Q1(Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to lessmore » than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. 29Si NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. 13C MAS NMR identified a possible reaction intermediate as (MgCO3)4-Mg(OH)2-5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed.« less

The Effects of Radiation on the Adsorption of CO2 by Nonice Materials Relevant to Icy Satellites

NASA Astrophysics Data System (ADS)

Hibbitts, C.; Stockstill-Cahill, K.; Paranicas, C.; Wing, B. R.

2017-12-01

Water-ice and water-rich non-ice materials dominate the surfaces of the icy satellites of Jupiter and Saturn, with CO2 detected at trace amounts largely in the nonice materials [1,2]. Although, the mechanism by which CO2 is entrained within the nonice material has not yet been understood, one hypothesis is adsorption by van der Waals forces or induced dipole interactions, with laboratory measurements demonstrating some analog materials can stably retain adsorbed CO2 while under vacuum at the temperatures of the icy satellites [3,4]. The strength and spectral signature of the adsorbed CO2 is dependent upon the composition and temperature of the host material. So far, the most adsorptive analogs are complex expansive clays, probably because of the large microporosity and presence of charge compensating cations to act as adsorption sites. However, the surfaces of the airless Galilean and Saturnian satellites are bombarded by high-energy particles from the planetary magnetospheres, which could alter the nonice material affecting adsorptivity towards CO2 (and other volatiles). Thus, we have conducted experiments to explore the possibility that irradiation could increase the adsorptivity of other analogs more consistent with the expected composition of the satellites surfaces. This hypothesis is explored for CO2 adsorption onto pressed powder pellets that are cooled to the surface temperatures of the satellites' surfaces under solar illumination ( 125-150 K) and dosed with CO2 from directly above the surface of the pellet, while collecting spectra of the asymmetric stretch fundamental of the CO2 absorption band near 4.25 microns. After this initial spectrum, the pellet is warmed to degas any adsorbed CO2 and then recooled. The pellet is then irradiated with 40 keV electrons for 48-72 hours at a fluence of 80 microamps and the adsorption experiment is repeated. The infrared spectrum is a bidirectional reflectance measurement using a Bruker Vertex 70 FTIR with and external MCT detector and the chamber pressure 1e-8 torr or lower. References: [1] McCord et al. 1998. J. Geophys. Res., 103, E4, 8603-8626; [2] Clark et al. 2005. Nature, 435, 66-69; [3] Hibbitts, C.A. and J. Szanyi. 2007. Icarus, 191, 371-380; [4] Berlanga, G. et al., 2016. Icarus, 280, 366-377.

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

ANTS-anchored Zn-Al-CO3-LDH particles as fluorescent probe for sensing of folic acid

NASA Astrophysics Data System (ADS)

Liu, Pengfei; Liu, Dan; Liu, Yanhuan; Li, Lei

2016-09-01

A novel fluorescent nanosensor for detecting folic acid (FA) in aqueous media has been developed based on 8-aminonaphthalene-1,3,6-trisulfonate (ANTS) anchored to the surface of Zn-Al-CO3-layered double hydroxides (LDH) particles. The nanosensor showed high fluorescence intensity and good photostability due to a strong coordination interaction between surface Zn2+ ions of Zn-Al-CO3-LDH and N atoms of ANTS, which were verified by result of X-ray photoelectron spectroscopy (XPS). ANTS-anchored on the surface of Zn-Al-CO3-LDH restricted the intra-molecular rotation leading to ANTS-anchored J-type aggregation emission enhancement. ANTS-anchored Zn-Al-CO3-LDH particles exhibited highly sensitive and selective response to FA over other common metal ions and saccharides present in biological fluids. The proposed mechanism was that oxygen atoms of -SO3 groups in ANTS-anchored on the surface of Zn-Al-CO3-LDH were easily collided by FA molecules to form potential hydrogen bonds between ANTS-anchored and FA molecules, which could effectively quench the ANTS-anchored fluorescence. Under the simulated physiological conditions (pH of 7.4), the fluorescence quenching was fitted to Stern-Volmer equation with a linear response in the concentration range of 1 μM to 200 μM with a limit of detection of 0.1 μM. The results indicate that ANTS-anchored Zn-Al-CO3-LDH particles can afford a very sensitive system for the sensing FA in aqueous solution.

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

Mohaghegh, Shahab D.

apability of underground carbon dioxide storage to confine and sustain injected CO2 for a very long time is the main concern for geologic CO2 sequestration. If a leakage from a geological CO2 sequestration site occurs, it is crucial to find the approximate amount and the location of the leak in order to implement proper remediation activity. An overwhelming majority of research and development for storage site monitoring has been concentrated on atmospheric, surface or near surface monitoring of the sequestered CO2. This study aims to monitor the integrity of CO2 storage at the reservoir level. This work proposes developing in-situmore » CO2 Monitoring and Verification technology based on the implementation of Permanent Down-hole Gauges (PDG) or “Smart Wells” along with Artificial Intelligence and Data Mining (AI&DM). The technology attempts to identify the characteristics of the CO2 leakage by de-convolving the pressure signals collected from Permanent Down-hole Gauges (PDG). Citronelle field, a saline aquifer reservoir, located in the U.S. was considered for this study. A reservoir simulation model for CO2 sequestration in the Citronelle field was developed and history matched. The presence of the PDGs were considered in the reservoir model at the injection well and an observation well. High frequency pressure data from sensors were collected based on different synthetic CO2 leakage scenarios in the model. Due to complexity of the pressure signal behaviors, a Machine Learning-based technology was introduced to build an Intelligent Leakage Detection System (ILDS). The ILDS was able to detect leakage characteristics in a short period of time (less than a day) demonstrating the capability of the system in quantifying leakage characteristics subject to complex rate behaviors. The performance of ILDS was examined under different conditions such as multiple well leakages, cap rock leakage, availability of an additional monitoring well, presence of pressure drift and noise in the pressure sensor and uncertainty in the reservoir model.« less

NO and NO2 Sensing Properties of WO3 and Co3O4 Based Gas Sensors

PubMed Central

Akamatsu, Takafumi; Itoh, Toshio; Izu, Noriya; Shin, Woosuck

2013-01-01

Semiconductor-based gas sensors that use n-type WO3 or p-type Co3O4 powder were fabricated and their gas sensing properties toward NO2 or NO (0.5–5 ppm in air) were investigated at 100 °C or 200 °C. The resistance of the WO3-based sensor increased on exposure to NO2 and NO. On the other hand, the resistance of the Co3O4-based sensor varied depending on the operating temperature and the gas species. The chemical states of the surface of WO3 or those of the Co3O4 powder on exposure to 1 ppm NO2 and NO were investigated by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. No clear differences between the chemical states of the metal oxide surface exposed to NO2 or NO could be detected from the DRIFT spectra. PMID:24048338

ANTS-anchored Zn-Al-CO{sub 3}-LDH particles as fluorescent probe for sensing of folic acid

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

Liu, Pengfei; Liu, Dan; Liu, Yanhuan

2016-09-15

A novel fluorescent nanosensor for detecting folic acid (FA) in aqueous media has been developed based on 8-aminonaphthalene-1,3,6-trisulfonate (ANTS) anchored to the surface of Zn-Al-CO{sub 3}-layered double hydroxides (LDH) particles. The nanosensor showed high fluorescence intensity and good photostability due to a strong coordination interaction between surface Zn{sup 2+} ions of Zn-Al-CO{sub 3}-LDH and N atoms of ANTS, which were verified by result of X-ray photoelectron spectroscopy (XPS). ANTS-anchored on the surface of Zn-Al-CO{sub 3}-LDH restricted the intra-molecular rotation leading to ANTS-anchored J-type aggregation emission enhancement. ANTS-anchored Zn-Al-CO{sub 3}-LDH particles exhibited highly sensitive and selective response to FA over othermore » common metal ions and saccharides present in biological fluids. The proposed mechanism was that oxygen atoms of -SO{sub 3} groups in ANTS-anchored on the surface of Zn-Al-CO{sub 3}-LDH were easily collided by FA molecules to form potential hydrogen bonds between ANTS-anchored and FA molecules, which could effectively quench the ANTS-anchored fluorescence. Under the simulated physiological conditions (pH of 7.4), the fluorescence quenching was fitted to Stern-Volmer equation with a linear response in the concentration range of 1 μM to 200 μM with a limit of detection of 0.1 μM. The results indicate that ANTS-anchored Zn-Al-CO{sub 3}-LDH particles can afford a very sensitive system for the sensing FA in aqueous solution. - Highlights: • A novel fluorescent nanosensor has been developed. • The sensor exhibited highly sensitive and selective response to FA. • The fluorescence quenching was fitted to Stern–Volmer equation. • The linear response range was 1–200 μM with a limit of detection of 0.1 μM.« less

The relationship between delta C-13 of organic matter and (CO2(aq)) in ocean surface water - Data from the JGOFS site in the northeast Atlantic Ocean and a model. [Joint Global Ocean Flux Study

NASA Technical Reports Server (NTRS)

Rau, G. H.; Takahashi, T.; Des Marais, D. J.; Repeta, D. J.; Martin, J. H.

1992-01-01

Consistent with the hypothesis that plankton delta C-14 and (CO2(aq)) are inversely related, increases in both sinking and suspended particulate organic matter (POM) delta C-13 detected by the Joint Global Ocean Flux Study (JGOFS) were highly negatively correlated with mixed-layer (CO2(aq)). A model of plant delta C-13 by Farquhar et al. (1982) is adapted to show that under a constant phytoplankton demand for CO2 an inverse nonlinear suspended POM delta C-13 response to ambient (CO2(aq)) is expected. Differences between predicted and observed suspended POM delta C-13 vs. (CO2(aq)) trends and among observed relationships can be reconciled if biological CO2 demand is allowed to vary.

Evolution of CO2, CH4, and OCS abundances relative to H2O in the coma of comet 67P around perihelion from Rosetta/VIRTIS-H observations

NASA Astrophysics Data System (ADS)

Bockelée-Morvan, Dominique; Crovisier, J.; Erard, S.; Capaccioni, F.; Leyrat, C.; Filacchione, G.; Drossart, P.; Encrenaz, T.; Biver, N.; de Sanctis, M.-C.; Schmitt, B.; Kührt, E.; Capria, M.-T.; Combes, M.; Combi, M.; Fougere, N.; Arnold, G.; Fink, U.; Ip, W.; Migliorini, A.; Piccioni, G.; Tozzi, G.

2016-11-01

Infrared observations of the coma of 67P/Churyumov-Gerasimenko were carried out from 2015 July to September, I.e. around perihelion (2015 August 13), with the high-resolution channel of the Visible and Infrared Thermal Imaging Spectrometer instrument onboard Rosetta. We present the analysis of fluorescence emission lines of H2O, CO2, 13CO2, OCS, and CH4 detected in limb sounding with the field of view at 2.7-5 km from the comet centre. Measurements are sampling outgassing from the illuminated Southern hemisphere, as revealed by H2O and CO2 raster maps, which show anisotropic distributions, aligned along the projected rotation axis. An abrupt increase of water production is observed 6 d after perihelion. In the meantime, CO2, CH4, and OCS abundances relative to water increased by a factor of 2 to reach mean values of 32, 0.47, and 0.18 per cent, respectively, averaging post-perihelion data. We interpret these changes as resulting from the erosion of volatile-poor surface layers. Sustained dust ablation due to the sublimation of water ice maintained volatile-rich layers near the surface until at least the end of the considered period, as expected for low thermal inertia surface layers. The large abundance measured for CO2 should be representative of the 67P nucleus original composition, and indicates that 67P is a CO2-rich comet. Comparison with abundance ratios measured in the Northern hemisphere shows that seasons play an important role in comet outgassing. The low CO2/H2O values measured above the illuminated Northern hemisphere are not original, but the result of the devolatilization of the uppermost layers.

Analysis of Pulsed Airborne Lidar Measurements of Atmospheric CO2 Column Absorption from 3-13 km Altitudes

NASA Technical Reports Server (NTRS)

Abshire, James B.; Weaver, Clark J.; Riris, Haris; Mao, Jianping; Sun, Xiaoli; Allan, Graham R.; Hasselbrack, William; Browell, Edward V.

2011-01-01

We have developed a pulsed lidar technique for measuring the tropospheric CO2 concentrations as a candidate for NASA's ASCENDS space mission [1]. It uses two pulsed laser transmitters allowing simultaneous measurement of a CO2 absorption line in the 1575 nm band, O2 extinction in the Oxygen A-band, surface height and backscatter profile. The lasers are precisely stepped in wavelength across the CO2 line and an O2 line region during the measurement. The direct detection receiver measures the energies of the laser echoes from the surface along with the range profile of scattering in the path. The column densities for the CO2 and O2 gases are estimated from the ratio of the on- and off-line signals via the integrated path differential absorption (IPDA) technique. The time of flight of the laser pulses is used to estimate the height of the scattering surface and to reject laser photons scattered in the atmosphere. We developed an airborne lidar to demonstrate an early version of the CO2 measurement from the NASA Glenn Lear-25 aircraft. The airborne lidar stepped the pulsed laser's wavelength across the selected CO2 line with 20 wavelength steps per scan. The line scan rate is 450 Hz, the laser pulse widths are 1 usec, and laser pulse energy is 24 uJ. The time resolved laser backscatter is collected by a 20 cm telescope, detected by a NIR photomultiplier and is recorded on every other reading by a photon counting system [2]. During August 2009 we made a series of 2.5 hour long flights and measured the atmospheric CO2 absorption and line shapes using the 1572.33 nm CO2 line. Measurements were made at stepped altitudes from 3-13 km over locations in the US, including the SGP ARM site in Oklahoma, central Illinois, north-eastern North Carolina, and over the Chesapeake Bay and the eastern shore of Virginia. Although the received signal energies were weaker than expected for ASCENDS, clear CO2 line shapes were observed at all altitudes, and some measurements were made through thin clouds. The Oklahoma and east coast flights were coordinated with a LaRC/ITT CO2 lidar on the LaRC UC-12 aircraft, and in-situ measurements were made using its CO2 sensor and radiosondes. We have conducted an analysis of the ranging and IPDA lidar measurements from these four flights. Most flights had 5-6 altitude steps with 200-300 seconds of recorded measurements per step. We used a cross-correlation approach to process the laser echo records. This was used to estimate the range to the scattering surface, to define the edges of the laser pulses and to determine echo pulse energy at each wavelength. We used a minimum mean square approach to fit an instrument response function and to solve for the best-fit CO2 absorption line shape. We then calculated the differential optical depth (DOD) of the fitted CO2 line. We computed its statistics at the various altitude steps, and compare them to the DODs calculated from spectroscopy based on HITRAN 2008 and the column conditions calculated from the airborne in-situ readings. The results show the lidar and in-situ measurements have very similar DOD change with altitude and greater than 10 segments per flight where the scatter in the lidar measurements are less than or equal to 1ppm. We also present the results from subsequent CO2 column absorption measurements, which were made with stronger detected signals during three flights on the NASA DC-8 over the southwestern US in during July 2010.

Selective electrochemical detection of 2,4,6-trinitrotoluene (TNT) in water based on poly(styrene-co-acrylic acid) PSA/SiO2/Fe3O4/AuNPs/lignin-modified glassy carbon electrode.

PubMed

Mahmoud, Khaled A; Abdel-Wahab, Ahmed; Zourob, Mohammed

2015-01-01

A new versatile electrochemical sensor based on poly(styrene-co-acrylic acid) PSA/SiO2/Fe3O4/AuNPs/lignin (L-MMS) modified glassy carbon electrode (GCE) was developed for the selective detection of trace trinitrotoluene (TNT) from aqueous media with high sensitivity. The fabricated magnetic microspheres were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). L-MMS films were cast on the GCE surface to fabricate the TNT sensing electrode. The limit of detection (LOD) of TNT determined by the amperometric i-t curve reached 35 pM. The lignin film and well packed Fe3O4/AuNPs facilitated the pre-concentration of trace TNT on the electrode surface resulting in a fast amperometric response of 3 seconds near the detection limit. The high sensitivity and excellent catalytic activity of the modified electrode could be attributed to the lignin layer and highly packed Fe3O4/AuNPs on the electrode surface. The total recovery of TNT from tapwater and seawater matrices was 98% and 96%, respectively. The electrode film was highly stable after five repeated adsorption/desorption cycles. The new electrochemical sensing scheme provides a highly selective, sensitive and versatile assay for the in-situ detection of TNT in complex water media.

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.

Assessing the impact of mineralogy on our ability to detect organic salts in Gale Crater, Mars, through thermal analyses.

NASA Astrophysics Data System (ADS)

Lewis, J. M. T.; Eigenbrode, J. L.; Franz, H. B.; Sutter, B.; Niles, P. B.; McAdam, A.

2016-12-01

Organic matter present in martian sediments analyzed by the Sample Analysis at Mars (SAM) instrument suite on the Curiosity rover and in martian meteorites suggests that there may be a widespread presence of organic molecules on the surface of Mars. This organic pool may be derived from exogenous sources such as interplanetary dust particles and from indigenous processes such as volcanism, serpentinization and life, if it has ever existed on Mars. Direct detection of an ancient organic geochemical record in martian materials is challenged by two issues. First, alteration at the surface can compromise organic matter preservation. It is expected that unprotected organic compounds undergo partial oxidative diagenesis, spurred by ionizing radiation and oxidants, to metastable organic salts (e.g., iron acetate, calcium oxalate, and sodium phthalate). Such organic salts are not directly detectable by pyrolysis, producing only CO2 and CO during heating. Second, exposed organic compounds in the SAM oven, i.e., those available for reaction, are susceptible to oxidation and chlorination by perchlorates, which are thought to be ubiquitous on Mars. In order to assess whether CO2 and CO may be derived from organic salts, as opposed to combustion of other organics or mineral decomposition, a comprehensive understanding of how sample mineralogy influences their decomposition profiles is required. Simplified mineral matrices, consistent with those detected by Curiosity's Chemistry and Mineralogy instrument or inferred from SAM instrument analyses, were prepared and mixed with standards of several organic salts expected to be present on Mars. The mixtures were then analyzed under SAM-like analytical conditions. Results address the influence of iron and sulfur mineralogies and perchlorate salts on the decomposition of metastable organic salts. The results are related to the interpretation of the sub-400 °C CO2 and CO observed by SAM that may be derived from these organic salts.

Effect of Fluoride on the Morphology and Electrochemical Property of Co3O4 Nanostructures for Hydrazine Detection

PubMed Central

Gao, Wanlin; Wang, Qiang; Umar, Ahmad

2018-01-01

In this paper, we systematically investigated the influence of fluoride on the morphology and electrochemical property of Co3O4 nanostructures for hydrazine detection. The results showed that with the introduction of NH4F during the synthesis process of Co3O4, both Co(CO3)0.5(OH)·0.11H2O and Co(OH)F precursors would be generated. To understand the influence of F on the morphology and electrochemical property of Co3O4, three Co3O4 nanostructures that were respectively obtained from bare Co(CO3)0.5(OH)·0.11H2O, Co(OH)F and Co(CO3)0.5(OH)·0.11H2O mixtures and bare Co(OH)F were successfully synthesized. The electrochemical tests revealed the sensing performance of prepared Co3O4 nanostructures decreased with the increase in the fluoride contents of precursors. The more that dosages of NH4F were used, the higher crystallinity and smaller specific surface area of Co3O4 was gained. Among these three Co3O4 nanostructures, the Co3O4 that was obtained from bare Co(CO3)0.5(OH)·0.11H2O-based hydrazine sensor displayed the best performances, which exhibited a great sensitivity (32.42 μA·mM−1), a low detection limit (9.7 μΜ), and a wide linear range (0.010–2.380 mM), together with good selectivity, great reproducibility and longtime stability. To the best of our knowledge, it was revealed for the first time that the sensing performance of prepared Co3O4 nanostructures decreased with the increase in fluoride contents of precursors. PMID:29382161

Laboratory Spectra of CO2 Vibrational Modes in Planetary Ice Analogs

NASA Technical Reports Server (NTRS)

White, Douglas; Mastrapa, Rachel M.; Sandford, Scott

2012-01-01

Laboratory spectra have shown that CO2 is a powerful diagnostic tool for analyzing infrared data from remote observations, as it has been detected on icy moons in the outer Solar System as well as dust grain surfaces in the interstellar medium (ISM). IR absorption band profiles of CO2 within ice mixtures containing H2O and CH3OH change with respect to temperature and mixture ratios. In this particular study, the CO2 asymmetric stretching mode near 4.3 m (2350 cm (exp-1)), overtone mode near 1.97 m (5080 cm (exp-1)), and the combination bands near 2.7 m (3700 cm (exp-1)), 2.8 m (3600 cm (exp-1)), and 2.02 m (4960 cm (exp -1)), are systematically observed in different mixtures with H2O and CH3OH in temperature ranges from 15K to 150 K. Additionally, some high-temperature deposits (T greater than 50 K) of H2O, CH3OH, and CO2 ice mixtures were performed. These data may then be used to interpret infrared observational data obtained from icy surfaces in the outer Solar System and beyond.

Detection of Atmospheric CO on Pluto with ALMA

NASA Astrophysics Data System (ADS)

Gurwell, Mark; Lellouch, Emmanuel; Butler, Bryan; Moullet, Arielle; Moreno, Raphael; Bockelée-Morvan, Dominique; Biver, Nicolas; Fouchet, Thierry; Lis, Darek; Stern, Alan; Young, Leslie; Young, Eliot; Weaver, Hal; Boissier, Jeremie; Stansberry, John

2015-11-01

We observed Pluto and Charon using the Atacama Large Millimeter/submillimeter Array (ALMA) interferometer in Northern Chile on June 12.2 and June 13.15, 2015, just one month prior to the New Horizons flyby of the system. The configuration of ALMA at the time provided ~0.3" resolution, allowing separation of emission from Pluto and Charon. This project targeted multiple science goals, including a search for HCN in Pluto's atmosphere [1] and high precision measurements of the individual brightness temperatures of Pluto and Charon [2], also presented at this meeting. Here we report the high SNR detection of carbon monoxide in the atmosphere of Pluto. The CO(3-2) rotational line, at 345.796 GHz (867 μm), was observed with 117 kHz spectral resolution for 45 min (on-source) on each date, providing ~3.5mJy/channel RMS. CO emission was clearly detected on both days, with a contrast of ~65 mJy above the Pluto continuum, and ~1.8 MHz FWHM linewidth, with the combined integrated line SNR >50. The presence of CO in Pluto's atmosphere is expected due to it's presence as ice on the surface in vapor pressure equilibrium with the atmosphere (e.g. [3],[4]), and it was previously detected at modest SNR in the near-IR using the VLT [5]. A preliminary assessment based upon the CO line wings shows the fractional abundance of CO is 500-750 ppm, consistent with that found in [5]. Further, the shape of the line core emission (assuming a constant CO mixing ratio), suggests that the atmospheric temperature rises quickly from the surface to ~100-110 K in the altitude range 20-70 km but decreases above that, falling to about 70 K by 200 km altitude. A detailed line inversion analysis will be performed and results presented.[1] Lellouch et al, this meeting. [2] Butler et al., this meeting. [3] Owen et al (1993), Science, 261, pp. 745-748. [4] Spencer et al (1993), In Pluto and Charon, pp. 435-473. Univ. of Arizona Press, Tucson. [5] Lellouch et al (2011), A&A, 530, L4.

Between ice and gas: CO2 on the icy satellites of Jupiter and Saturn

NASA Astrophysics Data System (ADS)

Hibbitts, C.

2010-12-01

CO2 exists in the surfaces of the icy Galilean and Saturnian satellites [1-6], yet despite its discovery over a decade ago on Ganymede, and five years ago on the Saturnian satellites, its nature is still debated [7]. On the Galilean satellites Callisto and Ganymede, the CO2 that is detected is bound to, or trapped within, the non-ice materials that prevent it from sublimating or otherwise escaping from the surface. On Europa, it resides within both the ice and nonice materials [8,9]. While greater abundances of CO2 may exist in the interiors of these moons, or small amounts may be continually created through particle bombardment of the surface, the observed CO2 is only a trace material, with a few hundred molecules responsible for the deepest absorption features and an estimated molar abundance of 0.1% [2; 10-12]. Yet its presence may provide essential clues to processes that shape the surfaces of the moon [13] and potentially key to understanding the composition of potential oceans in the subsurfaces. We continue measurements of the infrared properties associated with CO2 adsorbed onto nonice materials under pressures and at temperatures relevant to these icy satellites using bidirectional reflectance spectroscopy from ~ 1.5 to 5.5 μm. Previous measurements, using transmission spectroscopy, demonstrated both a compositional and a temperature dependence on the spectral signature of adsorbed CO2 [14]. Bidirectional spectroscopy enables detection of lower concentrations of adsorbate on fine-grained materials such as clays due to their large surface area to volume ratios and thus large surface areas that may be covered by adsorbate [15]. The effectiveness of transmission spectroscopy was also limited by the strong absorption of light within the pressed sample and its impermeability, which limited the coverage by adsorbate to the pellet’s outer surface. All measurements demonstrate that CO2 adsorbs onto montmorillonite clays, possibly due to its quadrupole moment, with the position of its ν3 fundament absorption band dependent on the cation composition and on the dosing temperature. It may also be that the presence of charge-compensating ions, and the resulting negative charge of the remaining structure, enables CO2 to adsorb through an induced dipole attraction. In general, the IR absorption band of CO2 in montmorillonite tends to shift toward longer wavelengths as the density of the electric field of the principle cation decreases, with the exception that the IR absorption band of the Na-rich endmember occurs at a shorter wavelength than for the Li-rich endmember. References: [1] Carlson et al., (1996) Science; [2] McCord et al., (1998) J. Geophys. Res.; [3] Buratti et al., (2005) Astrophys. J.; [4]Clark et al., (2005) Nature; [5] Brown et al., (2006) , Icarus; [6] Filacchione et al., (2006) , Icarus; [7] Cruikshank et al., (2010), Icarus, 206, 561-572; [9] Smythe et al., (1998),DPS,30, #55.P07, 1448; [9] Hansen and McCord, (2008), GRL, 35; [10] Hibbitts et al., (2000) J. Geophys. Res.; [11] Hibbitts et al., (2002) , J. Geophys. Res.; [12] Hibbitts et al., (2003) J. Geophys. Res.; [13] Moore et al., (2000), Icarus, 140, 294-312; [14] Hibbitts and Szanyi, (2007), Icarus. 191, 371-380; [15] Dyar et al., (2010), Icarus, 208, 425-437.

Simulation Studies for a Space-Based CO2 Lidar Mission

NASA Technical Reports Server (NTRS)

Kawa, S. R.; Mao, J.; Abshire, J. B.; Collatz, G. J.; Sun, X.; Weaver, C. J.

2010-01-01

We report results of initial space mission simulation studies for a laser-based, atmospheric CO2 sounder, which are based on real-time carbon cycle process modelling and data analysis. The mission concept corresponds to the Active Sensing of CO2 Emissions over Nights, Days and Seasons (ASCENDS) recommended by the US National Academy of Sciences' Decadal Survey. As a pre-requisite for meaningful quantitative evaluation, we employ a CO2 model that has representative spatial and temporal gradients across a wide range of scales. In addition, a relatively complete description of the atmospheric and surface state is obtained from meteorological data assimilation and satellite measurements. We use radiative transfer calculations, an instrument model with representative errors and a simple retrieval approach to quantify errors in 'measured' CO2 distributions, which are a function of mission and instrument design specifications along with the atmospheric/surface state. Uncertainty estimates based on the current instrument design point indicate that a CO2 laser sounder can provide data consistent with ASCENDS requirements and will significantly enhance our ability to address carbon cycle science questions. Test of a dawn/dusk orbit deployment, however, shows that diurnal differences in CO2 column abundance, indicative of plant photosynthesis and respiration fluxes, will be difficult to detect

Interstellar Antifreeze: Ethylene Glycol

NASA Technical Reports Server (NTRS)

Hollis, J. M.; Lovas, F. J.; Jewell, P. R.; Coudert, L. H.

2002-01-01

Interstellar ethylene glycol (HOCH2CH2,OH) has been detected in emission toward the Galactic center source Sagittarius B2(N-LMH) by means of several millimeter-wave rotational torsional transitions of its lowest energy conformer. The types and kinds of molecules found to date in interstellar clouds suggest a chemistry that favors aldehydes and their corresponding reduced alcohols-e.g., formaldehyde (H2CO)/methanol (CH3OH), acetaldehyde (CH3CHO)/ethanol (CH3CH2OH). Similarly, ethylene glycol is the reduced alcohol of glycolaldehyde (CH2OHCHO), which has also been detected toward Sgr B2(N-LMH). While there is no consensus as to how any such large complex molecules are formed in the interstellar clouds, atomic hydrogen (H) and carbon monoxide (CO) could form formaldehyde on grain surfaces, but such surface chemistry beyond that point is uncertain. However, laboratory experiments have shown that the gas-phase reaction of atomic hydrogen (H) and solid-phase CO at 10-20 K can produce formaldehyde and methanol and that alcohols and other complex molecules can be synthesized from cometary ice analogs when subject to ionizing radiation at 15 K. Thus, the presence of aldehyde/ reduced alcohol pairs in interstellar clouds implies that such molecules are a product of a low-temperature chemistry on grain surfaces or in grain ice mantles. This work suggests that aldehydes and their corresponding reduced alcohols provide unique observational constraints on the formation of complex interstellar molecules.

Label-Free LSPR Detection of Trace Lead(II) Ions in Drinking Water by Synthetic Poly(mPD-co-ASA) Nanoparticles on Gold Nanoislands.

PubMed

Qiu, Guangyu; Ng, Siu Pang; Liang, Xiongyi; Ding, Ning; Chen, Xiangfeng; Wu, Chi-Man Lawrence

2017-02-07

Using self-assembly gold nanoislands (SAM-AuNIs) functionalized by poly(m-phenylenediamine-co-aniline-2-sulfonic acid) (poly(mPD-co-ASA)) copolymer nanoparticles as specific receptors, a highly sensitive localized surface plasmon resonance (LSPR) optochemical sensor is demonstrated for detection of trace lead cation (Pb(II)) in drinking water. The copolymer receptor is optimized in three aspects: (1) mole ratio of mPD:ASA monomers, (2) size of copolymer nanoparticles, and (3) surface density of the copolymer. It is shown that the 95:5 (mPD:ASA mole ratio) copolymer with size less than 100 nm exhibits the best Pb(II)-sensing performance, and the 200 times diluted standard copolymer solution contributes to the most effective functionalization protocol. The resulting poly(mPD-co-ASA)-functionalized LSPR sensor attains the detection limit to 0.011 ppb toward Pb(II) in drinking water, and the linear dynamic range covers 0.011 to 5000 ppb (i.e., 6 orders of magnitude). In addition, the sensing system exhibits robust selectivity to Pb(II) in the presence of other metallic cations as well as common anions. The proposed functional copolymer functionalized on AuNIs is found to provide excellent Pb(II)-sensing performance using simple LSPR instrumentation for rapid drinking-water inspection.

Geochemical Analyses of Surface and Shallow Gas Flux and Composition Over a Proposed Carbon Sequestration Site in Eastern Kentucky

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

Thomas Parris; Michael Solis; Kathryn Takacs

2009-12-31

Using soil gas chemistry to detect leakage from underground reservoirs (i.e. microseepage) requires that the natural range of soil gas flux and chemistry be fully characterized. To meet this need, soil gas flux (CO{sub 2}, CH{sub 4}) and the bulk (CO{sub 2}, CH{sub 4}) and isotopic chemistry ({delta}{sup 13}C-CO2) of shallow soil gases (<1 m, 3.3 ft) were measured at 25 locations distributed among two active oil and gas fields, an active strip mine, and a relatively undisturbed research forest in eastern Kentucky. The measurements apportion the biologic, atmospheric, and geologic influences on soil gas composition under varying degrees ofmore » human surface disturbance. The measurements also highlight potential challenges in using soil gas chemistry as a monitoring tool where the surface cover consists of reclaimed mine land or is underlain by shallow coals. For example, enrichment of ({delta}{sup 13}C-CO2) and high CH{sub 4} concentrations in soils have been historically used as indicators of microseepage, but in the reclaimed mine lands similar soil chemistry characteristics likely result from dissolution of carbonate cement in siliciclastic clasts having {delta}{sup 13}C values close to 0{per_thousand} and degassing of coal fragments. The gases accumulate in the reclaimed mine land soils because intense compaction reduces soil permeability, thereby impeding equilibration with the atmosphere. Consequently, the reclaimed mine lands provide a false microseepage anomaly. Further potential challenges arise from low permeability zones associated with compacted soils in reclaimed mine lands and shallow coals in undisturbed areas that might impede upward gas migration. To investigate the effect of these materials on gas migration and composition, four 10 m (33 ft) deep monitoring wells were drilled in reclaimed mine material and in undisturbed soils with and without coals. The wells, configured with sampling zones at discrete intervals, show the persistence of some of the aforementioned anomalies at depth. Moreover, high CO{sub 2} concentrations associated with coals in the vadose zone suggest a strong affinity for adsorbing CO{sub 2}. Overall, the low permeability of reclaimed mine lands and coals and CO2 adsorption by the latter is likely to reduce the ability of surface geochemistry tools to detect a microseepage signal.« less

The study of 'microsurfaces' using thermal desorption spectroscopy

NASA Technical Reports Server (NTRS)

Thomas, M. E.; Poppa, H.; Pound, G. M.

1979-01-01

The use of a newly combined ultrahigh vacuum technique for studying continuous and particulate evaporated thin films using thermal desorption spectroscopy (TDS), transmission electron microscopy (TEM), and transmission electron diffraction (TED) is discussed. It is shown that (1) CO thermal desorption energies of epitaxially deposited (111) Ni and (111) Pd surfaces agree perfectly with previously published data on bulk (111) single crystal, (2) contamination and surface structural differences can be detected using TDS as a surface probe and TEM as a complementary technique, and (3) CO desorption signals from deposited metal coverages of one-thousandth of a monolayer should be detectable. These results indicate that the chemisorption properties of supported 'microsurfaces' of metals can now be investigated with very high sensitivity. The combined use of TDS and TEM-TED experimental methods is a very powerful technique for fundamental studies in basic thin film physics and in catalysis.

Valence-state reflectometry of complex oxide heterointerfaces

DOE PAGES

Hamann-Borrero, Jorge E.; Macke, Sebastian; Choi, Woo Seok; ...

2016-09-16

Emergent phenomena in transition-metal-oxide heterostructures such as interface superconductivity and magnetism have been attributed to electronic reconstruction, which, however, is difficult to detect and characterise. Here we overcome the associated difficulties to simultaneously address the electronic degrees of freedom and distinguish interface from bulk effects by implementing a novel approach to resonant X-ray reflectivity (RXR). Our RXR study of the chemical and valance profiles along the polar (001) direction of a LaCoO 3 film on NdGaO 3 reveals a pronounced valence-state reconstruction from Co 3+ in the bulk to Co 2+ at the surface, with an areal density close tomore » 0.5 Co 2+ ions per unit cell. An identical film capped with polar (001) LaAlO 3 maintains the Co 3+ valence over its entire thickness. As a result, we interpret this as evidence for electronic reconstruction in the uncapped film, involving the transfer of 0.5e – per unit cell to the subsurface CoO 2 layer at its LaO-terminated polar surface.« less

Improved detection of highly energetic materials traces on surfaces by standoff laser-induced thermal emission incorporating neural networks

NASA Astrophysics Data System (ADS)

Figueroa-Navedo, Amanda; Galán-Freyle, Nataly Y.; Pacheco-Londoño, Leonardo C.; Hernández-Rivera, Samuel P.

2013-05-01

Terrorists conceal highly energetic materials (HEM) as Improvised Explosive Devices (IED) in various types of materials such as PVC, wood, Teflon, aluminum, acrylic, carton and rubber to disguise them from detection equipment used by military and security agency personnel. Infrared emissions (IREs) of substrates, with and without HEM, were measured to generate models for detection and discrimination. Multivariable analysis techniques such as principal component analysis (PCA), soft independent modeling by class analogy (SIMCA), partial least squares-discriminant analysis (PLS-DA), support vector machine (SVM) and neural networks (NN) were employed to generate models, in which the emission of IR light from heated samples was stimulated using a CO2 laser giving rise to laser induced thermal emission (LITE) of HEMs. Traces of a specific target threat chemical explosive: PETN in surface concentrations of 10 to 300 ug/cm2 were studied on the surfaces mentioned. Custom built experimental setup used a CO2 laser as a heating source positioned with a telescope, where a minimal loss in reflective optics was reported, for the Mid-IR at a distance of 4 m and 32 scans at 10 s. SVM-DA resulted in the best statistical technique for a discrimination performance of 97%. PLS-DA accurately predicted over 94% and NN 88%.

Application of open-path Fourier transform infrared spectroscopy for atmospheric monitoring of a CO2 back-production experiment at the Ketzin pilot site (Germany).

PubMed

Sauer, Uta; Borsdorf, H; Dietrich, P; Liebscher, A; Möller, I; Martens, S; Möller, F; Schlömer, S; Schütze, C

2018-02-03

During a controlled "back-production experiment" in October 2014 at the Ketzin pilot site, formerly injected CO 2 was retrieved from the storage formation and directly released to the atmosphere via a vent-off stack. Open-path Fourier transform infrared (OP FTIR) spectrometers, on-site meteorological parameter acquisition systems, and distributed CO 2 point sensors monitored gas dispersion processes in the near-surface part of the atmospheric boundary layer. The test site provides a complex and challenging mosaic-like surface setting for atmospheric monitoring which can also be found at other storage sites. The main aims of the atmospheric monitoring of this experiment were (1) to quantify temporal and spatial variations in atmospheric CO 2 concentrations around the emitting vent-off stack and (2) to test if and how atmospheric monitoring can cope with typical environmental and operational challenges. A low environmental risk was encountered during the whole CO 2 back-production experiment. The study confirms that turbulent wind conditions favor atmospheric mixing processes and are responsible for rapid dilution of the released CO 2 leading to decreased detectability at all sensors. In contrast, calm and extremely stable wind conditions (especially occurring during the night) caused an accumulation of gases in the near-ground atmospheric layer with the highest amplitudes in measured gas concentration. As an important benefit of OP FTIR spectroscopic measurements and their ability to detect multiple gas species simultaneously, emission sources could be identified to a much higher certainty. Moreover, even simulation models using simplified assumptions help to find suitable monitoring network designs and support data analysis for certain wind conditions in such a complex environment.

The Value of Information: Assessing the Ability of Electrical Resistivity to Detect CO2 Leakage in a Shallow Aquifer

NASA Astrophysics Data System (ADS)

Trainor Guitton, W. J.; Yang, X.; Mansoor, K.; Ramirez, A. L.; Sun, Y.; Carroll, S.

2012-12-01

This study demonstrates a methodology for evaluating the value of electrical resistivity data to detect CO2 leakage in a shallow groundwater aquifer. This methodology adopts the value of information (VOI) metric from the field of decision analysis. We consider a stakeholder's decision of whether or not to remediate the aquifer, given that they are uncertain whether or not a CO2 leak has occurred from a deep storage source through a well-bore into the shallow aquifer and what the impact of that leak would be. Two themes of uncertainty are needed for VOI studies. The first is related to the uncertain state of the subsurface, which is directly related to the outcome of the decision. In our example, it is uncertain whether or not the shallow groundwater has been impacted by CO2 leakage. The impact may be determined by the existence of depressed pH or elevated TDS (total dissolved solids) plume. We utilize results from a previous work that investigated uncertainty quantification of spatial heterogeneity and leakage rates (Mansoor et al, 2011). Therefore, we have a comprehensive suite of 713 simulations that represent our uncertainty regarding the existence and extent of a CO2 plume. Given certain TDS and pH thresholds, the simulations are categorized into two groups: impacted (a plume exists) or not impacted (no plume) at time=50 years. The second theme is related to the information's accuracy to inform us about the existence of a plume (e.g. the state of the subsurface directly relevant to the decision). The uncertainty of the information is measured by the data likelihood and is used to determine the value of imperfect information. For this demonstration, we consider how electrical resistivity data can detect the existence of pH plumes (due to the dissolution of CO2) and TDS (due to the accompanying brine leakage). The pH and TDS output from the 713 simulations are used to determine the electrical resistivity at time = 0 and time=50 years. An empirical method is used to compare the time=0 and time=50 resistivities: the geometric log mean ratio (GLMR) of the 2 data sets is calculated (Daily et al, 2004). This requires only the forward response be calculated at the 2 different times. The GLMR is used as a sensitivity measure, representing how much the electrical resistivity would change given the conditions of the aquifer. The likelihood of electrical resistivity to detect the presence of a plume is estimated by comparing the GLMR and the category (plume or no plume) for all the 713 simulations. Electrical resistivity forward models were calculated for two acquisition configurations: surface electrodes only and surface-to-borehole. For the surface acquisition, a GLMR >0.05 exclusively identifies impacted simulations. Whereas GLMR <0.05 give a more ambiguous message: both simulations that are impacted and not have GMLR<0.05. The degree of this ambiguity changes with different definitions of the plume (i.e. pH and TDS thresholds). Surface-to-borehole forward models were performed for a borehole located 200m from the leaky well. Results show that surface-to-borehole resistivity data is more reliable at distinguishing between impacted and non-impacted simulations, and therefore the VOI is higher than for surface electrodes alone. Prepared by LLNL under Contract No. DE-AC52-07NA27344.

In situ XPS study of methanol reforming on PdGa near-surface intermetallic phases

PubMed Central

Rameshan, Christoph; Stadlmayr, Werner; Penner, Simon; Lorenz, Harald; Mayr, Lukas; Hävecker, Michael; Blume, Raoul; Rocha, Tulio; Teschner, Detre; Knop-Gericke, Axel; Schlögl, Robert; Zemlyanov, Dmitry; Memmel, Norbert; Klötzer, Bernhard

2012-01-01

In situ X-ray photoelectron spectroscopy and low-energy ion scattering were used to study the preparation, (thermo)chemical and catalytic properties of 1:1 PdGa intermetallic near-surface phases. Deposition of several multilayers of Ga metal and subsequent annealing to 503–523 K led to the formation of a multi-layered 1:1 PdGa near-surface state without desorption of excess Ga to the gas phase. In general, the composition of the PdGa model system is much more variable than that of its PdZn counterpart, which results in gradual changes of the near-surface composition with increasing annealing or reaction temperature. In contrast to near-surface PdZn, in methanol steam reforming, no temperature region with pronounced CO2 selectivity was observed, which is due to the inability of purely intermetallic PdGa to efficiently activate water. This allows to pinpoint the water-activating role of the intermetallic/support interface and/or of the oxide support in the related supported PdxGa/Ga2O3 systems, which exhibit high CO2 selectivity in a broad temperature range. In contrast, corresponding experiments starting on the purely bimetallic model surface in oxidative methanol reforming yielded high CO2 selectivity already at low temperatures (∼460 K), which is due to efficient O2 activation on PdGa. In situ detected partial and reversible oxidative Ga segregation on intermetallic PdGa is associated with total oxidation of intermediate C1 oxygenates to CO2. PMID:22875996

A multi-decade record of high-quality fCO2 data in version 3 of the Surface Ocean CO2 Atlas (SOCAT)

USGS Publications Warehouse

Bakker, Dorothee; Landa, Camilla S.; Pfeil, Benjamin; Metzl, Nicolas; O’Brien, Kevin; Olsen, Are; Smith, Karl; Cosca, Cathy; Harasawa, Sumiko; Nakaoka, Shin-ichiro; Jones, Stephen; Nojiri, Yukihiro; Steinhoff, Tobias; Sweeney, Colm; Schuster, Ute; Takahashi, Taro; Tilbrook, Bronte; Wada, Chisato; Wanninkhof, Rik; Alin, Simone R.; Balestrini, Carlos F.; Barbero, Leticia; Bates, Nicholas; Bianchi, Alejandro A.; Bonou, Frédéric; Boutin, Jacqueline; Bozec, Yann; Burger, Eugene F.; Cai, Wei-Jun; Castle, Robert D.; Chen, Liqi; Chierici, Melissa; Currie, Kim; Evans, Wiley; Featherstone, Charles; Feely, Richard; Fransson, Agneta; Goyet, Catherine; Greenwood, Naomi; Gregor, Luke; Hankin, Steven C.; Hardman-Mountford, Nick J.; Harlay, Jérôme; Hauck, Judith; Hoppema, Mario; Humphreys, Matthew P.; Hunt, Christopher W.; Huss, Betty; Ibánhez, J. Severino P.; Johannessen, Truls; Keeling, Ralph F.; Kitidis, Vassilis; Körtzinger, Arne; Kozyr, Alex; Krasakopoulou, Evangelia; Kuwata, Akira; Landschützer, Peter; Lauvset, Siv K.; Lefèvre, Nathalie; Lo Monaco, Claire; Manke, Ansley; Mathis, Jeremy T.; Merlivat, Liliane; Millero, Frank J.; Monteiro, Pedro M. S.; Munro, David R.; Murata, Akihiko; Newberger, Timothy; Omar, Abdirahman M.; Ono, Tsuneo; Paterson, Kristina; Pearce, David; Pierrot, Denis; Robbins, Lisa L.; Saito, Shu; Salisbury, Joe; Schlitzer, Reiner; Schneider, Bernd; Schweitzer, Roland; Sieger, Rainer; Skjelvan, Ingunn; Sullivan, Kevin F.; Sutherland, Stewart C.; Sutton, Adrienne J.; Tadokoro, Kazuaki; Telszewski, Maciej; Tuma, Matthias; van Heuven, Steven M. A. C.; Vandemark, Douglas; Ward, Brian; Watson, Andrew J.; Xu, Suqing

2016-01-01

The Surface Ocean CO2 Atlas (SOCAT) is a synthesis of quality-controlled f CO2 (fugacity of carbon dioxide) values for the global surface oceans and coastal seas with regular updates. Version 3 of SOCAT has 14.7 million f CO2 values from 3646 data sets covering the years 1957 to 2014. This latest version has an additional 4.6 million f CO2 values relative to version 2 and extends the record from 2011 to 2014. Version 3 also significantly increases the data availability for 2005 to 2013. SOCAT has an average of approximately 1.2 million surface water f CO2 values per year for the years 2006 to 2012. Quality and documentation of the data has improved. A new feature is the data set quality control (QC) flag of E for data from alternative sensors and platforms. The accuracy of surface water f CO2 has been defined for all data set QC flags. Automated range checking has been carried out for all data sets during their upload into SOCAT. The upgrade of the interactive Data Set Viewer (previously known as the Cruise Data Viewer) allows better interrogation of the SOCAT data collection and rapid creation of high-quality figures for scientific presentations. Automated data upload has been launched for version 4 and will enable more frequent SOCAT releases in the future. High-profile scientific applications of SOCAT include quantification of the ocean sink for atmospheric carbon dioxide and its long-term variation, detection of ocean acidification, as well as evaluation of coupled-climate and ocean-only biogeochemical models. Users of SOCAT data products are urged to acknowledge the contribution of data providers, as stated in the SOCAT Fair Data Use Statement. This ESSD (Earth System Science Data) “living data” publication documents the methods and data sets used for the assembly of this new version of the SOCAT data collection and compares these with those used for earlier versions of the data collection (Pfeil et al., 2013; Sabine et al., 2013; Bakker et al., 2014). 

Visual detection of cyanide ions by membrane-based nanozyme assay.

PubMed

Lien, Chia-Wen; Unnikrishnan, Binesh; Harroun, Scott G; Wang, Chih-Min; Chang, Jia-Yaw; Chang, Huan-Tsung; Huang, Chih-Ching

2018-04-15

In this paper, we report a simple one-step synthesis of well-dispersed amorphous cobalt hydroxide/oxide-modified graphene oxide (CoO x H-GO) possessing peroxidase-like catalytic activity, and its application for the detection of H 2 O 2 , glucose, and CN - ions. CoO x H is formed and deposited in situ on the GO surface through the reaction between GO (size ~ 240nm) and Co 2+ in basic solution at room temperature. We investigated the enzyme-mimicking activity of the CoO x H-GO nanohybrid in detail via the H 2 O 2 -mediated oxidation of Amplex Red (AR) to form fluorescent resorufin. The peroxidase-like activity of CoO x H-GO is utilized herein for the quantitation of H 2 O 2 in a wide concentration range, from 100nM to 100μM. When coupled with glucose oxidase (GOD), the AR/CoO x H-GO system can determine glucose level in blood samples. Interestingly, cyanide ions (CN - ) significantly inhibit the catalytic activity of the CoO x H-GO nanohybrid, which allows for the construction of a probe for the detection of CN - in water samples and laboratory wastes. We fabricated a membrane-based CoO x H-GO probe for the visual detection of CN - by preparing a thin film of CoO x H-GO on a positively charged and porous nylon membrane (N + M). The CoO x H-GO/N + M operates on the principle that CN - inhibits the catalytic activity of CoO x H-GO towards the H 2 O 2 -mediated oxidation of AR to form reddish resorufin on the membrane. The intensity of the red color of the membrane decreases with increasing CN - concentration, which can be easily observed with the naked eye at the nanomolar level. This cost-effective sensing system allows for the rapid and simple determination of the concentrations of CN - in complicated wastewater samples. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Cobalt oxide nanosheets wrapped onto nickel foam for non-enzymatic detection of glucose

NASA Astrophysics Data System (ADS)

Meng, Shangjun; Wu, Meiyan; Wang, Qian; Dai, Ziyang; Si, Weili; Huang, Wei; Dong, Xiaochen

2016-08-01

Ultra-sensitive and highly selective detection of glucose is essential for the clinical diagnosis of diabetes. In this paper, an ultra-sensitive glucose sensor was successfully fabricated based on cobalt oxide (Co3O4) nanosheets directly grown on nickel foam through a simple hydrothermal method. Characterizations indicated that the Co3O4 nanosheets are completely and uniformly wrapped onto the surface of nickel foam to form a three-dimensional heterostructure. The resulting self-standing electrochemical electrode presents a high performance for the non-enzymatic detection of glucose, including short response time (<10 s), ultra-sensitivity (12.97 mA mM-1 cm-2), excellent selectivity and low detection limit (0.058 μM, S/N = 3). These results indicate that Co3O4 nanosheets wrapped onto nickel foam are a low-cost, practical, and high performance electrochemical electrode for bio sensing.

Laboratory investigations: Low Earth orbit environment chemistry with spacecraft surfaces

NASA Technical Reports Server (NTRS)

Cross, Jon B.

1990-01-01

Long-term space operations that require exposure of material to the low earth orbit (LEO) environment must take into account the effects of this highly oxidative atmosphere on material properties and the possible contamination of the spacecraft surroundings. Ground-based laboratory experiments at Los Alamos using a newly developed hyperthermal atomic oxygen (AO) source have shown that not only are hydrocarbon based materials effected but that inorganic materials such as MoS2 are also oxidized and that thin protective coatings such as Al2O3 can be breached, producing oxidation of the underlying substrate material. Gas-phase reaction products, such as SO2 from oxidation of MoS2 and CO and CO2 from hydrocarbon materials, have been detected and have consequences in terms of spacecraft contamination. Energy loss through gas-surface collisions causing spacecraft drag has been measured for a few select surfaces and has been found to be highly dependent on the surface reactivity.

The Nickel(111)/Alkaline Electrolyte Interface

NASA Technical Reports Server (NTRS)

Wang, Kuilong; Chottiner, G. S.; Scherson, D. A.; Reid, Margaret A.

1991-01-01

The electrochemical properties of Ni (111) prepared and characterized in ultra high vacuum, UHV, by surface analytical techniques have been examined in alkaline media by cyclic voltammetry using an UHV-electrochemical cell transfer system designed and built in this laboratory. Prior to the transfer, the Ni(111) surfaces were exposed to saturation coverages of CO in UHV in an attempt to protect the surface from possible contamination with other gases during the transfer. Temperature Programmed Desorption, TPD, of CO-dosed Ni (111) surfaces displaying sharp c(4x2), LEED patterns, subsequently exposed to water-saturated Ar at atmospheric pressure in an auxiliary UHV compatible chamber and finally transferred back to the main UHV chamber, yielded CO2 and water as the only detectable products. This indicates that the CO-dosed surfaces react with water and/or bicarbonate and hydroxide as the most likely products. Based on the integration of the TPD peaks, the combined amounts of H2O and CO2 were found to be on the order of a single monolayer. The reacted c(4x2)CO/Ni(111) layer seems to protect the surface from undergoing spontaneous oxidation in strongly alkaline solutions. This was evidenced by the fact that the open circuit potential observed immediately after contact with deaerated 0.1 M KOH was about 0.38 V vs. DHE, drifting slightly towards more negative values prior to initiating the voltametric scans. The average ratio of the integrated charge obtained in the first positive linear scan in the range of 0.35 to 1.5 V vs. DHE (initiated at the open circuit potential) and the first (and subsequent) linear negative scans in the same solution yielded for various independent runs a value of 3.5 +/- 0.3. Coulometric analysis of the cyclic voltammetry curves indicate that the electrochemically formed oxyhydroxide layer involves a charge equivalent to 3.2 +/- 0.4 layers of Ni metal.

Seasonal reversal of temperature-moisture response of net carbon exchange of biocrusted soils in a cool desert ecosystem.

NASA Astrophysics Data System (ADS)

Tucker, C.; Reed, S.; Howell, A.

2017-12-01

Carbon cycling associated with biological soil crusts, which occur in interspaces between vascular plants in drylands globally, may be an important part of the coupled climate-carbon cycle of the Earth system. A major challenge to understanding CO2 fluxes in these systems is that much of the biotic and biogeochemical activity occurs in the upper few mm of the soil surface layer (i.e., the `mantle of fertility'), which exhibits highly dynamic and difficult to measure temperature and moisture fluctuations. Here, we report data collected in a cool desert ecosystem over one year using a multi-sensor approach to simultaneously measuring temperature and moisture of the biocrust surface layer (0-2 mm), and the deeper soil profile (5-20 cm), concurrent with automated measurement of surface soil CO2 effluxes. Our results illuminate robust relationships between microclimate and field CO2 pulses that have previously been difficult to detect and explain. The temperature of the biocrust surface layer was highly variable, ranging from minimum of -9 °C in winter to maximum of 77 °C in summer with a maximum diurnal range of 61 °C. Temperature cycles were muted deeper in the soil profile. During summer, biocrust and soils were usually hot and dry and CO2 fluxes were tightly coupled to pulse wetting events experienced at the biocrust surface, which consistently resulted in net CO2 efflux (i.e., respiration). In contrast, during the winter, biocrust and soils were usually cold and moist, and there was sustained net CO2 uptake via photosynthesis by biocrust organisms, although during cold dry periods CO2 fluxes were minimal. During the milder spring and fall seasons, short wetting events drove CO2 loss, while sustained wetting events resulted in net CO2 uptake. Thus, the upper and lower bounds of net CO2 exchange at a point in time were functions of the seasonal temperature regime, while the actual flux within those bounds was determined by the magnitude and duration of biocrust and soil wetting events. These patterns reflect both the low temperature sensitivity and slow initiation in response to wetting of photosynthesis compared to respiration by biocrust organisms. Our study highlights the importance of cool and cold periods for C uptake in biocrusted soils of the Colorado Plateau.

Low-cost and disposable sensors for the simultaneous determination of coenzyme Q10 and α-lipoic acid using manganese (IV) oxide-modified screen-printed graphene electrodes.

PubMed

Charoenkitamorn, Kanokwan; Chaiyo, Sudkate; Chailapakul, Orawon; Siangproh, Weena

2018-04-03

In this work, for the first time, manganese (IV) oxide-modified screen-printed graphene electrodes (MnO 2 /SPGEs) were developed for the simultaneous electrochemical detection of coenzyme Q10 (CoQ10) and α-lipoic acid (ALA). This sensor exhibits attractive benefits such as simplicity, low production costs, and disposability. Cyclic voltammetry (CV) was used to characterize the electrochemical behavior of the analyte and investigate the capacitance and electroactive surface area of the unmodified and modified electrode surfaces. The electrochemical behavior of CoQ10 and ALA on MnO 2 /SPGEs was also discussed. Additionally, square wave anodic stripping voltammetry (SWASV) was used for the quantitative determination of CoQ10 and ALA. Under optimal conditions, the obtained signals are linear in the concentration range from 2.0 to 75.0 μg mL -1 for CoQ10 and 0.3-25.0 μg mL -1 for ALA. The low limits of detection (LODs) were found to be 0.56 μg mL -1 and 0.088 μg mL -1 for CoQ10 and ALA, respectively. Moreover, we demonstrated the utility and applicability of the MnO 2 /SPGE sensor through simultaneous measurements of CoQ10 and ALA in dietary supplements. The sensor provides high accuracy measurements, exhibiting its high potential for practical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Detectability of Wellbore CO2 Leakage using the Magnetotelluric Method

NASA Astrophysics Data System (ADS)

Yang, X.; Buscheck, T. A.; Mansoor, K.; Carroll, S.

2016-12-01

We assessed the effectiveness of the magnetotelluric (MT) method in detecting CO2 and brine leakage through a wellbore, which penetrates a CO2 storage reservoir, into overlying aquifers, 0 to 1720 m in depth, in support of the USDOE National Risk Assessment Partnership (NRAP) monitoring program. Synthetic datasets based on the Kimberlina site in the southern San Joaquin Basin, California were created using CO2 storage reservoir models, wellbore leakage models, and groundwater/geochemical models of the overlying aquifers. The species concentrations simulated with the groundwater/geochemical models were converted into bulk electrical conductivity (EC) distributions as the MT model input. Brine and CO2 leakage into the overlying aquifers increases ion concentrations, and thus results in an EC increase, which may be detected by the MT method. Our objective was to estimate and maximize the probability of leakage detection using the MT method. The MT method is an electromagnetic geophysical technique that images the subsurface EC distribution by measuring natural electric and magnetic fields in the frequency range from 0.01 Hz to 1 kHz with sensors on the ground surface. The ModEM software was used to predict electromagnetic responses from brine and CO2 leakage and to invert synthetic MT data for recovery of subsurface conductivity distribution. We are in the process of building 1000 simulations for ranges of permeability, leakage flux, and hydraulic gradient to study leakage detectability and to develop an optimization method to answer when, where and how an MT monitoring system should be deployed to maximize the probability of leakage detection. This work was sponsored by the USDOE Fossil Energy, National Energy Technology Laboratory, managed by Traci Rodosta and Andrea McNemar. This work was performed under the auspices of the USDOE by LLNL under contract DE-AC52-07NA27344. LLNL IM release number is LLNL-ABS-699276.

CO2 splitting by H2O to CO and O2 under UV light in TiMCM-41silicate sieve

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

Lin, Wenyong; Han, Hongxian; Frei, Heinz

2004-04-06

The 266 nm light-induced reaction of CO{sub 2} and H{sub 2}O gas mixtures (including isotopic modifications {sup 13}CO{sub 2}, C{sup 18}O{sub 2}, and D{sub 2}O) in framework TiMCM-41 silicate sieve was monitored by in-situ FT-IR spectroscopy at room temperature. Carbon monoxide gas was observed as the sole product by infrared, and the growth was found to depend linearly on the photolysis laser power. H{sub 2}O was confirmed as stoichiometric electron donor. The work establishes CO as the single photon, 2-electron transfer product of CO{sub 2} photoreduction by H{sub 2}O at framework Ti centers for the first time. O{sub 2} wasmore » detected as co-product by mass spectrometric analysis of the photolysis gas mixture. These results are explained by single UV photon-induced splitting of CO{sub 2} by H{sub 2}O to CO and surface OH radical.« less

MOF-templated synthesis of porous Co(3)O(4) concave nanocubes with high specific surface area and their gas sensing properties.

PubMed

Lü, Yinyun; Zhan, Wenwen; He, Yue; Wang, Yiting; Kong, Xiangjian; Kuang, Qin; Xie, Zhaoxiong; Zheng, Lansun

2014-03-26

Porous metal oxides nanomaterials with controlled morphology have received great attention because of their promising applications in catalysis, energy storage and conversion, gas sensing, etc. In this paper, porous Co3O4 concave nanocubes with extremely high specific surface area (120.9 m(2)·g(-1)) were synthesized simply by calcining Co-based metal-organic framework (Co-MOF, ZIF-67) templates at the optimized temperature (300 °C), and the formation mechanism of such highly porous structures as well as the influence of the calcination temperature are well explained by taking into account thermal behavior and intrinsic structural features of the Co-MOF precursors. The gas-sensing properties of the as-synthesized porous Co3O4 concave nanocubes were systematically tested towards volatile organic compounds including ethanol, acetone, toluene, and benzene. Experimental results reveal that the porous Co3O4 concave nanocubes present the highest sensitivity to ethanol with fast response/recovery time (< 10 s) and a low detection limit (at least 10 ppm). Such outstanding gas sensing performance of the porous Co3O4 concave nanocubes benefits from their high porosity, large specific surface area, and remarkable capabilities of surface-adsorbed oxygen.

Detection of CO2•- in the Electrochemical Reduction of Carbon Dioxide in N,N-Dimethylformamide by Scanning Electrochemical Microscopy.

PubMed

Kai, Tianhan; Zhou, Min; Duan, Zhiyao; Henkelman, Graeme A; Bard, Allen J

2017-12-27

The electrocatalytic reduction of CO 2 has been studied extensively and produces a number of products. The initial reaction in the CO 2 reduction is often taken to be the 1e formation of the radical anion, CO 2 •- . However, the electrochemical detection and characterization of CO 2 •- is challenging because of the short lifetime of CO 2 •- , which can dimerize and react with proton donors and even mild oxidants. Here, we report the generation and quantitative determination of CO 2 •- in N,N-dimethylformamide (DMF) with the tip generation/substrate collection (TG/SC) mode of scanning electrochemical microscopy (SECM). CO 2 was reduced at a hemisphere-shaped Hg/Pt ultramicroelectrode (UME) or a Hg/Au film UME, which were utilized as the SECM tips. The CO 2 •- produced can either dimerize to form oxalate within the nanogap between SECM tip and substrate or collected at SECM substrate (e.g., an Au UME). The collection efficiency (CE) for CO 2 •- depends on the distance (d) between the tip and substrate. The dimerization rate (6.0 × 10 8 M -1 s -1 ) and half-life (10 ns) of CO 2 •- can be evaluated by fitting the collection efficiency vs distance curve. The dimerized species of CO 2 •- , oxalate, can also be determined quantitatively. Furthermore, the formal potential (E 0 ') and heterogeneous rate constant (k 0 ) for CO 2 reduction were determined with different quaternary ammonium electrolytes. The significant difference in k 0 is due to a tunneling effect caused by the adsorption of the electrolytes on the electrode surface at negative potentials.

A composite large-scale CO survey at high galactic latitudes in the second quadrant

NASA Technical Reports Server (NTRS)

Heithausen, A.; Stacy, J. G.; De Vries, H. W.; Mebold, U.; Thaddeus, P.

1993-01-01

Surveys undertaken in the 2nd quadrant of the Galaxy with the CfA 1.2 m telescope have been combined to produce a map covering about 620 sq deg in the 2.6 mm CO(J = 1 - 0) line at high galactic latitudes. There is CO emission from molecular 'cirrus' clouds in about 13 percent of the region surveyed. The CO clouds are grouped together into three major cloud complexes with 29 individual members. All clouds are associated with infrared emission at 100 micron, although there is no one-to-one correlation between the corresponding intensities. CO emission is detected in all bright and dark Lynds' nebulae cataloged in that region; however not all CO clouds are visible on optical photographs as reflection or absorption features. The clouds are probably local. At an adopted distance of 240 pc cloud sizes range from O.1 to 30 pc and cloud masses from 1 to 1600 solar masses. The molecular cirrus clouds contribute between 0.4 and 0.8 M solar mass/sq pc to the surface density of molecular gas in the galactic plane. Only 26 percent of the 'infrared-excess clouds' in the area surveyed actually show CO and about 2/3 of the clouds detected in CO do not show an infrared excess.

Elevated carbon dioxide alters the plasma composition and behaviour of a shark

PubMed Central

Green, Leon; Jutfelt, Fredrik

2014-01-01

Increased carbon emissions from fossil fuels are increasing the pCO2 of the ocean surface waters in a process called ocean acidification. Elevated water pCO2 can induce physiological and behavioural effects in teleost fishes, although there appear to be large differences in sensitivity between species. There is currently no information available on the possible responses to future ocean acidification in elasmobranch fishes. We exposed small-spotted catsharks (Scyliorhinus canicula) to either control conditions or a year 2100 scenario of 990 μatm pCO2 for four weeks. We did not detect treatment effects on growth, resting metabolic rate, aerobic scope, skin denticle ultrastructure or skin denticle morphology. However, we found that the elevated pCO2 group buffered internal acidosis via accumulation with an associated increase in Na+, indicating that the blood chemistry remained altered despite the long acclimation period. The elevated pCO2 group also exhibited a shift in their nocturnal swimming pattern from a pattern of many starts and stops to more continuous swimming. Although CO2-exposed teleost fishes can display reduced behavioural asymmetry (lateralization), the CO2-exposed sharks showed increased lateralization. These behavioural effects may suggest that elasmobranch neurophysiology is affected by CO2, as in some teleosts, or that the sharks detect CO2 as a constant stressor, which leads to altered behaviour. The potential direct effects of ocean acidification should henceforth be considered when assessing future anthropogenic effects on sharks. PMID:25232027

Enhanced Climatic Warming in the Tibetan Plateau Due to Double CO2: A Model Study

NASA Technical Reports Server (NTRS)

Chen, Baode; Chao, Winston C.; Liu, Xiao-Dong; Lau, William K. M. (Technical Monitor)

2001-01-01

The NCAR (National Center for Atmospheric Research) regional climate model (RegCM2) with time-dependent lateral meteorological fields provided by a 130-year transient increasing CO2 simulation of the NCAR Climate System Model (CSM) has been used to investigate the mechanism of enhanced ground temperature warming over the TP (Tibetan Plateau). From our model results, a remarkable tendency of warming increasing with elevation is found for the winter season, and elevation dependency of warming is not clearly recognized in the summer season. This simulated feature of elevation dependency of ground temperature is consistent with observations. Based on an analysis of surface energy budget, the short wave solar radiation absorbed at the surface plus downward long wave flux reaching the surface shows a strong elevation dependency, and is mostly responsible for enhanced surface warming over the TP. At lower elevations, the precipitation forced by topography is enhanced due to an increase in water vapor supply resulted from a warming in the atmosphere induced by doubling CO2. This precipitation enhancement must be associated with an increase in clouds, which results in a decline in solar flux reaching surface. At higher elevations, large snow depletion is detected in the 2xCO2run. It leads to a decrease in albedo, therefore more solar flux is absorbed at the surface. On the other hand, much more uniform increase in downward long wave flux reaching the surface is found. The combination of these effects (i.e. decrease in solar flux at lower elevations, increase in solar flux at higher elevation and more uniform increase in downward long wave flux) results in elevation dependency of enhanced ground temperature warming over the TP.

Three-dimensional crustal structure of Long Valley caldera, California, and evidence for the migration of CO2 under Mammoth Mountain

USGS Publications Warehouse

Foulger, G.R.; Julian, B.R.; Pitt, A.M.; Hill, D.P.; Malin, P.E.; Shalev, E.

2003-01-01

A temporary network of 69 three-component seismic stations captured a major seismic sequence in Long Valley caldera in 1997. We performed a tomographic inversion for crustal structure beneath a 28 km ?? 16 km area encompassing part of the resurgent dome, the south moat, and Mammoth Mountain. Resolution of crustal structure beneath the center of the study volume was good down to ???3 km below sea level (???5 km below the surface). Relatively high wave speeds are associated with the Bishop Tuff and lower wave speeds characterize debris in the surrounding moat. A low-Vp/Vs anomaly extending from near the surface to ???1 km below sea level beneath Mammoth Mountain may represent a CO2 reservoir that is supplying CO2-rich springs, venting at the surface, and killing trees. We investigated temporal variations in structure beneath Mammoth Mountain by differencing our results with tomographic images obtained using data from 1989/1990. Significant changes in both Vp and Vs were consistent with the migration of CO2 into the upper 2 km or so beneath Mammoth Mountain and its depletion in peripheral volumes that correlate with surface venting areas. Repeat tomography is capable of detecting the migration of gas beneath active silicic volcanoes and may thus provide a useful volcano monitoring tool.

Comparison of Carbon Dioxide Airborne Measurement over Land and Ocean using 2-μm Double-Pulse Integrated Path Differential Absorption Lidar

NASA Astrophysics Data System (ADS)

Refaat, T. F.; Singh, U. N.; Petros, M.; Yu, J.; Remus, R.; Ismail, S.

2017-12-01

An airborne Integrated Path Differential Absorption (IPDA) lidar has been developed and validated at NASA Langley Research Center for atmospheric carbon dioxide column measurements. The instrument consists of a tunable, high-energy 2-μm double pulse laser transmitter and 0.4 m telescope receiver coupled to an InGaAs pin detection system. The instrument was validated for carbon dioxide (CO2) measurements from ground and airborne platforms, using a movable lidar trailer and the NASA B-200 aircraft. Airborne validation was conducted over the ocean by comparing the IPDA CO2 optical depth measurement to optical depth model derived using NOAA airborne CO2 air-sampling. Another airborne validation was conducted over land vegetation by comparing the IPDA measurement to a model derived using on-board in-situ measurements using an absolute, non-dispersive infrared gas analyzer (LiCor 840A). IPDA range measurements were also compared to rangefinder and Global Positioning System (GPS) records during ground and airborne validation, respectively. Range measurements from the ground indicated a 0.93 m IPDA range measurement uncertainty, which is limited by the transmitted laser pulse and detection system properties. This uncertainty increased to 2.80 and 7.40 m over ocean and land, due to fluctuations in ocean surface and ground elevations, respectively. IPDA CO2 differential optical depth measurements agree with both models. Consistent CO2 optical depth biases were well correlated with the digitizer full scale input range settings. CO2 optical depth measurements over ocean from 3.1 and 6.1 km altitudes indicated 0.95% and 0.83% uncertainty, respectively, using 10 second (100 shots) averaging. Using the same averaging 0.40% uncertainty was observed over land, from 3.4 km altitude, due to higher surface reflectivity, which increases the return signal power and enhances the signal-to-noise ratio. However, less uncertainty is observed at higher altitudes due to reduced signal shot noise, indicating that detection system noise-equivalent-power dominates the error. These results show that the IPDA technique is well suited for space-based platforms, which includes larger column content integration that enhances the measurement sensitivity.

Assembly of multilayer microcapsules on CacO3 particles from biocompatible polysaccharides.

PubMed

Zhao, Qinghe; Mao, Zhengwei; Gao, Changyou; Shen, Jiacong

2006-01-01

Multilayer microcapsules were fabricated by layer-by-layer (LbL) assembly of natural polysaccharides onto CaCO3 particles, following with core removal. The micron-sized CaCO3 particles were synthesized by reaction between Ca(NO3)2 and Na2CO3 solutions in the existence of carboxylmethyl cellulose (CMC). The incorporated amount of CMC in the CaCO3 particles was found to be 5.3 wt% by thermogravimetric analysis. Two biocompatible polysaccharides, chitosan and sodium alginate were alternately deposited onto the CaCO3(CMC) templates to obtain hollow microcapsules. Regular oscillation of surface charge as detected by zeta potential demonstrated that the assembly proceeded surely in a LbL manner. The stability of the microcapsules was effectively improved by cross-linking of chitosan with glutaraldehyde. The chemical reaction was verified by infrared spectroscopy. The microcapsules thus fabricated could be spontaneously filled with positively charged low molecular weight substances such as rhodamine 6G and showed good biocompatibility, as detected by in vitro cell culture.

Ground penetrating radar survey and lineament analysis of the West Pearl Queen carbon sequestration pilot site, New Mexico

NASA Astrophysics Data System (ADS)

Wilson, T. H.; Wells, A. W.; Diehl, R. R.; Bromhal, G. S.; Carpenter, W.; Smith, D. H.

2004-05-01

The potential for leakage of injected CO2 at carbon sequestration sites is a significant concern in the design and deployment of long term carbon sequestration efforts. Effective and reliable monitoring of near-surface environments in the vicinity of these sites is essential to ensure the viability of sequestration activities as well as long term public and environmental safety. This study reports on near-surface geological and geophysical characterization efforts conducted at the NETL West Pearl Queen carbon sequestration pilot site in southeastern New Mexico and their use in uncovering possible mechanisms facilitating escape of small amounts (10e-13 liters) of tracer injected with the CO2. In this pilot test, a small amount of CO2 (2100 tonnes) was injected into the Shattuck sandstone member of the Permian Queen Formation early in 2003. Tracers injected with the CO2 were detected within a few days of injection and continued to escape for several months following injection. Geological and geophysical characterization of the near-surface environment in the vicinity of the injection well incorporated lineament interpretations and a detailed ground penetrating radar survey conducted over a circular area extending out 300 meters from the injection well. The near-surface geology consists of a few-feet thick veneer of late Pleistocene and Holocene sand dunes covering the middle Pleistocene Mescalero caliche. The lineament study incorporated interpretation of black and white aerial photos from 1949, digital orthophotos, and Landsat TM imagery. Analysis reveals distinct northeast and northwest trending lineament sets. The GPR survey defines the presence of a nearly continuous blanket of caliche beneath the area. However, the thickness of the caliche zone varies significantly, and it is disrupted by numerous fault-like features, amplitude anomalies, and reflection gaps. Some of these disruptions are traceable over distances of 25 to 200 meters and their aerial distribution shows some association with the distribution of tracers detected in the near-surface across the site. The observations suggest that the caliche has undergone significant karstification and could provide pathways along which CO2 could migrate through the near-surface from a leaky well casing or, less likely, along more extensive vertical migration pathways.

Standoff laser-induced thermal emission of explosives

NASA Astrophysics Data System (ADS)

Galán-Freyle, Nataly Y.; Pacheco-Londoño, Leonardo C.; Figueroa-Navedo, Amanda; Hernandez-Rivera, Samuel P.

2013-05-01

A laser mediated methodology for remote thermal excitation of analytes followed by standoff IR detection is proposed. The goal of this study was to determine the feasibility of using laser induced thermal emission (LITE) from vibrationally excited explosives residues deposited on surfaces to detect explosives remotely. Telescope based FT-IR spectral measurements were carried out to examine substrates containing trace amounts of threat compounds used in explosive devices. The highly energetic materials (HEM) used were PETN, TATP, RDX, TNT, DNT and ammonium nitrate with concentrations from 5 to 200 μg/cm2. Target substrates of various thicknesses were remotely heated using a high power CO2 laser, and their mid-infrared (MIR) thermally stimulated emission spectra were recorded. The telescope was configured from reflective optical elements in order to minimize emission losses in the MIR frequencies and to provide optimum overall performance. Spectral replicas were acquired at a distance of 4 m with an FT-IR interferometer at 4 cm- 1 resolution and 10 scans. Laser power was varied from 4-36 W at radiation exposure times of 10, 20, 30 and 60 s. CO2 laser powers were adjusted to improve the detection and identification of the HEM samples. The advantages of increasing the thermal emission were easily observed in the results. Signal intensities were proportional to the thickness of the coated surface (a function of the surface concentration), as well as the laser power and laser exposure time. For samples of RDX and PETN, varying the power and time of induction of the laser, the calculated low limit of detections were 2 and 1 μg/cm2, respectively.

Helicopter Surveys for Locating Wells and Leaking Oilfield Infrastructure

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

Hammack, R.W.; Veloski, G.A.; Hodges, G.

2006-10-01

Prior to the injection of CO2 into geological formations, either for enhanced oil recovery or for CO2 sequestration, it is necessary to locate wells that perforate the target formation and are within the radius of influence for planned injection wells. Locating and plugging wells is necessary because improperly plugged well bores provide the most rapid route for CO2 escape to the surface. This paper describes the implementation and evaluation of helicopter and ground-based well detection strategies at a 100+ year old oilfield in Wyoming where a CO2 flood is planned. This project was jointly funded by the U.S. Department ofmore » Energy’s National Energy Technology Laboratory and Fugro Airborne Surveys« less

The neuronal Ca(2+) -binding protein 2 (NECAB2) interacts with the adenosine A(2A) receptor and modulates the cell surface expression and function of the receptor.

PubMed

Canela, Laia; Luján, Rafael; Lluís, Carme; Burgueño, Javier; Mallol, Josefa; Canela, Enric I; Franco, Rafael; Ciruela, Francisco

2007-09-01

Heptaspanning membrane also known as G protein-coupled receptors (GPCR) do interact with a variety of intracellular proteins whose function is regulate receptor traffic and/or signaling. Using a yeast two-hybrid screen, NECAB2, a neuronal calcium binding protein, was identified as a binding partner for the adenosine A(2A) receptor (A(2A)R) interacting with its C-terminal domain. Co-localization, co-immunoprecipitation and pull-down experiments showed a close and specific interaction between A(2A)R and NECAB2 in both transfected HEK-293 cells and also in rat striatum. Immunoelectron microscopy detection of NECAB2 and A(2A)R in the rat striatopallidal structures indicated that both proteins are co-distributed in the same glutamatergic nerve terminals. The interaction of NECAB2 with A(2A)R modulated the cell surface expression, the ligand-dependent internalization and the receptor-mediated activation of the MAPK pathway. Overall, these results show that A(2A)R interacts with NECAB2 in striatal neurones co-expressing the two proteins and that the interaction is relevant for A(2A)R function.

Structure and magnetic properties of chromium doped cobalt molybdenum nitrides

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

Guskos, Niko; Żołnierkiewicz, Grzegorz; Typek, Janusz

Four nanocomposites containing mixed phases of Co{sub 3}Mo{sub 3}N and Co{sub 2}Mo{sub 3}N doped with chromium have been prepared. A linear fit is found for relation between Co{sub 2}Mo{sub 3}N and chromium concentrations. The magnetization in ZFC and FC modes at different temperatures (2–300 K) and in applied magnetic fields (up to 70 kOe) have been investigated. It has been detected that many magnetic characteristics of the studied four nanocomposites correlate not with the chromium concentration but with nanocrystallite sizes. The obtained results were interpreted in terms of magnetic core-shell model of a nanoparticle involving paramagnetic core with two magneticmore » sublattices and a ferromagnetic shell related to chromium doping. - Highlights: • A new chromium doped mixed Co-Mn-N nanocomposites were synthesized. • Surface ferromagnetism was detected in a wide temperature range. • Core-shell model was applied to explain nanocomposites magnetism.« less

Assessment of the Potential for Flux Estimation Using Concentration Data from Mobile Surveys

NASA Astrophysics Data System (ADS)

Gyenis, A.; Zahasky, C.; Moriarty, D. M.; Benson, S. M.

2014-12-01

Carbon capture and storage is a climate change mitigation technology with the potential to serve as a bridge technology as society transitions from a fossil fuel dependent energy system to a renewable energy dominated system. One of the greatest concerns associated with wide-scale adoption of carbon capture and storage technology is the risk of carbon dioxide leakage from sequestration reservoirs. Thus there is a need to develop efficient and effective strategies for monitoring and verification of geologically stored carbon dioxide. To evaluate the potential for estimating leakage fluxes based on mobile surveys, we establish correlations between concentration data and flux measurements made with a flux chamber. These correlations are then used to estimate leakage fluxes over a 70-meter long horizontal well buried approximately 1.8 meters below the surface at the Zero Emissions Research and Technology (ZERT) facility operated by Montana State University. The CO2 had a leakage rate of 0.15 t/d, which is comparable to a small leak in an industrial scale project (0.005% of a 1 Mt/yr storage project). A Picarro gas analyzer was used to measure 12CO2 and 13CO2 at heights of 3 cm above the ground surface. Previous studies (Moriarty, 2014) show that concentration data at this height provides a very high likelihood (>95%) of detecting leaks within a distance of 2.5 m of the leak. Measured concentration data show a noisy but significant correlation with flux measurements, thus providing the possibility to obtain rough estimates of leakage fluxes from mobile measurements. Moriarty, Dylan, 2014. Rapid Surface Detection of CO2 Leaks from Geologic Sequestration Sites. MS Thesis, Stanford University.

Winter crop CO2 uptake inferred from CONTRAIL measurements over Delhi, India

NASA Astrophysics Data System (ADS)

Umezawa, Taku; Niwa, Yosuke; Sawa, Yousuke; Machida, Toshinobu; Matsueda, Hidekazu

2016-11-01

Recent studies have shown the impact of expanding agricultural activities on atmospheric CO2 variations and the global carbon cycle. In this study, we show clear evidence of the measureable impact of Indian wintertime crops (mainly wheat) on the regional carbon budget using high-frequency atmospheric CO2 measurements by Comprehensive Observation Network for Trace gases by Airliners (CONTRAIL) over Delhi; this phenomenon is not detected by the existing network of surface CO2 sites. While a general increase in the vertical profiles of CO2 toward the ground in the boundary layer was observed throughout December-April, we frequently observed sharp decreases below 2 km during January-March. Seasonal circulations during these 3 months indicated influences from neighboring croplands (with patchy urban areas) located upwind. We conclude that the observed CO2 decrease is attributable to active uptake by the crops grown in winter and that the uptake exceeds in magnitude the urban CO2 emissions from the Delhi metropolitan area.

Probing Metal Carbonation Reactions of CO2 in a Model System Containing Forsterite and H2O Using Si-29, C-13 Magic Angle Sample Spinning NMR Spectroscopy

NASA Astrophysics Data System (ADS)

Hu, J.; Kwak, J.; Hoyt, D. W.; Sears, J. A.; Rosso, K. M.; Felmy, A. R.

2009-12-01

Ex situ solid state NMR have been used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration using a model silicate mineral forsterite (Mg2SiO4)+scCO2 with and without H2O. Run conditions were 80C and 96 bar. Si-29 NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce Mg2+, and mono- and oligomeric hydroxylated silica species. The surface hydrolysis products contain only Q0 (Si(OH)4) and Q1 (Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to less than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. Si-29 NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. C-13 MAS NMR identified a possible reaction intermediates as (MgCO3)4*Mg(OH)2*5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed. This research is part of a broader effort at PNNL to develop experimental tools and fundamental insights into chemical transformations affecting subsurface CO2 reactive transport. Si-29 (left) and C-13 (right) MAS NMR spectra of Mg2SiO4 under various reaction conditions. Si-29 NMR reveals that in scCO2 without H2O, no reaction is observed (b). In H2O without scCO2, only surface hydrolysis products Q0 and Q1 are present (c). In a mixture of both H2O and scCO2, the products are Q2, Q3 and Q4 (d). C-13 NMR (e-f) reveals the formation of MgCO3 at long reaction times with (MgCO3)4*Mg(OH)2*5H2O as a possible reaction intermediate.

Interfacial Engineering of Hierarchical Transition Metal Oxide Heterostructures for Highly Sensitive Sensing of Hydrogen Peroxide.

PubMed

Zhang, Wen; Fan, Guozheng; Yi, Huan; Jia, Gan; Li, Zhaosheng; Yuan, Chunwei; Bai, Yunfei; Fu, Degang

2018-05-01

Hydrogen peroxide (H 2 O 2 ) is a major messenger molecule in cellular signal transduction. Direct detection of H 2 O 2 in complex environments provides the capability to illuminate its various biological functions. With this in mind, a novel electrochemical approach is here proposed by integrating a series of CoO nanostructures on CuO backbone at electrode interfaces. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction, and X-ray photoelectron spectroscopy demonstrate successful formation of core-shell CuO-CoO hetero-nanostructures. Theoretical calculations further confirm energy-favorable adsorption of H 2 O 2 on surface sites of CuO-CoO heterostructures. Contributing to the efficient electron transfer path and enhanced capture of H 2 O 2 in the unique leaf-like CuO-CoO hierarchical 3D interface, an optimal biosensor-based CuO-CoO-2.5 h electrode exhibits an ultrahigh sensitivity (6349 µA m m -1 cm -2 ), excellent selectivity, and a wide detection range for H 2 O 2 , and is capable of monitoring endogenous H 2 O 2 derived from human lung carcinoma cells A549. The synergistic effects for enhanced H 2 O 2 adsorption in integrated CuO-CoO nanostructures and performance of the sensor suggest a potential for exploring pathological and physiological roles of reactive oxygen species like H 2 O 2 in biological systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Passive wireless surface acoustic wave sensors for monitoring sequestration sites CO 2 emission

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

Wang, Yizhong; Chyu, Minking; Wang, Qing-Ming

2013-02-14

University of Pittsburgh’s Transducer lab has teamed with the U.S. Department of Energy’s National Energy Technology Laboratory (DOE NETL) to conduct a comprehensive study to develop/evaluate low-cost, efficient CO 2 measuring technologies for geological sequestration sites leakage monitoring. A passive wireless CO 2 sensing system based on surface acoustic wave technology and carbon nanotube nanocomposite was developed. Surface acoustic wave device was studied to determine the optimum parameters. Delay line structure was adopted as basic sensor structure. CNT polymer nanocomposite was fabricated and tested under different temperature and strain condition for natural environment impact evaluation. Nanocomposite resistance increased for 5more » times under pure strain, while the temperature dependence of resistance for CNT solely was -1375ppm/°C. The overall effect of temperature on nanocomposite resistance was -1000ppm/°C. The gas response of the nanocomposite was about 10% resistance increase under pure CO 2 . The sensor frequency change was around 300ppm for pure CO 2 . With paralyne packaging, the sensor frequency change from relative humidity of 0% to 100% at room temperature decreased from over 1000ppm to less than 100ppm. The lowest detection limit of the sensor is 1% gas concentration, with 36ppm frequency change. Wireless module was tested and showed over one foot transmission distance at preferred parallel orientation.« less

Detection and Retrieval of Multi-Layered Cloud Properties Using Satellite Data

NASA Technical Reports Server (NTRS)

Minnis, Patrick; Sun-Mack, Sunny; Chen, Yan; Yi, Helen; Huang, Jian-Ping; Nguyen, Louis; Khaiyer, Mandana M.

2005-01-01

Four techniques for detecting multilayered clouds and retrieving the cloud properties using satellite data are explored to help address the need for better quantification of cloud vertical structure. A new technique was developed using multispectral imager data with secondary imager products (infrared brightness temperature differences, BTD). The other methods examined here use atmospheric sounding data (CO2-slicing, CO2), BTD, or microwave data. The CO2 and BTD methods are limited to optically thin cirrus over low clouds, while the MWR methods are limited to ocean areas only. This paper explores the use of the BTD and CO2 methods as applied to Moderate Resolution Imaging Spectroradiometer (MODIS) and Advanced Microwave Scanning Radiometer EOS (AMSR-E) data taken from the Aqua satellite over ocean surfaces. Cloud properties derived from MODIS data for the Clouds and the Earth's Radiant Energy System (CERES) Project are used to classify cloud phase and optical properties. The preliminary results focus on a MODIS image taken off the Uruguayan coast. The combined MW visible infrared (MVI) method is assumed to be the reference for detecting multilayered ice-over-water clouds. The BTD and CO2 techniques accurately match the MVI classifications in only 51 and 41% of the cases, respectively. Much additional study is need to determine the uncertainties in the MVI method and to analyze many more overlapped cloud scenes.

Detection and retrieval of multi-layered cloud properties using satellite data

NASA Astrophysics Data System (ADS)

Minnis, Patrick; Sun-Mack, Sunny; Chen, Yan; Yi, Helen; Huang, Jianping; Nguyen, Louis; Khaiyer, Mandana M.

2005-10-01

Four techniques for detecting multilayered clouds and retrieving the cloud properties using satellite data are explored to help address the need for better quantification of cloud vertical structure. A new technique was developed using multispectral imager data with secondary imager products (infrared brightness temperature differences, BTD). The other methods examined here use atmospheric sounding data (CO2-slicing, CO2), BTD, or microwave data. The CO2 and BTD methods are limited to optically thin cirrus over low clouds, while the MWR methods are limited to ocean areas only. This paper explores the use of the BTD and CO2 methods as applied to Moderate Resolution Imaging Spectroradiometer (MODIS) and Advanced Microwave Scanning Radiometer EOS (AMSR-E) data taken from the Aqua satellite over ocean surfaces. Cloud properties derived from MODIS data for the Clouds and the Earth's Radiant Energy System (CERES) Project are used to classify cloud phase and optical properties. The preliminary results focus on a MODIS image taken off the Uruguayan coast. The combined MW visible infrared (MVI) method is assumed to be the reference for detecting multilayered ice-over-water clouds. The BTD and CO2 techniques accurately match the MVI classifications in only 51 and 41% of the cases, respectively. Much additional study is need to determine the uncertainties in the MVI method and to analyze many more overlapped cloud scenes.

Enrichment of Extracellular Carbonic Anhydrase in the Sea Surface Microlayer and Its Effect on Air-Sea CO2 Exchange

NASA Astrophysics Data System (ADS)

Mustaffa, N. I. H.; Striebel, M.; Wurl, O.

2017-12-01

This paper describes the quantification of extracellular carbonic anhydrase (eCA) concentrations in the sea surface microlayer (SML), the boundary layer between the ocean and the atmosphere of the Indo-West Pacific. We demonstrated that the SML is enriched with eCA by 1.5 ± 0.7 compared to the mixed underlying water. Enrichment remains up to a wind speed of 7 m s-1 (i.e., under typical oceanic conditions). As eCA catalyzes the interconversion of HCO3- and CO2, it has been hypothesized that its enrichment in the SML enhances the air-sea CO2 exchange. We detected concentrations in the range of 0.12 to 0.76 nM, which can enhance the exchange by up to 15% based on the model approach described in the literature.

The Monitoring of Sallow CO2 Leakage From the CO2 Release Experiment in South Korea

NASA Astrophysics Data System (ADS)

Kim, H. J.; Han, S. H.; Kim, S.; Son, Y.

2017-12-01

This study was conducted to analyze the in-soil CO2 gas diffusion from the K-COSEM shallow CO2 release experiment. The study site consisting of five zones was built in Eumseong, South Korea, and approximately 1.8 t CO2 were injected from the perforated release well at Zones 1 to 4 from June 1 to 30, 2016. In-soil CO2 concentrations were measured once a day at 15 cm and 60 cm depths at 0 m, 2.5 m, 5.0 m, and 10.0 m away from the CO2 releasing well using a portable gas analyzer (GA5000) from May 11 to July 27, 2016. On June 4, CO2 leakage was simultaneously detected at 15 cm (8.8 %) and 60 cm (44.0 %) depths at 0 m from the well at Zone 3, and were increased up to about 30 % and 70 %, respectively. During the CO2 injection period, CO2 concentrations measured at 15 cm depth were significantly lower than those measured at 60 cm depth because of the atmospheric pressure effect. After stopping the CO2 injection, CO2 concentrations gradually decreased until July 27, but were still higher than the natural background concentration. This result suggested the possibility of long-term CO2 leakage. In addition, low levels of CO2 leakage were determined using CO2 regression analysis and CO2:O2 ratio. CO2 concentrations measured at 60 cm depth at 0 m from the well at Zones 1 to 4 consistently showed sigmoid increasing patterns with the injection time (R2=0.60-0.99). O2 concentrations at 15 cm and 60 cm depths from the CO2 release experiment were reached 0 % at about 76 % and 84 % of CO2 concentrations, respectively, whereas, those from biological reaction approached 0 % when CO2 increased to about 21 %. Therefore, deep underground monitoring would be able to detect CO2 leakage faster than near-surface monitoring, and CO2 regression and CO2:O2 ratio analyses seemed to be useful as clear indicators of CO2 leakage.

SFG study of the ethanol in an acidic medium--Pt(110) interface: effects of the alcohol concentration.

PubMed

Gomes, Janaina F; Busson, Bertrand; Tadjeddine, Abderrahmane

2006-03-23

Ethanol in an acidic solution-Pt(110) interface was studied by SFG spectroscopy (between 1820 and 2325 cm(-1)) to explore primarily the effects of the alcohol concentration. Stretching bands of H-Pt (ca. 1970 or 2050 cm(-1)) and CO (ca. 1980 and 2040 cm(-1)) species, produced by the ethanol oxidation, were detected during the adsorption and oxidation of 0-1 mol L(-1) ethanol in a 0.1 mol L(-1) HClO(4) solution on the electrode surface. Hydrogen and CO coadsorb stably on Pt(110) between 0.05 and 0.15 V in ethanol-containing solutions. In this potential range, the blue shift of the hydrogen resonance (ca. 80 cm(-1)) reveals a weakening of the hydrogen bonding between adsorbed hydrogen and water molecules in the double layer. After the hydrogen desorption (0.15 V), the formation of compact CO islands, depending on the ethanol concentration, lifts the Pt(110) surface reconstruction. In ethanol-free solution, the surface remains reconstructed. The lower-frequency CO band is assigned to the CO species adsorbed on (1 x 2) reconstructed Pt(110) domains, having smaller local coverages, while the higher-frequency CO band is attributed to the close-packed CO species adsorbed on (1 x 1) patches. The reaction pathway forming CO(2) is less favored with increasing ethanol concentration.

Detection of CN emission from (2060) Chiron

NASA Technical Reports Server (NTRS)

Bus, Schelte J.; Schleicher, David G.; Bowell, Edward; A'Hearn, Michael F.

1991-01-01

The detection of CN emission the spectrum of (2060) Chiron not only underscores its cometary nature, but represents, at a heliocentric distance in excess of 11 AU, the most distantly detected instance of a cometary gas species. These observations are noted to be consistent with a driving of Chiron's outgassing by isolated outbursts of CO2 from a small fraction of Chiron's surface. If dusty particles or icy grains are dragged out by the gas with unit dust-to-gas mass ratio, outbursts need occur only once every several months. Such small-surface outgassings appear to characterize comets which have made many passages close to the sun.

Detecting deep crustal magma movement: Exploring linkages between increased gas emission, deep seismicity, and deformation (Invited)

NASA Astrophysics Data System (ADS)

Werner, C. A.; Poland, M. P.; Power, J. A.; Sutton, A. J.; Elias, T.; Grapenthin, R.; Thelen, W. A.

2013-12-01

Typically in the weeks to days before a volcanic eruption there are indisputable signals of unrest that can be identified in geophysical and geochemical data. Detection of signals of volcanic unrest months to years prior to an eruption, however, relies on our ability to recognize and link more subtle changes. Deep long-period earthquakes, typically 10-45 km beneath volcanoes, are thought to represent magma movement and may indicate near future unrest. Carbon dioxide (CO2 ) exsolves from most magmas at similar depths and increases in CO2 discharge may also provide a months-to-years precursor as it emits at the surface in advance of the magma from which it exsolved. Without the use of sensitive monitoring equipment and routine measurements, changes in CO2 can easily go undetected. Finally, inflation of the surface, through use of InSAR or GPS stations (especially at sites tens of km from the volcano) can also indicate accumulation of magma in the deep crust. Here we present three recent examples, from Redoubt, Kilauea, and Mammoth Mountain volcanoes, where increases in CO2 emission, deep long-period earthquakes, and surface deformation data indicate either the intrusion of magma into the deep crust in the months to years preceding volcanic eruptions or a change in ongoing volcanic unrest. At Redoubt volcano, Alaska, elevated CO2 emission (~ 1200 t/d, or roughly 20 times the background emission) was measured in October, 2008, over 5 months prior to the first magmatic eruption in March, 2009. In addition to CO2 release, deep long-period earthquakes were first recorded in December, 2008, and a deep deformation signal was detected starting in May 2008, albeit retrospectively. At Kilauea, Hawaii, increases in CO2 emissions from the summit (up to nearly 25 kt/d, over three times the background emission) were measured mid-2004, roughly coincident with a change in deformation behavior from deflation to inflation. Nearly 3 years later, a change in eruptive activity occurred as a result of a burgeoning supply of magma to the volcano, which overwhelmed the ability of the ongoing east rift zone eruption to accommodate the increased flux of magma into the edifice. At Mammoth Mountain, California, diffuse CO2 degassing doubled between 2007 and 2012 following three swarms of deep earthquakes that began in 2006. In contrast to Redoubt and Kilauea, the CO2 emission rate at Mammoth is on the order of hundreds of t/d as opposed to thousands. This reasonably indicates a smaller volume of magma at depth, and changes do not suggest volcanic activity is imminent. In these examples there was no visual indication of increased CO2 emission, and geophysical signals of unrest were often subtle. Routine measurement of all volcanic gases, most importantly CO2 , coupled with a geophysical monitoring, therefore, has better potential to recognize changes in deep (10s of km) magmatic processes. Such indicators are key to better eruption forecasts, especially on the months-to years timescales that often elude volcanologists.

Development of a 1 x N Fiber Optic Sensor Array for Carbon Sequestration Site Monitoring

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

Repasky, Kevin

2014-02-01

A fiber sensor array for sub-surface CO 2 concentrations measurements was developed for monitoring geologic carbon sequestration sites. The fiber sensor array uses a single temperature tunable distributed feedback (DFB) laser operating with a nominal wavelength of 2.004 μm. Light from this DFB laser is direct to one of the 4 probes via an in-line 1 x 4 fiber optic switch. Each of the 4 probes are buried and allow the sub-surface CO 2 to enter the probe through Millipore filters that allow the soil gas to enter the probe but keeps out the soil and water. Light from themore » DFB laser interacts with the CO 2 before it is directed back through the in-line fiber optic switch. The DFB laser is tuned across two CO 2 absorption features where a transmission measurement is made allowing the CO 2 concentration to be retrieved. The fiber optic switch then directs the light to the next probe where this process is repeated allowing sub-surface CO 2 concentration measurements at each of the probes to be made as a function of time. The fiber sensor array was deployed for fifty-eight days beginning June 19, 2012 at the Zero Emission Research Technology (ZERT) field site where sub-surface CO 2 concentrations were monitored. Background measurements indicate the fiber sensor array can monitor background levels as low as 1,000 parts per million (ppm). A thirty four day sub-surface release of 0.15 tones CO 2/day began on July 10, 2012. The elevated subsurface CO 2 concentration was easily detected by each of the four probes with values ranging to over 60,000 ppm, a factor of greater than 6 higher than background measurements. The fiber sensor array was also deploy at the Big Sky Carbon Sequestration Partnership (BSCSP) site in north-central Montana between July 9th and August 7th, 2013 where background measurements were made in a remote sequestration site with minimal infrastructure. The project provided opportunities for two graduate students to participate in research directly related to geologic carbon sequestration. Furthermore, commercialization of the technology developed is being pursued with five different companies via the Department of energy SBIR/STTR program« less

Estimation of seismically detectable portion of a gas plume: CO2CRC Otway project case study

NASA Astrophysics Data System (ADS)

Pevzner, Roman; Caspari, Eva; Bona, Andrej; Galvin, Robert; Gurevich, Boris

2013-04-01

CO2CRC Otway project comprises of several experiments involving CO2/CH4 or pure CO2 gas injection into different geological formations at the Otway test site (Victoria, Australia). During the first stage of the project, which was finished in 2010, more than 64,000 t of gas were injected into the depleted gas reservoir at ~2 km depth. At the moment, preparations for the next stage of the project aiming to examine capabilities of seismic monitoring of small scale injection (up to 15,000 t) into saline formation are ongoing. Time-lapse seismic is one of the most typical methods for CO2 geosequestration monitoring. Significant experience was gained during the first stage of the project through acquisition and analysis of the 4D surface seismic and numerous time-lapse VSP surveys. In order to justify the second stage of the project and optimise parameters of the experiment, several modelling studies were conducted. In order to predict seismic signal we populate realistic geological model with elastic properties, model their changes using fluid substitution technique applied to the fluid flow simulation results and compute synthetic seismic baseline and monitor volumes. To assess detectability of the time-lapse signal caused by the injection, we assume that the time-lapse noise level will be equivalent to the level of difference between the last two Otway 3D surveys acquired in 2009 and 2010 using conventional surface technique (15,000 lbs vibroseis sources and single geophones as the receivers). In order to quantify the uncertainties in plume imaging/visualisation due to the time-lapse noise realisation we propose to use multiple noise realisations with the same F-Kx-Ky amplitude spectra as the field noise for each synthetic signal volume. Having signal detection criterion defined in the terms of signal/time- lapse noise level on a single trace we estimate visible portion of the plume as a function of this criterion. This approach also gives an opportunity to attempt to evaluate probability of the signal detection. The authors acknowledge the funding provided by the Australian government through its CRC program to support this CO2CRC research project. We also acknowledge the CO2CRC's corporate sponsors and the financial assistance provided through Australian National Low Emissions Coal Research and Development (ANLEC R&D). ANLEC R&D is supported by Australian Coal Association Low Emissions Technology Limited and the Australian Government through the Clean Energy Initiative.

Applying monitoring, verification, and accounting techniques to a real-world, enhanced oil recovery operational CO2 leak

USGS Publications Warehouse

Wimmer, B.T.; Krapac, I.G.; Locke, R.; Iranmanesh, A.

2011-01-01

The use of carbon dioxide (CO2) for enhanced oil recovery (EOR) is being tested for oil fields in the Illinois Basin, USA. While this technology has shown promise for improving oil production, it has raised some issues about the safety of CO2 injection and storage. The Midwest Geological Sequestration Consortium (MGSC) organized a Monitoring, Verification, and Accounting (MVA) team to develop and deploy monitoring programs at three EOR sites in Illinois, Indiana, and Kentucky, USA. MVA goals include establishing baseline conditions to evaluate potential impacts from CO2 injection, demonstrating that project activities are protective of human health and the environment, and providing an accurate accounting of stored CO2. This paper focuses on the use of MVA techniques in monitoring a small CO2 leak from a supply line at an EOR facility under real-world conditions. The ability of shallow monitoring techniques to detect and quantify a CO2 leak under real-world conditions has been largely unproven. In July of 2009, a leak in the pipe supplying pressurized CO2 to an injection well was observed at an MGSC EOR site located in west-central Kentucky. Carbon dioxide was escaping from the supply pipe located approximately 1 m underground. The leak was discovered visually by site personnel and injection was halted immediately. At its largest extent, the hole created by the leak was approximately 1.9 m long by 1.7 m wide and 0.7 m deep in the land surface. This circumstance provided an excellent opportunity to evaluate the performance of several monitoring techniques including soil CO2 flux measurements, portable infrared gas analysis, thermal infrared imagery, and aerial hyperspectral imagery. Valuable experience was gained during this effort. Lessons learned included determining 1) hyperspectral imagery was not effective in detecting this relatively small, short-term CO2 leak, 2) even though injection was halted, the leak remained dynamic and presented a safety risk concern during monitoring activities and, 3) the atmospheric and soil monitoring techniques used were relatively cost-effective, easily and rapidly deployable, and required minimal manpower to set up and maintain for short-term assessments. However, characterization of CO2 distribution near the land surface resulting from a dynamic leak with widely variable concentrations and fluxes was challenging. ?? 2011 Published by Elsevier Ltd.

Field evaluation of open and closed-path CO2 flux systems over asphalt surface

NASA Astrophysics Data System (ADS)

Bogoev, I.; Santos, E.

2016-12-01

Eddy covariance (EC) is a widely used method for quantifying surface fluxes of heat, water vapor and carbon dioxide between ecosystems and the atmosphere. A typical EC system consists of an ultrasonic anemometer measuring the 3D wind vector and a fast-response infrared gas analyzer for sensing the water vapor and CO2 density in the air. When using an open-path analyzer that detects the constituent's density in situ a correction for concurrent air temperature and humidity fluctuations must be applied, Webb et al. (1980). In environments with small magnitudes of CO2 flux (<5µmol m-2 s-1) and in the presence of high sensible heat flux, like wintertime over boreal forest, open-path flux measurements have been challenging since the magnitude of the density corrections are as large as the uncorrected CO2 flux itself. A new technology merging the sensing paths of the gas analyzer and the sonic anemometer has been recently developed. This new integrated instrument allows a direct measurement of CO2 mixing ratio in the open air and has the potential to improve the quality of the temperature related density corrections by synchronously measuring the sensible heat flux in the optical path of the gas analyzer. We evaluate the performance and the accuracy of this new sensor over a large parking lot with an asphalt surface where the CO2 fluxes are considered low and the interfering sensible heat fluxes are above 200 Wm-2. A co-located closed-path EC system is used as a reference measurement to examine any systematic biases and apparent CO2 uptake observed with open-path sensors under high sensible heat flux regimes. Half-hour mean and variance of CO2 and water vapor concentrations are evaluated. The relative spectral responses, covariances and corrected turbulent fluxes using a common sonic anemometer are analyzed. The influence of sensor separation and frequency response attenuation on the density corrections is discussed.

Degradation of Adenine on the Martian Surface in the Presence of Perchlorates and Ionizing Radiation: A Reflectron Time-of-flight Mass Spectrometric Study

NASA Astrophysics Data System (ADS)

Góbi, Sándor; Bergantini, Alexandre; Kaiser, Ralf I.

2017-04-01

The aim of the present work is to unravel the radiolytic decomposition of adenine (C5H5N5) under conditions relevant to the Martian surface. Being the fundamental building block of (deoxy)ribonucleic acids, the possibility of survival of this biomolecule on the Martian surface is of primary importance to the astrobiology community. Here, neat adenine and adenine-magnesium perchlorate mixtures were prepared and irradiated with energetic electrons that simulate the secondary electrons originating from the interaction of the galactic cosmic rays with the Martian surface. Perchlorates were added to the samples since they are abundant—and therefore relevant oxidizers on the surface of Mars—and they have been previously shown to facilitate the radiolysis of organics such as glycine. The degradation of the samples were monitored in situ via Fourier transformation infrared spectroscopy and the electron ionization quadruple mass spectrometric method; temperature-programmed desorption profiles were then collected by means of the state-of-the-art single photon photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS), allowing for the detection of the species subliming from the sample. The results showed that perchlorates do increase the destruction rate of adenine by opening alternative reaction channels, including the concurrent radiolysis/oxidation of the sample. This new pathway provides a plethora of different radiolysis products that were identified for the first time. These are carbon dioxide (CO2), isocyanic acid (HNCO), isocyanate (OCN-), carbon monoxide (CO), and nitrogen monoxide (NO); an oxidation product containing carbonyl groups (R1R2-C=O) with a constrained five-membered cyclic structure could also be observed. Cyanamide (H2N-C≡N) was detected in both irradiated samples as well.

High Surface Area MoS 2/Graphene Hybrid Aerogel for Ultrasensitive NO 2 Detection

DOE PAGES

Long, Hu; Harley-Trochimczyk, Anna; Pham, Thang; ...

2016-05-23

A MoS 2/graphene hybrid aerogel synthesized with two-dimensional MoS 2 sheets coating a high surface area graphene aerogel scaffold is characterized and used for ultrasensitive NO 2 detection. The combination of graphene and MoS 2 leads to improved sensing properties with the graphene scaffold providing high specific surface area and high electrical and thermal conductivity and the single to few-layer MoS2 sheets providing high sensitivity and selectivity to NO 2. The hybrid aerogel is integrated onto a low-power microheater platform to probe the gas sensing performance. At room temperature, the sensor exhibits an ultralow detection limit of 50 ppb NOmore » 2. By heating the material to 200 °C, the response and recovery times to reach 90% of the final signal decrease to <1 min, while retaining the low detection limit. The MoS 2/graphene hybrid also shows good selectivity for NO 2 against H 2 and CO, especially when compared to bare graphene aerogel. The unique structure of the hybrid aerogel is responsible for the ultrasensitive, selective, and fast NO 2 sensing. The improved sensing performance of this hybrid aerogel also suggests the possibility of other 2D material combinations for further sensing applications.« less

Ambient Seismic Noise Monitoring of Time-lapse Velocity Changes During CO2 Injection at Otway, South Australia

NASA Astrophysics Data System (ADS)

Saygin, E.; Lumley, D. E.

2017-12-01

We use continuous seismic data recorded with an array of 909 buried geophones at Otway, South Australia, to investigate the potential of using ambient seismic noise for time-lapse monitoring of the subsurface. The array was installed prior to a 15,000 ton CO2 injection in 2016-17, in order to detect and monitor the evolution of the injected CO2 plume, and any associated microseismic activity. Continuously recorded data from the vertical components of the geophone array were cross-correlated to retrieve the inter-station Green's functions. The dense collection of Green's functions contains diving body waves and surface Rayleigh waves. Green's Functions were then compared with each other at different time frames including the pre-injection period to track subtle changes in the travel times due to the CO2 injection. Our results show a clear change in the velocities of Green's functions at the start of injection for both body waves and surface waves for wave paths traversing the injection area, whereas the observed changes are much smaller for areas which are far from the injection well.

Potential for iron oxides to control metal releases in CO2 sequestration scenarios

USGS Publications Warehouse

Berger, P.M.; Roy, W.R.

2011-01-01

The potential for the release of metals into groundwater following the injection of carbon dioxide (CO2) into the subsurface during carbon sequestration projects remains an open research question. Changing the chemical composition of even the relatively deep formation brines during CO2 injection and storage may be of concern because of the recognized risks associated with the limited potential for leakage of CO2-impacted brine to the surface. Geochemical modeling allows for proactive evaluation of site geochemistry before CO2 injection takes place to predict whether the release of metals from iron oxides may occur in the reservoir. Geochemical modeling can also help evaluate potential changes in shallow aquifers were CO2 leakage to occur near the surface. In this study, we created three batch-reaction models that simulate chemical changes in groundwater resulting from the introduction of CO2 at two carbon sequestration sites operated by the Midwest Geological Sequestration Consortium (MGSC). In each of these models, we input the chemical composition of groundwater samples into React??, and equilibrated them with selected mineral phases and CO 2 at reservoir pressure and temperature. The model then simulated the kinetic reactions with other mineral phases over a period of up to 100 years. For two of the simulations, the water was also at equilibrium with iron oxide surface complexes. The first model simulated a recently completed enhanced oil recovery (EOR) project in south-central Illinois in which the MGSC injected into, and then produced CO2, from a sandstone oil reservoir. The MGSC afterwards periodically measured the brine chemistry from several wells in the reservoir for approximately two years. The sandstone contains a relatively small amount of iron oxide, and the batch simulation for the injection process showed detectable changes in several aqueous species that were attributable to changes in surface complexation sites. After using the batch reaction configuration to match measured geochemical changes due to CO2 injection, we modeled potential changes in groundwater chemistry at the Illinois Basin - Decatur Project (IBDP) site in Decatur, Illinois, USA. At the IBDP, the MGSC will inject 1 million tonnes of CO2 over the course of three years at a depth of about 2 km below the surface into the Mt. Simon Formation. Sections of the Mt. Simon Formation contain up to 10 percent iron oxide, and therefore surface complexes on iron oxides should play a major role in controlling brine chemistry. The batch simulation of this system showed a significant decrease in pH after the injection of CO2 with corresponding changes in brine chemistry resulting from both mineral precipitation/dissolution reactions and changes in the chemistry on iron oxide surfaces. To ensure the safety of shallow drinking water sources, there are several shallow monitoring wells at the IBDP that the MGSC samples regularly to determine baseline chemical concentrations. Knowing what geochemical parameters are most sensitive to CO2 disturbances allows us to focus monitoring efforts. Modeling a major influx of CO2 into the shallow groundwater allowed us to determine that were an introduction of CO2 to occur, the only immediate effect will be dolomite dissolution and calcite precipitation. ?? 2011 Published by Elsevier Ltd.

Elevated carbon dioxide alters the plasma composition and behaviour of a shark.

PubMed

Green, Leon; Jutfelt, Fredrik

2014-09-01

Increased carbon emissions from fossil fuels are increasing the pCO2 of the ocean surface waters in a process called ocean acidification. Elevated water pCO2 can induce physiological and behavioural effects in teleost fishes, although there appear to be large differences in sensitivity between species. There is currently no information available on the possible responses to future ocean acidification in elasmobranch fishes. We exposed small-spotted catsharks (Scyliorhinus canicula) to either control conditions or a year 2100 scenario of 990 μatm pCO2 for four weeks. We did not detect treatment effects on growth, resting metabolic rate, aerobic scope, skin denticle ultrastructure or skin denticle morphology. However, we found that the elevated pCO2 group buffered internal acidosis via [Formula: see text] accumulation with an associated increase in Na(+), indicating that the blood chemistry remained altered despite the long acclimation period. The elevated pCO2 group also exhibited a shift in their nocturnal swimming pattern from a pattern of many starts and stops to more continuous swimming. Although CO2-exposed teleost fishes can display reduced behavioural asymmetry (lateralization), the CO2-exposed sharks showed increased lateralization. These behavioural effects may suggest that elasmobranch neurophysiology is affected by CO2, as in some teleosts, or that the sharks detect CO2 as a constant stressor, which leads to altered behaviour. The potential direct effects of ocean acidification should henceforth be considered when assessing future anthropogenic effects on sharks. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

THE DETECTION OF A HOT MOLECULAR CORE IN THE LARGE MAGELLANIC CLOUD WITH ALMA

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

Shimonishi, Takashi; Onaka, Takashi; Kawamura, Akiko

We report the first detection of a hot molecular core outside our Galaxy based on radio observations with ALMA toward a high-mass young stellar object (YSO) in a nearby low metallicity galaxy, the Large Magellanic Cloud (LMC). Molecular emission lines of CO, C{sup 17}O, HCO{sup +}, H{sup 13}CO{sup +}, H{sub 2}CO, NO, SiO, H{sub 2}CS, {sup 33}SO, {sup 32}SO{sub 2}, {sup 34}SO{sub 2}, and {sup 33}SO{sub 2} are detected from a compact region (∼0.1 pc) associated with a high-mass YSO, ST11. The temperature of molecular gas is estimated to be higher than 100 K based on rotation diagram analysis ofmore » SO{sub 2} and {sup 34}SO{sub 2} lines. The compact source size, warm gas temperature, high density, and rich molecular lines around a high-mass protostar suggest that ST11 is associated with a hot molecular core. We find that the molecular abundances of the LMC hot core are significantly different from those of Galactic hot cores. The abundances of CH{sub 3}OH, H{sub 2}CO, and HNCO are remarkably lower compared to Galactic hot cores by at least 1–3 orders of magnitude. We suggest that these abundances are characterized by the deficiency of molecules whose formation requires the hydrogenation of CO on grain surfaces. In contrast, NO shows a high abundance in ST11 despite the notably low abundance of nitrogen in the LMC. A multitude of SO{sub 2} and its isotopologue line detections in ST11 imply that SO{sub 2} can be a key molecular tracer of hot core chemistry in metal-poor environments. Furthermore, we find molecular outflows around the hot core, which is the second detection of an extragalactic protostellar outflow. In this paper, we discuss the physical and chemical characteristics of a hot molecular core in the low metallicity environment.« less

Vertical observation of molecular hydrogen and carbon monoxide: Implication for non-photochemical H2 production at ocean surface and subsurface

NASA Astrophysics Data System (ADS)

Kawagucci, S.; Narita, T.; Obata, H.; Ogawa, H.; Gamo, T.

2009-12-01

Biological nitrogen fixation is a key metabolism controlling marine N-cycling and also known as a main H2 source. Recently, it was proposed that a monitoring of surface H2 concentration could be used quickly to figure out the spatial extent of biological nitrogen fixation activity without onboard incubation required for currently used methods for detecting the activity. However, H2 behavior in ocean water was still unresolved. This study carried out vertical observation of H2 and CO concentrations in south of Japan, western North Pacific. Because carbon monoxide, CO, in seawater has no relation with nitrogen fixation metabolism and is produced dominantly by the photochemical reaction, which is an altanative H2 source, simultaneous observation and comparison of H2 and CO concentration is helpful to investigate H2 behavior in ocean water. Reductive gases in seawater were observed during the R/V Tansei-maru KT-08-14 cruise by using a wired CTD-CMS (CTD-carousel multiple sampling) system to conduct vertical sampling (at most 200 m depth) and by using a plastic bucket for sampling surface seawater. The sample in the Niskin-X bottle was directed to the bottom of a 120 mL brown-colored glass vial allowed to overflow by 2 volumes before the tube was slowly withdrawn. After the addition of 0.5 mL HgCl2-saturated solution for poisoning, the PTFE-lined butyl-gum septum was used to cap the vials. Molecular hydrogen (H2) and carbon monoxide (CO) were analyzed at an onboard laboratory within 6 hours after subsampling. 20 mL of sample water was substituted by 20 mL of H2- and CO-free air using a gas-tight syringe; then the vial was put on an automatic shaker and shaken upside down for 6 minutes to achieve a complete equilibrium between the dissolved and head space gases in the vial. The equilibrated headspace was taken by another gas-tight syringe and then injected into a gas chromatograph equipped with a trace reduced gas detector. Vertical distribution of dissolved H2 and CO concentration were observed. Apparently different vertical distributions between H2 and CO concentration were revealed at all the observed stations. At a station where N-nutrient was depleted through surface mixed layer, H2 was supersaturated at the surface while CO concentration was constant through the depths. In contrast, at another station where some amount of terrestrial humic matter was introduced into the surface, H2 concentration was constantly undersaturated through the depth while vertical distribution of CO concentration showed the highest at the surface and exponentially decreased to deep. These facts suggest that H2 production involved with nitrogen fixation played an important role for H2 behavior in ocean water while photochemical H2 production would be a minor process. In addition to the surface, H2 supersaturation accoumpanied with little CO concentration rise were observed at depths just below the mixed layer in pycnocline with Chlorophyll maximum.

Linking water and carbon cycles through salinity observed from space

NASA Astrophysics Data System (ADS)

Xie, X.; Liu, W. T.

2017-12-01

The association of ocean surface salinity in global hydrological cycle and climate change has been traditionally studied through the examination of its tendency and advection as manifestation of ocean's heat and water fluxes with the atmosphere. The variability of surface heat and water fluxes are linked to top of atmosphere radiation, whose imbalance is the main cause of global warming. Besides the link of salinity to greenhouse warming through water balance, this study will focus on the effect of changing salinity on carbon dioxide flux between the ocean and the atmosphere. We have built statistical models to estimate the partial pressure of carbon dioxide (pCO2) and ocean acidification (in terms of total alkalinity and pH) using spacebased data. PCO2 is a critical parameter governing ocean as source and sink of the accumulated greenhouse gas in the atmosphere. The exchange also causes ocean acidification, which is detrimental to marine lives and ecology. Before we had sufficient spacebased salinity measurements coincident with in situ pCO2 measurement, we trained our statistical models to use satellite sea surface temperature and chlorophyll, with one model using salinity climatology and the other without. We found significant differences between the two models in regions of strong water input through river discharge and surface water flux. The pCO2 output follows the seasonal salinity advection of the Amazon outflow. The seasonal salinity advection between Bay of Bengal and Arabian Sea are followed by change of pCO2 and total alkalinity. At shorter time scales, the signatures of rain associated with intraseasonal organized convection of summer monsoon can be detected. We have observed distribution agreement of among pCO2, surface salinity, and surface water flux for variation from a few days to a few years under the Pacific ITCZ; the agreement varies slightly with season and longitudes and the reason is under study.

Removal of Cr(VI) from groundwater by Fe(0)

NASA Astrophysics Data System (ADS)

Gao, Yanjiao; Liu, Rui

2017-11-01

This research was conducted to investigate the treatment of hexavalent chromium (Cr(VI)) by iron powder (Fe(0)) columns of simulated permeable reactive barriers with and without calcium carbonate (CaCO3). Two columns filled with Fe(0) were used as Cr(VI) removal equipment running at a flow velocity of 10 ml/min at room temperature. After 200 days running of the two columns, the results showed that Fe(0) was an effective material for Cr(VI) reduction with an average removal rate of above 84.6%. The performance of Column 2 with CaCO3 was better than Column 1 without CaCO3 in terms of average Cr(VI) removal rate. The presence of CaCO3 buffered the increasing pH caused by Fe(0) corrosion in Column 2 and enhanced the removal rate of Column 2. Scanning Electron Microscopy (SEM) images of Fe(0) in the three stages of running of the two columns illustrated that the coat layer of Column 1 was a little thicker than that of Column 2. Energy-dispersive spectrometry (EDS) results showed that the surface of Fe(0) of Column 2 contained more chromium elements. Raman spectroscopy found that all iron oxide was generated on the Fe(0) surface of Column 1 and Column 2 and chromium class objects were only detected on Fe(0) surface in Column 2.

Surface Condensation of CO2 onto Kaolinite

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

Schaef, Herbert T.; Glezakou, Vassiliki Alexandra; Owen, Antionette T.

2014-02-11

The fundamental adsorption behavior of gaseous and supercritical carbon dioxide (CO2) onto poorly crystalline kaolinite (KGa-2) at conditions relevant to geologic sequestration has been investigated using a quartz crystal microbalance (QCM) and density functional theory (DFT) methods. The QCM data indicated linear adsorption of CO2 (0-0.3 mmol CO2/g KGa-2) onto the kaolinite surface up through the gaseous state (0.186 g/cm3). However in the supercritical region, CO2 adsorption increases dramatically, reaching a peak (0.9-1.0 mmol CO2/g KGa-2) near 0.43 g/cm3, before declining rapidly to surface adsorption values equivalent or below gaseous CO2. This adsorption profile was not observed with He ormore » N2. Comparative density functional studies of CO2 interactions with kaolinite surface models rule out CO2 intercalation and confirm that surface adsorption is favored up to approximately 0.35 g/cm3 of CO2, showing distorted T-shaped CO2-CO2 clustering, typical of supercritical CO2 aggregation over the surface as the density increases. Beyond this point, the adsorption energy gain for any additional CO2 becomes less than the CO2 interaction energy (~0.2 eV) in the supercritical medium resulting in overall desorption of CO2 from the kaolinite surface.« less

Air-water CO2 and CH4 fluxes along a river-reservoir continuum: Case study in the Pengxi River, a tributary of the Yangtze River in the Three Gorges Reservoir, China.

PubMed

Huang, Yang; Yasarer, Lindsey M W; Li, Zhe; Sturm, Belinda S M; Zhang, Zengyu; Guo, Jinsong; Shen, Yu

2017-05-01

Water surface greenhouse gas (GHG) emissions in freshwater reservoirs are closely related to limnological processes in the water column. Affected by both reservoir operation and seasonal changes, variations in the hydro-morphological conditions in the river-reservoir continuum will create distinctive patterns in water surface GHG emissions. A one-year field survey was carried out in the Pengxi River-reservoir continuum, a part of the Three Gorges Reservoir (TGR) immediately after the TGR reached its maximum water level. The annual average water surface CO 2 and CH 4 emissions at the riverine background sampling sites were 6.23 ± 0.93 and 0.025 ± 0.006 mmol h -1  m -2 , respectively. The CO 2 emissions were higher than those in the downstream reservoirs. The development of phytoplankton controlled the downstream decrease in water surface CO 2 emissions. The presence of thermal stratification in the permanent backwater area supported extensive phytoplankton blooms, resulting in a carbon sink during several months of the year. The CH 4 emissions were mainly impacted by water temperature and dissolved organic carbon. The greatest water surface CH 4 emission was detected in the fluctuating backwater area, likely due to a shallower water column and abundant organic matter. The Pengxi River backwater area did not show significant increase in water surface GHG emissions reported in tropical reservoirs. In evaluating the net GHG emissions by the impoundment of TGR, the net change in the carbon budget and the contribution of nitrogen and phosphorus should be taken into consideration in this eutrophic river-reservoir continuum.

Detecting structural variances of Co 3O 4 catalysts by controlling beam-induced sample alterations in the vacuum of a transmission electron microscope

DOE PAGES

Kisielowski, C.; Frei, H.; Specht, P.; ...

2016-11-02

This article summarizes core aspects of beam-sample interactions in research that aims at exploiting the ability to detect single atoms at atomic resolution by mid-voltage transmission electron microscopy. Investigating the atomic structure of catalytic Co 3O 4 nanocrystals underscores how indispensable it is to rigorously control electron dose rates and total doses to understand native material properties on this scale. We apply in-line holography with variable dose rates to achieve this goal. Genuine object structures can be maintained if dose rates below ~100 e/Å 2s are used and the contrast required for detection of single atoms is generated by capturing largemore » image series. Threshold doses for the detection of single atoms are estimated. An increase of electron dose rates and total doses to common values for high resolution imaging of solids stimulates object excitations that restructure surfaces, interfaces, and defects and cause grain reorientation or growth. We observe a variety of previously unknown atom configurations in surface proximity of the Co 3O 4 spinel structure. These are hidden behind broadened diffraction patterns in reciprocal space but become visible in real space by solving the phase problem. Finallly, an exposure of the Co 3O 4 spinel structure to water vapor or other gases induces drastic structure alterations that can be captured in this manner.« less

Measurements of CO2 Column Abundance in the Low Atmosphere Using Ground Based 1.6 μm CO2 DIAL

NASA Astrophysics Data System (ADS)

Abo, M.; Shibata, Y.; Nagasawa, C.

2017-12-01

Changes in atmospheric carbon dioxide (CO2) concentration are believed to produce the largest radiative forcing for the current climate system. Accurate predictions of atmospheric CO2 concentration rely on the knowledge of its sinks and sources, transports, and its variability with time. Although this knowledge is currently unsatisfactory, numerical models use it as a way in simulating CO2 fluxes. Validating and improving the global atmospheric transport model, therefore, requires precise measurement of the CO2 concentration profile. There are two further variations on Lidar: the differential absorption Lidar (DIAL) and the integrated path differential absorption (IPDA) Lidar. DIAL/IPDA are basically for profile/total column measurement, respectively. IPDA is a special case of DIAL and can measure the total column-averaged mixing ratio of trace gases using return signals from the Earth's surface or from thick clouds based on an airborne or a satellite. We have developed a ground based 1.6 μm DIAL to measure vertical CO2 mixing ratio profiles from 0.4 to 2.5 km altitude. The goals of the CO2 DIAL are to produce atmospheric CO2 mixing ratio measurements with much smaller seasonal and diurnal biases from the ground surface. But, in the ground based lidar, return signals from around ground surface are usually suppressed in order to handle the large dynamic range. To receive the return signals as near as possible from ground surface, namely, the field of view (FOV) of the telescope must be wide enough to reduce the blind range of the lidar. While the return signals from the far distance are very weak, to enhance the sensitivity and heighten the detecting distance, the FOV must be narrow enough to suppress the sky background light, especially during the daytime measurements. To solve this problem, we propose a total column measurement method from the ground surface to 0.4 km altitude. Instead of strong signals from thick clouds such as the IPDA, the proposed method uses atmospheric return signals from 0.4 km altitude. Although laser outputs of two wavelengths, which are the system parameter of DIAL, are canceled, the proposed method needs to constantly monitor laser outputs. When the laser output ratio with two wavelengths is 1.0 ± 0.01, the error simulation result of the CO2 mixing ratio is 420.0 ± 3.9 ppm.

Amplified electrochemiluminescence of luminol based on hybridization chain reaction and in situ generate co-reactant for highly sensitive immunoassay.

PubMed

Xiao, Lijuan; Chai, Yaqin; Yuan, Ruo; Cao, Yaling; Wang, Haijun; Bai, Lijuan

2013-10-15

In this work, we described a simple and highly sensitive electrochemiluminescence (ECL) strategy for IgG detection. Firstly, L-cysteine functionalized reduced graphene oxide composite (L-cys-rGO) was decorated on the glassy carbon electrode (GCE) surface. Then anti-IgG was immobilized on the modified electrode surface through the interaction between the carboxylic groups of the L-cys-rGO and the amine groups in anti-IgG. And then biotinylated anti-IgG (bio-anti-IgG) was assembled onto the electrode surface based on the sandwich-type immunoreactions. By the conjunction of biotin and streptavidin (SA), SA was immobilized, which in turn, combined with the biotin labeled initiator strand (S1). In the presence of two single DNA strands of glucose oxidase labeled S2 (GOD-S2) and complementary strand (S3), S1 could trigger the hybridization chain reaction (HCR) among S1, GOD-S2 and S3. Herein, due to HCR, numerous GOD was efficiently immobilizated on the sensing surface and exhibited excellent catalysis towards glucose to in situ generate amounts of hydrogen peroxide (H2O2), which acted as luminol's co-reactant to significantly enhance the ECL signal. The proposed ECL immunosensor presented predominate stability and high sensibility for determination of IgG in the range from 0.1 pg mL(-1) to 100 ng mL(-1) with a detection limit of 33 fg mL(-1) (S/N=3). Additionally, the designed ECL immunosensor exhibited a promising application for other protein detection. Copyright © 2013 Elsevier B.V. All rights reserved.

Airborne Lidar measurements of Atmospheric CO2 Column Absorption and Line Shapes from 3-11 km altitudes

NASA Astrophysics Data System (ADS)

Abshire, J. B.; Riris, H.; Allan, G. R.; Weaver, C.; Mao, J.; Hasselbrack, W.

2009-04-01

Accurate measurements of tropospheric CO2 abundances with global-coverage are needed to quantify processes that regulate CO2 exchange with the land and oceans. The 2007 Decadal Survey for Earth Science by the US National Research Council recommended a space-based CO2 measuring mission called ASCENDS. We have been developing a technique for the remote measurement of tropospheric CO2 concentrations from aircraft and as a candidate for the ASCENDS mission. It uses the 1570-nm CO2 band and a dual channel laser absorption spectrometer (ie DIAL used in altimeter mode). It uses several tunable laser transmitters allowing simultaneous measurement of the absorption from a CO2 absorption line in the 1570 nm band, O2 extinction in the oxygen A-band, and surface height and aerosol backscatter in the same path. It directs the narrow co-aligned laser beams toward nadir, and measures the energy of the laser echoes reflected from land and water surfaces. During the measurement, the lasers are stepped in wavelength across the CO2 line and an O2 line (near 765 nm) at a ~ 1 kHz rate. The receiver uses a telescope and photon counting detectors, and measures the background light and energies of the laser echoes from the surface along with scattering from any aerosols in the path. The gas extinction and column densities for the CO2 and O2 gases are estimated from the ratio of the on- and off- line signals via the DIAL technique. We use pulsed laser signals and time gating to isolate the laser echo signals from the surface, and to reject photons scattered from thin clouds and aerosols in the path. Previously we had constructed breadboard versions of our CO2 and O2 sensors, using tunable diode lasers, fiber laser amplifiers and 20 cm diameter telescopes. We have used them to make measurements of gas absorptions over 0.2, 0.4 and 1.3 km long outdoor paths. We also have also calculated several characteristics of the technique for space and have performed an initial space mission accommodation study. During 2008 we reconfigured our lidar for airborne use and made measurements of atmospheric CO2 absorption in the nadir column from the aircraft to the surface during 5 flights. The airborne lidar sweeps the laser wavelength across the CO2 line in either 10 or 20 steps per measurement. The line scan rate is ~ 1 KHz and the laser pulse widths are 1 usec. The time resolved laser backscatter is collected by the telescope and detected by a photomultiplier and recorded by a photon counting timing system. We installed our lidar on the NASA Glenn Lear-25 aircraft in October and first made measurements using the 1571.4 nm CO2 absorption line while flying in northern Ohio. We made laser backscatter and absorption measurements over a variety of land surface types, water surfaces and through thin clouds, broken clouds and to cloud tops. Strong laser signals were observed at altitudes from 2.5 to 11 km on two flights. We completed three additional flights during December 2008 and gathered over 6 hours of atmospheric CO2 column measurements using the 1572.02 and 1572.33 nm CO2 lines. Airborne CO2 line shape and absorption measurements were made while flying at 3-11 km altitudes over southwestern Ohio. Subsequently two flights were made from Ponca City OK, just east of the US Department of Energy's (DOE) ARM site. We made 4 hours of airborne measurements in square patterns around the ARM site at altitudes from 3-8 km. The increased CO2 line absorptions at higher altitudes were evident in all flights. The December flights were also coordinated with DOE investigators who flew an in-situ CO2 sensor on a Cessna aircraft inside the CO2 sounder's flight pattern. These yielded two height resolved profiles of CO2 concentrations from 5 km to the surface, which are being analyzed with radiosonde measurements for comparisons. More details of the flights, measurements and their analysis will be described in the presentation.

Electrochemical and density functional theory investigation on the differential behaviors of core-ring structured NiCo2O4 nanoplatelets toward heavy metal ions.

PubMed

Liao, Jianjun; Zhang, Junping; Wang, Cai-Zhuang; Lin, Shiwei

2018-08-31

In order to further improve the electroanalytical performance toward heavy metal ions, core-ring structured NiCo 2 O 4 nanoplatelets were used to modify glass carbon electrode (GCE) for the determination of heavy metal ions in water. Owing to the high surface area of NiCo 2 O 4 nanoplatelets, the Pb(II) sensitivity increased by a factor of 1.70, and the detection limit decreased by a factor of 2.64 as compared to solid NiCo 2 O 4 nanoparticles modified GCE. Interestingly, NiCo 2 O 4 nanoplatelets showed different sensitivities toward heavy metal ions with the same valence states, following the order Pb(II) > Cd(II) > Hg(II) > Cu(II). To better and scientifically understand the difference in sensitivity, adsorption and desorption abilities were integrated into account. Density functional theory calculations verified that the adsorption capability of NiCo 2 O 4 toward Pb(II) was strongest among all heavy metal ions, thereby resulting in the largest sensitivity. Further desorption current measurements indicated the large desorption barrier of Cu(II) was another important factor leading to its lowest sensitivity. Finally, the applicability of the proposed method was demonstrated by the detection of heavy metal ions in real seawater. Copyright © 2018 Elsevier B.V. All rights reserved.

CoxFe1-x oxide coatings on metallic interconnects for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shen, Fengyu; Lu, Kathy

2016-10-01

In order to improve the performance of Cr-containing steel as an interconnect material for solid oxide fuel cells, CoFe alloy coatings with Co:Fe ratios of 9:1, 8:2, 7:3, 6:4, and 5:5 are deposited by electrodeposition and then oxidized to CoxFe1-x oxide coatings with a thickness of ∼6 μm as protective layers on the interconnect. The area specific resistance of the coated interconnect increases with the Fe content. Higher Co content oxide coatings are more effective in limiting the growth of the chromia scale while all coatings are effective in inhibiting Cr diffusion and evaporation. With the Co0.8Fe0.2 oxide coated interconnect, the electrochemical performance of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode is improved. Only 1.54 atomic percentage of Cr is detected on the surface of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode while no Cr is detected 0.66 μm or more into the cathode. CoxFe1-x oxide coatings are promising candidates for solid oxide fuel cell interconnects with the advantage of using existing cathode species for compatibility and performance enhancement.

Structure and Dynamics of Forsterite-scCO2/H2O Interfaces as a Function of Water Content

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

Kerisit, Sebastien N.; Weare, John H.; Felmy, Andrew R.

Molecular dynamics (MD) simulations of forsterite surfaces in contact with supercritical carbon dioxide (scCO2) fluids of varying water content were performed to determine the partition of water between the scCO2 fluid and the mineral surface, the nature of CO2 and H2O bonding at the interface, and the regions of the interface that may be conducive to HxCO3(2-x)- formation. Calculations of the free energy of the associative adsorption of water onto the (010) forsterite surface from the scCO2 phase indicated that the formation of a water film up to three-monolayer thick can be exothermic even for water contents below the watermore » saturation concentration of the scCO2 fluid. In MD simulations of scCO2/H2O mixtures in contact with the (010) forsterite surface, H2O was found to readily displace CO2 at the surface and, therefore, CO2 directly contacted the surface only for water coverages below two monolayers. For thicker water films, a two-monolayer hydration layer formed that CO2 could not penetrate. Simulations of the hydroxylated (010) surface and of the (011) surface suggested that this conclusion can be extended to forsterite surfaces with different surface structures and/or compositions. The density, diffusion, and degree of hydration of CO2 as well as the extent of CO2/H2O mixing at the interface were all predicted to depend strongly on the thickness of the water-rich film, i.e., on the water content of the scCO2 fluid.« less

Photoactive roadways: Determination of CO, NO and VOC uptake coefficients and photolabile side product yields on TiO2 treated asphalt and concrete

NASA Astrophysics Data System (ADS)

Toro, C.; Jobson, B. T.; Haselbach, L.; Shen, S.; Chung, S. H.

2016-08-01

This work reports uptake coefficients and by-product yields of ozone precursors onto two photocatalytic paving materials (asphalt and concrete) treated with a commercial TiO2 surface application product. The experimental approach used a continuously stirred tank reactor (CSTR) and allowed for testing large samples with the same surface morphology encountered with real urban surfaces. The measured uptake coefficient (γgeo) and surface resistances are useful for parametrizing dry deposition velocities in air quality model evaluation of the impact of photoactive surfaces on urban air chemistry. At 46% relative humidity, the surface resistance to NO uptake was ∼1 s cm-1 for concrete and ∼2 s cm-1 for a freshly coated older roadway asphalt sample. HONO and NO2 were detected as side products from NO uptake to asphalt, with NO2 molar yields on the order of 20% and HONO molar yields ranging between 14 and 33%. For concrete samples, the NO2 molar yields increased with the increase of water vapor, ranging from 1% to 35% and HONO was not detected as a by-product. Uptake of monoaromatic VOCs to the asphalt sample set displayed a dependence on the compound vapor pressure, and was influenced by competitive adsorption from less volatile VOCs. Formaldehyde and acetaldehyde were detected as byproducts, with molar yields ranging from 5 to 32%.

Change detection and classification of land cover in multispectral satellite imagery using clustering of sparse approximations (CoSA) over learned feature dictionaries

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

Moody, Daniela I.; Brumby, Steven P.; Rowland, Joel C.

Neuromimetic machine vision and pattern recognition algorithms are of great interest for landscape characterization and change detection in satellite imagery in support of global climate change science and modeling. We present results from an ongoing effort to extend machine vision methods to the environmental sciences, using adaptive sparse signal processing combined with machine learning. A Hebbian learning rule is used to build multispectral, multiresolution dictionaries from regional satellite normalized band difference index data. Land cover labels are automatically generated via our CoSA algorithm: Clustering of Sparse Approximations, using a clustering distance metric that combines spectral and spatial textural characteristics tomore » help separate geologic, vegetative, and hydrologie features. We demonstrate our method on example Worldview-2 satellite images of an Arctic region, and use CoSA labels to detect seasonal surface changes. In conclusion, our results suggest that neuroscience-based models are a promising approach to practical pattern recognition and change detection problems in remote sensing.« less

Change detection and classification of land cover in multispectral satellite imagery using clustering of sparse approximations (CoSA) over learned feature dictionaries

DOE PAGES

Moody, Daniela I.; Brumby, Steven P.; Rowland, Joel C.; ...

2014-10-01

Neuromimetic machine vision and pattern recognition algorithms are of great interest for landscape characterization and change detection in satellite imagery in support of global climate change science and modeling. We present results from an ongoing effort to extend machine vision methods to the environmental sciences, using adaptive sparse signal processing combined with machine learning. A Hebbian learning rule is used to build multispectral, multiresolution dictionaries from regional satellite normalized band difference index data. Land cover labels are automatically generated via our CoSA algorithm: Clustering of Sparse Approximations, using a clustering distance metric that combines spectral and spatial textural characteristics tomore » help separate geologic, vegetative, and hydrologie features. We demonstrate our method on example Worldview-2 satellite images of an Arctic region, and use CoSA labels to detect seasonal surface changes. In conclusion, our results suggest that neuroscience-based models are a promising approach to practical pattern recognition and change detection problems in remote sensing.« less

A low-luminosity type-1 QSO sample . IV. Molecular gas contents and conditions of star formation in three nearby Seyfert galaxies

NASA Astrophysics Data System (ADS)

Moser, Lydia; Krips, Melanie; Busch, Gerold; Scharwächter, Julia; König, Sabine; Eckart, Andreas; Smajić, Semir; García-Marin, Macarena; Valencia-S., Mónica; Fischer, Sebastian; Dierkes, Jens

2016-03-01

We present a pilot study of ~3'' resolution observations of low CO transitions with the Submillimeter Array in three nearby Seyfert galaxies, which are part of the low-luminosity quasi-stellar object (LLQSOs) sample consisting of 99 nearby (z = 0.06) type-1 active galactic nuclei (AGN) taken from the Hamburg/ESO quasi-stellar object (QSO) survey. Two sources were observed in 12CO(2-1) and 13CO(2-1) and the third in 12CO(3-2) and HCO+(4-3). None of the sources is detected in continuum emission. More than 80% of the 12CO detected molecular gas is concentrated within a diameter (FWHM) < 1.8 kpc. 13CO is tentatively detected, while HCO+ emission could not be detected. All three objects show indications of a kinematically decoupled central unresolved molecular gas component. The molecular gas masses of the three galaxies are in the range Mmol = (0.7-8.7) × 109M⊙. We give lower limits for the dynamical masses of Mdyn> 1.5 × 109M⊙ and for the dust masses of Mdust> 1.6 × 106M⊙. The R21 = 12CO/13CO(2-1) line luminosity ratios show Galactic values of R21 ~ 5-7 in the outskirts and R21 ≳ 20 in the central region, similar to starbursts and (ultra)luminous infrared galaxies ((U)LIRGs; I.e. LIRGs and ULIRGs), implying higher temperatures and stronger turbulence. All three sources show indications of 12CO(2-1)/12CO(1-0) ratios of ~0.5, suggesting a cold or diffuse gas phase. Strikingly, the 12CO(3-2)/(1-0) ratio of ~1 also indicates a higher excited phase. Since these galaxies have high infrared luminosities of LIR ≥ 1011L⊙ and seem to contain a circumnuclear starburst with minimum surface densities of gas and star formation rate (SFR) around Σmol = 50-550 M⊙pc-2 and ΣSFR = 1.1-3.1 M⊙ kpc-2 yr-1, we conclude that the interstellar medium in the centers of these LIRG Seyferts is strongly affected by violent star formation and better described by the ULIRG mass conversion factor.

Organic Combustion in the Presence of Ca-Carbonate and Mg-Perchlorate: A Possible Source for the Low Temperature CO2 Release Seen in Mars Phoenix Thermal and Evolved Gas Analyzer Data

NASA Technical Reports Server (NTRS)

Archer, Douglas; Ming, D.; Niles, P.; Sutter, B.; Lauer, H.

2012-01-01

Two of the most important discoveries of the Phoenix Lander were the detection of approx.0.6% perchlorate [1] and 3-5% carbonate [2] in landing site soils. The Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander could heat samples up to approx.1000 C and monitor evolved gases with a mass spectrometer. TEGA detected a low (approx.350 C) and high (approx.750 C) temperature CO2 release. The high temp release was attributed to the thermal decomposition of Ca-carbonate (calcite). The low temperature CO2 release could be due to desorption of CO2, decomposition of a different carbonate mineral, or the combustion of organic material. A new hypothesis has also been proposed that the low temperature CO2 release could be due to the early breakdown of calcite in the presence of the decomposition products of certain perchlorate salts [3]. We have investigated whether or not this new hypothesis is also compatible with organic combustion. Magnesium perchlorate is stable as Mg(ClO4)2-6H2O on the martian surface [4]. During thermal decomposition, this perchlorate salt releases H2O, Cl2, and O2 gases. The Cl2 can react with water to form HCl which then reacts with calcite, releasing CO2 below the standard thermal decomposition temperature of calcite. However, when using concentrations of perchlorate and calcite similar to what was detected by Phoenix, the ratio of high:low temperature CO2 evolved is much larger in the lab, indicating that although this process might contribute to the low temp CO2 release, it cannot account for all of it. While H2O and Cl2 cause calcite decomposition, the O2 evolved during perchlorate decomposition can lead to the combustion of any reduced carbon present in the sample [5]. We investigate the possible contribution of organic molecules to the low temperature CO2 release seen on Mars.

Excitation of luminescence of the nanoporous bioactive nanocrystalline carbonate-substituted hydroxyapatite for early tooth disease detection

NASA Astrophysics Data System (ADS)

Goloshchapov, D. L.; Minakov, D. A.; Domashevskaya, E. P.; Seredin, P. V.

This paper deals with the luminescence characteristics of an analogue of the mineral component of dental enamel of the nanocrystalline B-type carbonate-substituted hydroxyapatite (CHAP) with 3D defects (i.e. nanopores of ∼2-5 nm) on the nanocrystalline surface. The laser-induced luminescence (LIL) of the synthesized CHAP samples was in the range of ∼515 nm (∼2.4 eV) and is due to CO3 groups replacing the PO4 group. It was found that the intensity of the luminescence of the CHAP is caused by structurally incorporated CO3 groups in the HAP structure. Furthermore, the intensity of the luminescence also decreases as the number of the above intracentre defects (CO3) in the apatite structure declines. These results are potentially promising for developing the foundations for precise methods for the early detection of caries in human solid dental tissue.

Study of the nanoporous CHAP photoluminiscence for developing the precise methods of early caries detection

NASA Astrophysics Data System (ADS)

Goloshchapov, D.; Seredin, P.; Minakov, D.; Domashevskaya, E.

2018-02-01

This paper deals with the luminescence characteristics of an analogue of the mineral component of dental enamel of the nanocrystalline B-type carbonate-substituted hydroxyapatite (CHAP) with 3D defects (i.e. nanopores of ∼2-5 nm) on the nanocrystalline surface. The laser-induced luminescence of the synthesized CHAP samples was in the range of ∼515 nm (∼2.4 eV) and is due to CO3 groups replacing the PO4 group. It was found that the intensity of the luminescence of the CHAP is caused by structurally incorporated CO3 groups in the HAP structure. Furthermore, the intensity of the luminescence also decreases as the number of the above intracentre defects (CO3) in the apatite structure declines. These results are potentially promising for developing the foundations for precise methods for the early detection of caries in human solid dental tissue.

In-Situ MVA of CO 2 Sequestration Using Smart Field Technology

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

Mohaghegh, Shahab D.

2014-09-01

Capability of underground carbon dioxide storage to confine and sustain injected CO 2 for a long period of time is the main concern for geologic CO 2 sequestration. If a leakage from a geological CO 2 sequestration site occurs, it is crucial to find the approximate amount and the location of the leak, in a timely manner, in order to implement proper remediation activities. An overwhelming majority of research and development for storage site monitoring has been concentrated on atmospheric, surface or near surface monitoring of the sequestered CO 2 . This study aims to monitor themore » integrity of CO 2 storage at the reservoir level. This work proposes developing in-situ CO 2 Monitoring and Verification technology based on the implementation of Permanent Down-hole Gauges (PDG) or “Smart Wells” along with Artificial Intelligence and Data Mining (AI&DM). The technology attempts to identify the characteristics of the CO 2 leakage by de-convolving the pressure signals collected from Permanent Down-hole Gauges (PDG). Citronelle field, a saline aquifer reservoir, located in the U.S. was considered as the basis for this study. A reservoir simulation model for CO 2 sequestration in the Citronelle field was developed and history matched. PDGs were installed, and therefore were considered in the numerical model, at the injection well and an observation well. Upon completion of the history matching process, high frequency pressure data from PDGs were generated using the history matched numerical model using different CO 2 leakage scenarios. Since pressure signal behaviors were too complicated to de-convolute using any existing mathematical formulations, a Machine Learning-based technology was introduced for this purpose. An Intelligent Leakage Detection System (ILDS) was developed as the result of this effort using the machine learning and pattern recognition technologies. The ILDS is able to detect leakage characteristics in a short period of time (less than a day from its occurrence) demonstrating the capability of the system in quantifying leakage characteristics subject to complex rate behaviors. The performance of ILDS is examined under different conditions such as multiple well leakages, cap rock leakage, availability of an additional monitoring well, presence of pressure drift and noise in the pressure sensor and uncertainty in the reservoir model.« less

Surface thermodynamic stability, electronic and magnetic properties in various (001) surfaces of Zr2CoSn Heusler alloy

NASA Astrophysics Data System (ADS)

Yang, Yan; Feng, Zhong-Ying; Zhang, Jian-Min

2018-05-01

The spin-polarized first-principles are used to study the surface thermodynamic stability, electronic and magnetic properties in various (001) surfaces of Zr2CoSn Heusler alloy, and the bulk Zr2CoSn Heusler alloy are also discussed to make comparison. The conduction band minimum (CBM) of half-metallic (HM) bulk Zr2CoSn alloy is contributed by ZrA, ZrB and Co atoms, while the valence band maximum (VBM) is contributed by ZrB and Co atoms. The SnSn termination is the most stable surface with the highest spin polarizations P = 77.1% among the CoCo, ZrCo, ZrZr, ZrSn and SnSn terminations of the Zr2CoSn (001) surface. In the SnSn termination of the Zr2CoSn (001) surface, the atomic partial density of states (APDOS) of atoms in the surface, subsurface and third layers are much influenced by the surface effect and the total magnetic moment (TMM) is mainly contributed by the atomic magnetic moments of atoms in fourth to ninth layers.

Plant-Sediment Interactions in Salt Marshes - An Optode Imaging Study of O2, pH, and CO 2 Gradients in the Rhizosphere.

PubMed

Koop-Jakobsen, Ketil; Mueller, Peter; Meier, Robert J; Liebsch, Gregor; Jensen, Kai

2018-01-01

In many wetland plants, belowground transport of O 2 via aerenchyma tissue and subsequent O 2 loss across root surfaces generates small oxic root zones at depth in the rhizosphere with important consequences for carbon and nutrient cycling. This study demonstrates how roots of the intertidal salt-marsh plant Spartina anglica affect not only O 2 , but also pH and CO 2 dynamics, resulting in distinct gradients of O 2 , pH, and CO 2 in the rhizosphere. A novel planar optode system (VisiSens TD ® , PreSens GmbH) was used for taking high-resolution 2D-images of the O 2 , pH, and CO 2 distribution around roots during alternating light-dark cycles. Belowground sediment oxygenation was detected in the immediate vicinity of the roots, resulting in oxic root zones with a 1.7 mm radius from the root surface. CO 2 accumulated around the roots, reaching a concentration up to threefold higher than the background concentration, and generally affected a larger area within a radius of 12.6 mm from the root surface. This contributed to a lowering of pH by 0.6 units around the roots. The O 2 , pH, and CO 2 distribution was recorded on the same individual roots over diurnal light cycles in order to investigate the interlinkage between sediment oxygenation and CO 2 and pH patterns. In the rhizosphere, oxic root zones showed higher oxygen concentrations during illumination of the aboveground biomass. In darkness, intraspecific differences were observed, where some plants maintained oxic root zones in darkness, while others did not. However, the temporal variation in sediment oxygenation was not reflected in the temporal variations of pH and CO 2 around the roots, which were unaffected by changing light conditions at all times. This demonstrates that plant-mediated sediment oxygenation fueling microbial decomposition and chemical oxidation has limited impact on the dynamics of pH and CO 2 in S. anglica rhizospheres, which may in turn be controlled by other processes such as root respiration and root exudation.

Photocatalytic reduction of CO2 with H2O to CH4 on Cu(I) supported TiO2 nanosheets with defective {001} facets.

PubMed

Zhu, Shuying; Liang, Shijing; Tong, Yuecong; An, Xiaohan; Long, Jinlin; Fu, Xianzhi; Wang, Xuxu

2015-04-21

Highly dispersed Cu2O clusters loaded on TiO2 nanosheets with dominant exposed {001} facets are prepared by a hydrothermal treatment followed by photodeposition. The physicochemical properties of the as-prepared samples are characterized carefully. The deposition position and chemical state of the Cu2O clusters are characterized by X-ray diffraction, transmission electron microscopy, UV-vis diffuse reflectance spectroscopy, EPR spectroscopy, and in situ CO-adsorbed FTIR spectroscopy, respectively. The results show that in situ Cu deposition leads to in situ formation of abundant oxygen vacancies (Vo) on the surface of the TiO2 nanosheets. Interestingly, the co-existence of Vo and Cu2O clusters could promote the photoactivity of CO2 reduction efficiently. The surface Vo play a significant role in the reduction of CO2. Meanwhile, the deposited Cu(I) species serve also as active sites for the formation of CH4, and then protect CH4 from degradation by generated oxidation species. For the photoreduction of CO2 to CH4, it is found that the content level of Cu2O has a significant influence on the activity. Cu-TiO2-1.0 shows the highest photocatalytic activity, which is over 30 times higher than that of the parent TiO2. This great enhancement of photocatalytic activity may be contributed by high CO2 adsorption capacity, high electron mobility, and high concentration of Vo. However, the effect of the surface area of the samples on the activity is negligible. All of this evidence is obtained by CO2-sorption, electrochemistry, in situ FTIR spectroscopy, in situ ERP techniques, etc. The reaction intermediates are detected by in situ FTIR spectroscopy. Finally, a probable mechanism is proposed based on the experimental results. It is hoped that our work could render one of the most effective strategies to achieve advanced properties over photofunctional materials for solar energy conversion of CO2.

Modeling of time-lapse multi-scale seismic monitoring of CO2 injected into a fault zone to enhance the characterization of permeability in enhanced geothermal systems

NASA Astrophysics Data System (ADS)

Zhang, R.; Borgia, A.; Daley, T. M.; Oldenburg, C. M.; Jung, Y.; Lee, K. J.; Doughty, C.; Altundas, B.; Chugunov, N.; Ramakrishnan, T. S.

2017-12-01

Subsurface permeable faults and fracture networks play a critical role for enhanced geothermal systems (EGS) by providing conduits for fluid flow. Characterization of the permeable flow paths before and after stimulation is necessary to evaluate and optimize energy extraction. To provide insight into the feasibility of using CO2 as a contrast agent to enhance fault characterization by seismic methods, we model seismic monitoring of supercritical CO2 (scCO2) injected into a fault. During the CO2 injection, the original brine is replaced by scCO2, which leads to variations in geophysical properties of the formation. To explore the technical feasibility of the approach, we present modeling results for different time-lapse seismic methods including surface seismic, vertical seismic profiling (VSP), and a cross-well survey. We simulate the injection and production of CO2 into a normal fault in a system based on the Brady's geothermal field and model pressure and saturation variations in the fault zone using TOUGH2-ECO2N. The simulation results provide changing fluid properties during the injection, such as saturation and salinity changes, which allow us to estimate corresponding changes in seismic properties of the fault and the formation. We model the response of the system to active seismic monitoring in time-lapse mode using an anisotropic finite difference method with modifications for fracture compliance. Results to date show that even narrow fault and fracture zones filled with CO2 can be better detected using the VSP and cross-well survey geometry, while it would be difficult to image the CO2 plume by using surface seismic methods.

Perovskite nanoparticle-sensitized Ga 2O 3 nanorod arrays for CO detection at high temperature

DOE PAGES

Lin, Hui -Jan; Baltrus, John P.; Gao, Haiyong; ...

2016-04-04

Here, noble metal nanoparticles are extensively used for sensitizing metal oxide chemical sensors through the catalytic spillover mechanism. However, due to earth-scarcity and high cost of noble metals, finding replacements presents a great economic benefit. Besides, high temperature and harsh environment sensor applications demand material stability under conditions approaching thermal and chemical stability limits of noble metals. In this study, we employed thermally stable perovskite-type La 0.8Sr 0.2FeO 3 (LSFO) nanoparticle surface decoration on Ga 2O 3 nanorod array gas sensors and discovered an order of magnitude enhanced sensitivity to carbon monoxide at 500 °C. The LSFO nanoparticle catalysts wasmore » of comparable performance to that achieved by Pt nanoparticles, with a much lower weight loading than Pt. Detailed electron microscopy and X-ray photoelectron spectroscopy studies suggested the LSFO nanoparticle sensitization effect is attributed to a spillover-like effect associated with the gas-LSFO-Ga 2O 3 triple-interfaces that spread the negatively charged surface oxygen ions from LSFO nanoparticles surfaces over to β-Ga 2O 3 nanorod surfaces with faster surface CO oxidation reactions.« less

Perovskite Nanoparticle-Sensitized Ga2O3 Nanorod Arrays for CO Detection at High Temperature.

PubMed

Lin, Hui-Jan; Baltrus, John P; Gao, Haiyong; Ding, Yong; Nam, Chang-Yong; Ohodnicki, Paul; Gao, Pu-Xian

2016-04-13

Noble metal nanoparticles are extensively used for sensitizing metal oxide chemical sensors through the catalytic spillover mechanism. However, due to earth-scarcity and high cost of noble metals, finding replacements presents a great economic benefit. Besides, high temperature and harsh environment sensor applications demand material stability under conditions approaching thermal and chemical stability limits of noble metals. In this study, we employed thermally stable perovskite-type La(0.8)Sr(0.2)FeO3 (LSFO) nanoparticle surface decoration on Ga2O3 nanorod array gas sensors and discovered an order of magnitude enhanced sensitivity to carbon monoxide at 500 °C. The LSFO nanoparticle catalysts was of comparable performance to that achieved by Pt nanoparticles, with a much lower weight loading than Pt. Detailed electron microscopy and X-ray photoelectron spectroscopy studies suggested the LSFO nanoparticle sensitization effect is attributed to a spillover-like effect associated with the gas-LSFO-Ga2O3 triple-interfaces that spread the negatively charged surface oxygen ions from LSFO nanoparticles surfaces over to β-Ga2O3 nanorod surfaces with faster surface CO oxidation reactions.

Layered double hydroxide-enhanced luminescence in a Fenton-like system for selective sensing of cobalt in Hela cells

NASA Astrophysics Data System (ADS)

Yu, Mei; Yuan, Zhiqin; Lu, Chao

2017-09-01

This work presented a facile and eco-friendly method for the determination of cobalt ions (Co(II)) in living cells based on layered double hydroxides (Mg-Al CO3-LDHs) enhanced chemiluminescence (CL) emission of a Co(II)-hydrogen peroxide-sodium hydroxide system. The enhanced CL emission was attributed to the large specific surface area of Mg-Al CO3-LDHs, which facilitates the generation of an excited-stated intermediate. The proposed method displayed high selectivity toward Co(II) over other metal ions. Under the optimal conditions, the increased CL intensity showed a linear response versus Co(II) concentration in the range of 5.0-1000 nM with a detection limit of 3.7 nM (S/N = 3). The relative standard deviation for nine repeated measurements of 100 nM Co(II) was 3.2%. Furthermore, the proposed method was successfully applied to detect Co(II) in living cell samples, and the results were agreed with those obtained by the standard ICP-MS method.

Selective detection of target proteins by peptide-enabled graphene biosensor.

PubMed

Khatayevich, Dmitriy; Page, Tamon; Gresswell, Carolyn; Hayamizu, Yuhei; Grady, William; Sarikaya, Mehmet

2014-04-24

Direct molecular detection of biomarkers is a promising approach for diagnosis and monitoring of numerous diseases, as well as a cornerstone of modern molecular medicine and drug discovery. Currently, clinical applications of biomarkers are limited by the sensitivity, complexity and low selectivity of available indirect detection methods. Electronic 1D and 2D nano-materials such as carbon nanotubes and graphene, respectively, offer unique advantages as sensing substrates for simple, fast and ultrasensitive detection of biomolecular binding. Versatile methods, however, have yet to be developed for simultaneous functionalization and passivation of the sensor surface to allow for enhanced detection and selectivity of the device. Herein, we demonstrate selective detection of a model protein against a background of serum protein using a graphene sensor functionalized via self-assembling multifunctional short peptides. The two peptides are engineered to bind to graphene and undergo co-assembly in the form of an ordered monomolecular film on the substrate. While the probe peptide displays the bioactive molecule, the passivating peptide prevents non-specific protein adsorption onto the device surface, ensuring target selectivity. In particular, we demonstrate a graphene field effect transistor (gFET) biosensor which can detect streptavidin against a background of serum bovine albumin at less than 50 ng/ml. Our nano-sensor design, allows us to restore the graphene surface and utilize each sensor in multiple experiments. The peptide-enabled gFET device has great potential to address a variety of bio-sensing problems, such as studying ligand-receptor interactions, or detection of biomarkers in a clinical setting. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anticorrosion performance of chromized coating prepared by pack cementation in simulated solution with H2S and CO2

NASA Astrophysics Data System (ADS)

Wang, Qin-Ying; Behnamian, Yashar; Luo, Hong; Wang, Xian-Zong; Leitch, Michael; Zeng, Hongbo; Luo, Jing-Li

2017-10-01

A hash service environment containing H2S and CO2 in oil industry usually causes corrosion of carbon steel. In this study, the chromized coatings with different deposited time were prepared on the surface of carbon steel by the method of pack cementation to enhance its corrosion resistance. Then the microstructure, hardness, corrosion resistance as well as the semiconductor behavior of coatings in the simulated solution with saturated H2S and CO2 were investigated. The results show that the content of Cr in coating was increased by prolonging deposited time, and both chromium carbides and chromium nitrides were formed. Furthermore, coatings display higher polarization resistance, Rp, than that of the substrate, indicating a higher resistance to charge transfer on coating surface. The corrosion rates of coatings with different deposited time were significantly lower than that of substrate. Chemical analysis showed the formation of heavy sulfides on the surface of substrates after corrosion, while the least corrosion products were detected on the surface of coating with deposited time of 12 h. Mott-Schottky results indicated that coating of 12 h displayed less defects than the other two coatings with deposited time of 4 h and 8 h, which will be beneficial to improve corrosion resistance. The investigation showed that chromized coatings exhibited high corrosion resistance and owned a potential application in oil industry for corrosion prevention.

Eighteen years of geochemical monitoring at the oceanic active volcanic island of El Hierro (Canary Islands, Spain)

NASA Astrophysics Data System (ADS)

Asensio-Ramos, María; Alonso, Mar; Sharp, Emerson; Woods, Hannah; Barrancos, José; Pérez, Nemesio M.

2016-04-01

We report herein the latest results of a diffuse CO2 efflux survey at El Hierro volcanic system carried out during the summer period of 2015 to constrain the total CO2 output from the studied area a during post-eruptive period. 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. On October 10, 2011, the dominant character of seismicity changed dramatically from discrete earthquakes to continuous tremor, a clear indication that magma was rapidly approaching the surface immediately before the onset of the eruption, October 12. Eruption was declared over on 5 March, 2012. In order to monitor the volcanic activity of El Hierro Island, from 1998 to 2015 diffuse CO2 emission studies have been performed at El Hierro volcanic system in a yearly basis (˜600 observation sites) according to the accumulation chamber method. Spatial distribution maps were constructed following the sequential Gaussian simulation (sGs) procedure. To quantify the total CO2 emission from the studied area, 100 simulations for each survey have been performed. During the eruption period, soil CO2 efflux values range from non-detectable (˜0.5 g m-2 d-1) up to 457 g m-2 d-1, reaching in November 27, 2011, the maximum CO2 output estimated value of all time series, 2,398 t d-1, just before the episodes of maximum degassing observed as vigorous bubbling at the sea surface and an increment in the amplitude of the tremor signal. During the 2015 survey, soil CO2 efflux values ranged from non-detectable up to 41 g m-2 d-1. The spatial distribution of diffuse CO2 emission values seemed to be controlled by the main volcano structural features of the island. The total diffuse CO2 output released to atmosphere was estimated at 575 ± 24 t d-1, value slightly higher that the background CO2 emission estimated at 422 t d-1 (Melián et al., 2014). The above data demonstrate that 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. References: Melián et al., 2014. J. Geophys. Res. DOI: 10.1002/2014JB011013.

CO and CO2 dual-gas detection based on mid-infrared wideband absorption spectroscopy

NASA Astrophysics Data System (ADS)

Dong, Ming; Zhong, Guo-qiang; Miao, Shu-zhuo; Zheng, Chuan-tao; Wang, Yi-ding

2018-03-01

A dual-gas sensor system is developed for CO and CO2 detection using a single broadband light source, pyroelectric detectors and time-division multiplexing (TDM) technique. A stepper motor based rotating system and a single-reflection spherical optical mirror are designed and adopted for realizing and enhancing dual-gas detection. Detailed measurements under static detection mode (without rotation) and dynamic mode (with rotation) are performed to study the performance of the sensor system for the two gas samples. The detection period is 7.9 s in one round of detection by scanning the two detectors. Based on an Allan deviation analysis, the 1σ detection limits under static operation are 3.0 parts per million (ppm) in volume and 2.6 ppm for CO and CO2, respectively, and those under dynamic operation are 9.4 ppm and 10.8 ppm for CO and CO2, respectively. The reported sensor has potential applications in various fields requiring CO and CO2 detection such as in the coal mine.

Poroelastic Seismic Wave Propagation Modeling of CO2 Sequestration Effects

NASA Astrophysics Data System (ADS)

Aldridge, D. F.; Bartel, L. C.

2009-12-01

Long term geologic sequestration of carbon dioxide (CO2) is considered a viable approach for removing large amounts of excess carbon from the earth’s surface environment. As CO2 is injected into a subsurface porous formation, it displaces (or mixes with) in situ pore fluids. Seismic reflection and transmission responses of the formation depend on the degree of CO2 substitution. Additionally, geochemical reactions involving CO2 and mineral grains alter the bulk and shear moduli of the solid constituent and/or the matrix of the porous medium. We examine full waveform, wide-angle, amplitude vs. offset (AVO) responses of sandstone and carbonate layers. Synthetic seismic data are calculated with a 3D poroelastic wave propagation algorithm that solves Biot’s system of thirteen coupled partial differential equations via an explicit, time-domain, finite-difference method. All common seismological phases (primary and multiple reflections, mode conversions, head waves, surface and interface waves) are generated with fidelity, provided spatial and temporal gridding intervals are sufficiently fine. Initial calculations indicate that full or partial replacement of H2O by CO2 is readily detected by the AVO recording configuration, particularly with long offset events. Difference seismogram amplitudes of surface-recorded particle velocities range up to ~25%. Equivalent elastic medium responses, with elastic parameters assigned by Gassmann formulae, are inadequate at higher frequencies. Finally, these sensitivity modeling experiments are being extended to vertical seismic profiling geometries. Sandia National Laboratories is a multiprogram science and engineering facility operated by Sandia Corporation, a Lockheed-Martin company, for the US Department of Energy’s National Nuclear Security Administration, under contract DE-AC04-94AL85000.

High sensitivity and accuracy dissolved oxygen (DO) detection by using PtOEP/poly(MMA-co-TFEMA) sensing film.

PubMed

Zhang, Ke; Zhang, Honglin; Wang, Ying; Tian, Yanqing; Zhao, Jiupeng; Li, Yao

2017-01-05

Fluorinated acrylate polymer has received great interest in recent years due to its extraordinary characteristics such as high oxygen permeability, good stability, low surface energy and refractive index. In this work, platinum octaethylporphyrin/poly(methylmethacrylate-co-trifluoroethyl methacrylate) (PtOEP/poly(MMA-co-TFEMA)) oxygen sensing film was prepared by the immobilizing of PtOEP in a poly(MMA-co-TFEMA) matrix and the technological readiness of optical properties was established based on the principle of luminescence quenching. It was found that the oxygen-sensing performance could be improved by optimizing the monomer ratio (MMA/TFEMA=1:1), tributylphosphate(TBP, 0.05mL) and PtOEP (5μg) content. Under this condition, the maximum quenching ratio I0/I100 of the oxygen sensing film is obtained to be about 8.16, Stern-Volmer equation is I0/I=1.003+2.663[O2] (R(2)=0.999), exhibiting a linear relationship, good photo-stability, high sensitivity and accuracy. Finally, the synthesized PtOEP/poly(MMA-co-TFEMA) sensing film was used for DO detection in different water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

High sensitivity and accuracy dissolved oxygen (DO) detection by using PtOEP/poly(MMA-co-TFEMA) sensing film

NASA Astrophysics Data System (ADS)

Zhang, Ke; Zhang, Honglin; Wang, Ying; Tian, Yanqing; Zhao, Jiupeng; Li, Yao

2017-01-01

Fluorinated acrylate polymer has received great interest in recent years due to its extraordinary characteristics such as high oxygen permeability, good stability, low surface energy and refractive index. In this work, platinum octaethylporphyrin/poly(methylmethacrylate-co-trifluoroethyl methacrylate) (PtOEP/poly(MMA-co-TFEMA)) oxygen sensing film was prepared by the immobilizing of PtOEP in a poly(MMA-co-TFEMA) matrix and the technological readiness of optical properties was established based on the principle of luminescence quenching. It was found that the oxygen-sensing performance could be improved by optimizing the monomer ratio (MMA/TFEMA = 1:1), tributylphosphate(TBP, 0.05 mL) and PtOEP (5 μg) content. Under this condition, the maximum quenching ratio I0/I100 of the oxygen sensing film is obtained to be about 8.16, Stern-Volmer equation is I0/I = 1.003 + 2.663[O2] (R2 = 0.999), exhibiting a linear relationship, good photo-stability, high sensitivity and accuracy. Finally, the synthesized PtOEP/poly(MMA-co-TFEMA) sensing film was used for DO detection in different water samples.

Facile synthesis of electrospun MFe2O4 (M = Co, Ni, Cu, Mn) spinel nanofibers with excellent electrocatalytic properties for oxygen evolution and hydrogen peroxide reduction

NASA Astrophysics Data System (ADS)

Li, Mian; Xiong, Yueping; Liu, Xiaotian; Bo, Xiangjie; Zhang, Yufan; Han, Ce; Guo, Liping

2015-05-01

Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m2 g-1) than those of the CoFe2O4 NPs (5.93 m2 g-1)) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media.Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m2 g-1) than those of the CoFe2O4 NPs (5.93 m2 g-1)) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07243j

Buried CO2 Ice traces in South Polar Layered Deposits of Mars detected by radar sounder

NASA Astrophysics Data System (ADS)

Castaldo, L.; Mège, D.; Orosei, R.; Séjourné, A.

2014-12-01

SHARAD (SHAllow RADar) is the subsurface sounding radar provided by the Italian Space Agency (ASI) as a facility instrument to NASA's 2005 Mars Reconnaissance Orbiter (MRO). The Reduced Data Record of SHARAD data covering the area of the South Polar Layered Deposits (SPLD), has been used. The elaboration and interpretation of the data, aimed to estimate electromagnetic properties of surface layers, has been performed in terms of permittivity. The theory of electromagnetic scattering from fractal surfaces, and the estimation of geometric parameters from topographic data by Mars Orbiter Laser Altimeter (MOLA) which was one of five instruments on board the Mars Global Surveyor (MGS) spacecraft, has been used. A deep analysis of inversion has been made on all Mars and extended to the South Polar Caps in order to extract the area with a permittivity constant of CO2 ice. Several corrections have been applied to the data, moreover the calibration of the signal requires the determination of a constant that takes into account the power gain due to the radar system and the surface in order to compensate the power losses due to the orbitographic phenomena. The determination of regions with high probability of buried CO2 ice in the first layer of the Martian surface, is obtained extracting the real part of the permittivity constant of the CO2 ice (~2), estimated by other means. The permittivity of CO2ice is extracted from the Global Permittivity Map of Mars using the global standard deviation of itself as following: ɛCO2ice=ɛCO2ice+ Σ (1)where Σ=±std(ɛMapMars)/2Figure 1(a) shows the south polar areas where the values of the permittivity point to the possibility of a CO2 ice layer. Figure 1(b) is the corresponding geologic map. The comparison between the two maps indicates that the area with probable buried CO2 overlaps Hesperian and Amazonian polar units (Hp, Hesperian plains-forming deposits marked by narrow sinuous, anabranching ridges and irregular depressions, and Apu, Amazonian layered plateaus). From this analysis, the south polar cap could be covered by a thin frozen carbon dioxide coating. The perennial south polar cap is probably made of frozen carbon dioxide ca. 8 meters thick.

Absorption of CO2 on Carbon-based Sensors: First-Principle Analysis

NASA Astrophysics Data System (ADS)

Tit, Nacir; Elezzi, Mohammed; Abdullah, Hasan; Bahlouli, Hocine; Yamani, Zain

We present first-principle investigation of the adsorption properties of CO and CO2 molecules on both graphene and carbon nano-tubes (CNTs) in presence of metal catalysis, mainly iron (Fe). The relaxations were carried out using the self-consistent-charge density-functional tight-binding (SCC-DFTB) code in neglect of heat effects. The results show the following: (1) Defected graphene is found to have high sensitivity and high selectivity towards chemisorption of CO molecules and weak physisorption with CO2 molecules. (2) In case of CNTs, the iron ``Fe'' catalyst plays an essential role in capturing CO2 molecules. The Fe ad-atoms on the surface of CNT introduce huge density of states at Fermi level, but the capture of CO2 molecules would reduce that density and consequently reduce conductivity and increase sensitivity. Concerning the selectivity, we have studied the sensitivity versus various gas molecules (such as: O2, N2, H2, H2O, and CO). Furthermore, to assess the effect of catalysis on sensitivity, we have studied the sensitivity of other metal catalysts (such as: Ni, Co, Ti, and Sc). We found that CNT-Fe is highly sensitive and selective towards detection of CO and CO2 molecules. CNT being conductive or semiconducting does not matter much on the adsorption properties.

Radiolytic Model for Chemical Composition of Europa's Atmosphere and Surface

NASA Technical Reports Server (NTRS)

Cooper, John F.

2004-01-01

The overall objective of the present effort is to produce models for major and selected minor components of Europa s neutral atmosphere in 1-D versus altitude and in 2-D versus altitude and longitude or latitude. A 3-D model versus all three coordinates (alt, long, lat) will be studied but development on this is at present limited by computing facilities available to the investigation team. In this first year we have focused on 1-D modeling with Co-I Valery Shematovich s Direct Simulation Monte Carlo (DSMC) code for water group species (H2O, O2, O, OH) and on 2-D with Co-I Mau Wong's version of a similar code for O2, O, CO, CO2, and Na. Surface source rates of H2O and O2 from sputtering and radiolysis are used in the 1-D model, while observations for CO2 at the Europa surface and Na detected in a neutral cloud ejected from Europa are used, along with the O2 sputtering rate, to constrain source rates in the 2-D version. With these separate approaches we are investigating a range of processes important to eventual implementation of a comprehensive 3-D atmospheric model which could be used to understand present observations and develop science requirements for future observations, e.g. from Earth and in Europa orbit. Within the second year we expect to merge the full water group calculations into the 2-D version of the DSMC code which can then be extended to 3-D, pending availability of computing resources. Another important goal in the second year would be the inclusion of sulk and its more volatile oxides (SO, SO2).

Theoretical study of methanol synthesis from CO2 and CO hydrogenation on the surface of ZrO2 supported In2O3 catalyst

NASA Astrophysics Data System (ADS)

Dou, Maobin; Zhang, Minhua; Chen, Yifei; Yu, Yingzhe

2018-06-01

The interactions between ZrO2 support and In2O3 catalyst play pivotal role in the catalytic conversion of CO2 to methanol. Herein, a density functional theory study has been conducted to research the mechanism of methanol synthesis from CO2 and CO hydrogenation on the defective ZrO2 supported In2O3(110) surface (D surface). The calculations reveal that methanol is produced mainly via the HCOO reaction pathway from CO2 hydrogenation on D surface, and the hydrogenation of HCOO to form H2COO species with an activation barrier of 1.21 eV plays the rate determining step for the HCOO reaction pathway. The direct dissociation of CO2 to CO on D surface is kinetically and energetically prohibited. Methanol synthesis from CO hydrogenation on D surface is much facile comparing with the elementary steps involved in CO2 hydrogenation. The rate determining step of CO hydrogenation to methanol is the formation of H3CO species on the vacancy site with a barrier of 0.51 eV. ZrO2 support has significant effect on the suppressing of the dissociation of CO2 and stabilization of H2COO species on the surface of In2O3 catalyst.

Toward improving CO2 dissociation and conversion to methanol via CO-hydrogenation on Cu(100) surface by introducing embedded Co nanoclusters as promoters: A DFT study

NASA Astrophysics Data System (ADS)

Qiu, Mei; Tao, Huilin; Li, Yali; Li, Yi; Ding, Kaining; Huang, Xin; Chen, Wenkai; Zhang, Yongfan

2018-01-01

The dissociation and hydrogenation of CO2 on Cu(100) surfaces that are modified by introducing Co nanoclusters with different size into the top layer have been investigated using density functional theory method. Our results show that on all surfaces the Co atoms are the sites for the adsorption of CO2, and in the early stage of introducing Co dopant, the chemisorption behavior of CO2 is sensitive to the amount of Co atom. According to the predicted pathways for the dissociation of CO2 to CO, it is interesting that the energy barrier decreases first and then increases as more Co atoms are dispersed on the surface, forming a ;V; shape. The minimum energy barrier of CO2 decomposition is predicted on the Cu(100) surface that contains four Co atoms aggregated together on the top layer, namely Co4/Cu(100) bimetallic surface. The most favorable reaction pathway for the hydrogenation of CO to methanol on such surface is further determined, which follows the sequence of CO* → HCO* → H2CO* → H3CO* → H3COH*, and the rate-limiting step is the hydrogenation of H3CO species with an activation barrier of 106.4 kJ/mol. It is noted that with respect to the pure Cu(100), since more stronger Cosbnd O adsorption bonds are formed on the Co-modified surface, the stability of formaldehyde intermediate is significantly enhanced. Correspondingly, the introducing of Co4 cluster tends to improve the productivity and selectivity towards methanol synthesis on Cu(100) surface.

Role of water and carbonates in photocatalytic transformation of CO{sub 2} to CH{sub 4} on titania.

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

Dimitrijevic, N. M.; Vijayan, B. K.; Poluektov, O. G.

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and {center_dot}OH radicals (oxidation product) from water, and CO{sub 3}{sup -} radical anions (oxidation product) from carbonates, was detected in CO{sub 2}-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, {center_dot}OCH{sub 3}, and methyl, {center_dot}CH{sub 3}, radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO{sub 2} on the surface of TiO{sub 2} ismore » supported by the results of first-principles calculations.« less

Role of Water and Carbonates in Photocatalytic Transformation of CO2 to CH4 on Titania

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

Dimitrijevic, Nada; Vijayan, Baiju K.; Poluektov, Oleg G.

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and {sm_bullet}OH radicals (oxidation product) from water, and CO{sub 3}{sup -} radical anions (oxidation product) from carbonates, was detected in CO{sub 2}-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, {sm_bullet}OCH{sub 3}, and methyl, {sm_bullet}CH{sub 3}, radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO{sub 2}, on the surface of TiO{sub 2}, ismore » supported by the results of first-principles calculations.« less

New insights into proton surface mobility processes in PEMFC catalysts using isotopic exchange methods.

PubMed

Ferreira-Aparicio, Paloma

2009-09-01

The surface chemistry and the adsorption/desorption/exchange behavior of a proton-exchange membrane fuel cell catalyst are analyzed as a case study for the development of tailor-made support materials of enhanced performance and stability. By using H2, D2, and CO as probe molecules, the relevance of some surface functional groups of the catalyst support on several diffusion processes taking place during the adsorption is shown. Sulfonic groups associated with the vulcanized carbon black surface have been detected by means of spectroscopic techniques (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) and by analysis of the desorbed products during temperature-programmed desorption tests by mass spectrometry. Such hydrophilic species have been observed to favor proton surface mobility and exchange with Pt-adsorbed deuterium even in the presence of adsorbed CO. This behavior is relevant both for the proper characterization of these kinds of catalysts using adsorption probes and for the design of new surface-modified carbon supports, enabling alternative proton-transfer pathways throughout the catalytic layers toward the membrane.

Airborne 2-Micron Double-Pulsed Integrated Path Differential Absorption Lidar for Column CO2 Measurement

NASA Technical Reports Server (NTRS)

Singh, Upendra N.; Yu, Jirong; Petros, Mulugeta; Refaat, Tamer F.; Remus, Ruben G.; Fay, James J.; Reithmaier, Karl

2014-01-01

Double-pulse 2-micron lasers have been demonstrated with energy as high as 600 millijouls and up to 10 Hz repetition rate. The two laser pulses are separated by 200 microseconds and can be tuned and locked separately. Applying double-pulse laser in DIAL system enhances the CO2 measurement capability by increasing the overlap of the sampled volume between the on-line and off-line. To avoid detection complicity, integrated path differential absorption (IPDA) lidar provides higher signal-to-noise ratio measurement compared to conventional range-resolved DIAL. Rather than weak atmospheric scattering returns, IPDA rely on the much stronger hard target returns that is best suited for airborne platforms. In addition, the IPDA technique measures the total integrated column content from the instrument to the hard target but with weighting that can be tuned by the transmitter. Therefore, the transmitter could be tuned to weight the column measurement to the surface for optimum CO2 interaction studies or up to the free troposphere for optimum transport studies. Currently, NASA LaRC is developing and integrating a double-Pulsed 2-micron direct detection IPDA lidar for CO2 column measurement from an airborne platform. The presentation will describe the development of the 2-micron IPDA lidar system and present the airborne measurement of column CO2 and will compare to in-situ measurement for various ground target of different reflectivity.

Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life

PubMed Central

Krissansen-Totton, Joshua; Olson, Stephanie; Catling, David C.

2018-01-01

Chemical disequilibrium in planetary atmospheres has been proposed as a generalized method for detecting life on exoplanets through remote spectroscopy. Among solar system planets with substantial atmospheres, the modern Earth has the largest thermodynamic chemical disequilibrium due to the presence of life. However, how this disequilibrium changed over time and, in particular, the biogenic disequilibria maintained in the anoxic Archean or less oxic Proterozoic eons are unknown. We calculate the atmosphere-ocean disequilibrium in the Precambrian using conservative proxy- and model-based estimates of early atmospheric and oceanic compositions. We omit crustal solids because subsurface composition is not detectable on exoplanets, unlike above-surface volatiles. We find that (i) disequilibrium increased through time in step with the rise of oxygen; (ii) both the Proterozoic and Phanerozoic may have had remotely detectable biogenic disequilibria due to the coexistence of O2, N2, and liquid water; and (iii) the Archean had a biogenic disequilibrium caused by the coexistence of N2, CH4, CO2, and liquid water, which, for an exoplanet twin, may be remotely detectable. On the basis of this disequilibrium, we argue that the simultaneous detection of abundant CH4 and CO2 in a habitable exoplanet’s atmosphere is a potential biosignature. Specifically, we show that methane mixing ratios greater than 10−3 are potentially biogenic, whereas those exceeding 10−2 are likely biogenic due to the difficulty in maintaining large abiotic methane fluxes to support high methane levels in anoxic atmospheres. Biogenicity would be strengthened by the absence of abundant CO, which should not coexist in a biological scenario. PMID:29387792

Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life.

PubMed

Krissansen-Totton, Joshua; Olson, Stephanie; Catling, David C

2018-01-01

Chemical disequilibrium in planetary atmospheres has been proposed as a generalized method for detecting life on exoplanets through remote spectroscopy. Among solar system planets with substantial atmospheres, the modern Earth has the largest thermodynamic chemical disequilibrium due to the presence of life. However, how this disequilibrium changed over time and, in particular, the biogenic disequilibria maintained in the anoxic Archean or less oxic Proterozoic eons are unknown. We calculate the atmosphere-ocean disequilibrium in the Precambrian using conservative proxy- and model-based estimates of early atmospheric and oceanic compositions. We omit crustal solids because subsurface composition is not detectable on exoplanets, unlike above-surface volatiles. We find that (i) disequilibrium increased through time in step with the rise of oxygen; (ii) both the Proterozoic and Phanerozoic may have had remotely detectable biogenic disequilibria due to the coexistence of O 2 , N 2 , and liquid water; and (iii) the Archean had a biogenic disequilibrium caused by the coexistence of N 2 , CH 4 , CO 2 , and liquid water, which, for an exoplanet twin, may be remotely detectable. On the basis of this disequilibrium, we argue that the simultaneous detection of abundant CH 4 and CO 2 in a habitable exoplanet's atmosphere is a potential biosignature. Specifically, we show that methane mixing ratios greater than 10 -3 are potentially biogenic, whereas those exceeding 10 -2 are likely biogenic due to the difficulty in maintaining large abiotic methane fluxes to support high methane levels in anoxic atmospheres. Biogenicity would be strengthened by the absence of abundant CO, which should not coexist in a biological scenario.

Co-sputter deposited nickel-copper bimetallic nanoalloy embedded carbon films for electrocatalytic biomarker detection

NASA Astrophysics Data System (ADS)

Shiba, Shunsuke; Kato, Dai; Kamata, Tomoyuki; Niwa, Osamu

2016-06-01

We report the fabrication of a nickel (Ni)-copper (Cu) bimetallic nanoalloy (~3 nm) embedded carbon film electrode with the unbalanced magnetron (UBM) co-sputtering technique, which requires only a one-step process at room temperature. Most of each nanoalloy body was firmly embedded in a chemically stable carbon matrix with an atomically flat surface (Ra: 0.21 nm), suppressing the aggregation and/or detachment of the nanoalloy from the electrode surface. The nanoalloy size and composition can be controlled simply by individually controlling the target powers of carbon, Ni and Cu, which also makes it possible to localize the nanoalloys near the electrode surface. This electrode exhibited excellent electrocatalytic activity for d-mannitol, which should be detected with a low detection limit in urine samples for the diagnosis of severe intestinal diseases. With a Ni/Cu ratio of around 64/36, the electrocatalytic current per metal area was 3.4 times larger than that of an alloy film electrode with a similar composition (~70/30). This improved electrocatalytic activity realized higher stability (n = 60, relative standard deviation (RSD): 4.6%) than the alloy film (RSD: 32.2%) as demonstrated by continuous measurements of d-mannitol.We report the fabrication of a nickel (Ni)-copper (Cu) bimetallic nanoalloy (~3 nm) embedded carbon film electrode with the unbalanced magnetron (UBM) co-sputtering technique, which requires only a one-step process at room temperature. Most of each nanoalloy body was firmly embedded in a chemically stable carbon matrix with an atomically flat surface (Ra: 0.21 nm), suppressing the aggregation and/or detachment of the nanoalloy from the electrode surface. The nanoalloy size and composition can be controlled simply by individually controlling the target powers of carbon, Ni and Cu, which also makes it possible to localize the nanoalloys near the electrode surface. This electrode exhibited excellent electrocatalytic activity for d-mannitol, which should be detected with a low detection limit in urine samples for the diagnosis of severe intestinal diseases. With a Ni/Cu ratio of around 64/36, the electrocatalytic current per metal area was 3.4 times larger than that of an alloy film electrode with a similar composition (~70/30). This improved electrocatalytic activity realized higher stability (n = 60, relative standard deviation (RSD): 4.6%) than the alloy film (RSD: 32.2%) as demonstrated by continuous measurements of d-mannitol. Electronic supplementary information (ESI) available: The concept of UBM co-sputtering for fabricating nanoalloy embedded carbon films. HRTEM images of the NiNP and Ni32Cu68 nanoalloy embedded carbon films. The experimental conditions for sputter deposition, HRTEM, HAADF-STEM, STEM-EDS measurements and continuous flow injection analysis. XPS analysis of the nanoalloy embedded carbon film. Repeated CVs of both the nanoalloy embedded carbon film and the alloy film. Amperometric detection of d-mannitol in the presence of chloride ions. See DOI: 10.1039/c6nr02287a

The Design of The Monitoring Tools Of Clean Air Condition And Dangerous Gas CO, CO2 CH4 In Chemical Laboratory By Using Fuzzy Logic Based On Microcontroller

NASA Astrophysics Data System (ADS)

Widodo, Slamet; Miftakul, Amin M.; Sutrisman, Adi

2018-02-01

There are many phenomena that human are exposed to toxins from certain types such as of CO2, CO2 and CH4 gases. The device used to detect large amounts of CO, CO2, and CH4 gas in air in enclosed spaces using MQ 135 gas sensors of different types based on the three sensitivity of the Gas. The results of testing the use of sensors MQ 135 on the gas content of CO, CO2 and CH4 received by the sensor is still in the form of ppm based on the maximum ppm detection range of each sensor. Active sensor detects CO 120 ppm gas, CO2 1600 ppm and CH4 1ppm "standby 1" air condition with intermediate rotary fan. Active sensor detects CO 30 ppm gas, CO2 490 ppm and CH4 7 ppm "Standby 2" with low rotating fan output. Fuzzy rulebase logic for motor speed when gas detection sensor CO, CO2, and CH4 output controls the motion speed of the fan blower. Active sensors detect CO 15 ppm, CO2 320 ppm and CH4 45 ppm "Danger" air condition with high fan spin fan. At the gas level of CO 15 ppm, CO2 390 ppm and CH4 3 ppm detect "normal" AC sensor with fan output stop spinning.

Measuring CO2 from Space: The NASA Orbiting Carbon Observatory-2

NASA Technical Reports Server (NTRS)

Crisp, D.

2010-01-01

The Orbiting Carbon Observatory (OCO) was the first NASA satellite designed to measure atmospheric carbon dioxide (CO2) from space with the precision, resolution, and coverage needed to detect CO2 surface fluxes. OCO was designed to collect 0.5 to 1 million soundings each day. Typical measurements over land were expected to have precisions of 0.3% within surface footprints smaller less than 3 square km. This project suffered a major setback in February 2009 when the OCO launch vehicle failed to achieve orbit and the satellite was lost. The U.S. Congress has since authorized a restart of the OCO project, and the President's 2010 budget proposal includes funding to develop and fly a replacement for OCO that could be ready for launch no later than February 2013. This mission has been designated OCO-2. While this mission will be a near "carbon copy" of OCO, some changes were needed to replace components that were no longer available. Here, we describe the capabilities, of the OCO-2 mission, highlighting its differences from OCO.

CO2 sensing properties of electro-spun Ca-doped ZnO fibres.

PubMed

Pantò, Fabiola; Leonardi, Salvatore Gianluca; Fazio, Enza; Frontera, Patrizia; Bonavita, Anna; Neri, Giovanni; Antonucci, Pierluigi; Neri, Fortunato; Santangelo, Saveria

2018-07-27

The availability of low-cost, high-performing sensors for carbon dioxide detection in the environment may play a crucial role for reducing CO 2 emissions and limiting global warming. In this study, calcium-doped zinc oxide nanofibres with different Ca to Zn loading ratios (1:40 or 1:20) are synthesised via electro-spinning, thoroughly characterised and, for the first time, tested as an active material for the detection of carbon dioxide. The results of their characterisation show that the highly porous fibres consist of interconnected grains of oxide with the hexagonal wurtzite structure of zincite. Depending on the Ca:Zn loading ratio, calcium fully or partly segregates to form calcite on the fibre surface. The high response of the sensor based on the fibres with the highest Ca-doping level can be attributed to the synergy between the fibre morphology and the basicity of Ca-ion sites, which favour the diffusion of the gas molecules within the sensing layer and the CO 2 adsorption, respectively.

An In-Line Photonic Biosensor for Monitoring of Glucose Concentrations

PubMed Central

Al-Halhouli, Ala'aldeen; Demming, Stefanie; Alahmad, Laila; LIobera, Andreu; Büttgenbach, Stephanus

2014-01-01

This paper presents two PDMS photonic biosensor designs that can be used for continuous monitoring of glucose concentrations. The first design, the internally immobilized sensor, consists of a reactor chamber, micro-lenses and self-alignment structures for fiber optics positioning. This sensor design allows optical detection of glucose concentrations under continuous glucose flow conditions of 33 μL/h based on internal co-immobilization of glucose oxidase (GOX) and horseradish peroxidase (HRP) on the internal PDMS surface of the reactor chamber. For this design, two co-immobilization methods, the simple adsorption and the covalent binding (PEG) methods were tested. Experiments showed successful results when using the covalent binding (PEG) method, where glucose concentrations up to 5 mM with a coefficient of determination (R2) of 0.99 and a limit of detection of 0.26 mM are detectable. The second design is a modified version of the internally immobilized sensor, where a microbead chamber and a beads filling channel are integrated into the sensor. This modification enabled external co-immobilization of enzymes covalently onto functionalized silica microbeads and allows binding a huge amount of HRP and GOX enzymes on the microbeads surfaces which increases the interaction area between immobilized enzymes and the analyte. This has a positive effect on the amount and rate of chemical reactions taking place inside the chamber. The sensor was tested under continuous glucose flow conditions and was found to be able to detect glucose concentrations up to 10 mM with R2 of 0.98 and a limit of detection of 0.7 mM. Such results are very promising for the application in photonic LOC systems used for online analysis. PMID:25157552

Intriguing differences and similarities in the surface compositions of the icy Saturnian and Galilean satellites

NASA Astrophysics Data System (ADS)

Hibbitts, C.

2006-12-01

Many materials in addition to water ice have been discovered in the surfaces of the icy Galilean and Saturnian satellites. Spacecraft infrared spectroscopy show intriguing differences and similarities suggestive of variations in primordial compositions and subsequent alteration. However, within the diverse compositions in their surfaces are similarities that cross between the systems. For instance, when nonice material is detected on these satellites, it is always hydrated. CO2 is detected in both systems where it is trapped in a host material except possibly for Enceladus where it may be deposited as ice from plumes [1-7]. Satellites in both systems contain aromatic hydrocarbons [8] and possibly CN-bearing materials [9]. The surfaces of Callisto, Ganymede, Europa, Iapetus, Phoebe, Hyperion, and Dione each contain some low albedo non-ice materials. The spectra have a broad 3-micron absorption feature due to structural OH or adsorbed water. However, the band is not sharp like a well-ordered clay mineral but broad, similar in some regards to less well-structured palagonite, goethite, or Murchison meteorite. The hydration of Jovian satellite nonice materials is greater for surfaces that have experienced more tectonism and alteration (i.e. increases from Callisto inward to Europa). The nonice material on Callisto appears to be a single composition (though itself possibly a mixture) that is slightly hydrated [10]. The nonice material on Europa is also of uniform composition everywhere observed, a very heavily hydrated material, perhaps a salt, hydrated SO4 (i.e. sulfuric acid), or both, that either originates from the subsurface ocean, radiolytically altered surface material, or both [11-13]. Ganymede appears to contain two types nonice materials; one an unidentified heavily hydrated material spectrally distinct from the Europa hydrate [11] and a second much less-abundant, less hydrated material spectrally similar to the Callisto nonice material that is largely associated with dark ray craters, possibly impactor contamination or desiccated Ganymede hydrate. The nonice materials on Phoebe and Iapetus is redder (from 1-2.5 microns) than the reddest material on the Galilean satellites (on Callisto) and compositionally different from each other. Iapetus appears to contain some (more) tholin material than Phoebe [14]. The CO2 on both satellites is similar to the CO2 detected in the nonice materials on Callisto and Ganymede with a reflectance minimum ~ 4.258 microns. The spectrum of the CO2 detected on Hyperion and Dione is distinct from that on Iapetus and Phoebe, having a reflectance minimum 10nm shorter at ~ 4.246 microns. This suggests a different bonding energy and possibly a different host material. In summary, the compositions of the icy Galilean satellites reflect the evolutionary state of their surfaces. The compositions of the icy Saturnian satellites are also complex, but with the exception of Enceladus, do not yet show any obvious dependencies on surface structure. There may some commonality in primordial compositions between the satellites of the two systems. References: [1]1Carlson et al., (1996) Science; [2] McCord et al., (1998) J. Geophys. Res.;[3] Hibbitts et al., (2000), J. Geophys. Res; [4] Hibbitts et al., (2003) J. Geophys. Res; [5] Clark et al., (2005) Nature; [6] Buratti et al., (2005) Astrophys. J.; [7] Brown et al., (2006) , Icarus; [8] Clark et al., (2005), Fall AGU; [9] Cruikshank et al., (2005), DPS [10] Calvin et al., (1991), Icarus; [11] McCord et al., 2000; [12]Carlson et al., 1999; [13]Orlando et al., (2005) Icarus; [14] Owens et al., (2001) Icarus;.

Space-Based CO2 Active Optical Remote Sensing using 2-μm Triple-Pulse IPDA Lidar

NASA Astrophysics Data System (ADS)

Singh, Upendra; Refaat, Tamer; Ismail, Syed; Petros, Mulugeta

2017-04-01

Sustained high-quality column CO2 measurements from space are required to improve estimates of regional and global scale sources and sinks to attribute them to specific biogeochemical processes for improving models of carbon-climate interactions and to reduce uncertainties in projecting future change. Several studies show that space-borne CO2 measurements offer many advantages particularly over high altitudes, tropics and southern oceans. Current satellite-based sensing provides rapid CO2 monitoring with global-scale coverage and high spatial resolution. However, these sensors are based on passive remote sensing, which involves limitations such as full seasonal and high latitude coverage, poor sensitivity to the lower atmosphere, retrieval complexities and radiation path length uncertainties. CO2 active optical remote sensing is an alternative technique that has the potential to overcome these limitations. The need for space-based CO2 active optical remote sensing using the Integrated Path Differential Absorption (IPDA) lidar has been advocated by the Advanced Space Carbon and Climate Observation of Planet Earth (A-Scope) and Active Sensing of CO2 Emission over Nights, Days, and Seasons (ASCENDS) studies in Europe and the USA. Space-based IPDA systems can provide sustained, high precision and low-bias column CO2 in presence of thin clouds and aerosols while covering critical regions such as high latitude ecosystems, tropical ecosystems, southern ocean, managed ecosystems, urban and industrial systems and coastal systems. At NASA Langley Research Center, technology developments are in progress to provide high pulse energy 2-μm IPDA that enables optimum, lower troposphere weighted column CO2 measurements from space. This system provides simultaneous ranging; information on aerosol and cloud distributions; measurements over region of broken clouds; and reduces influences of surface complexities. Through the continual support from NASA Earth Science Technology Office, current efforts are focused on developing an aircraft-based 2-μm triple-pulse IPDA lidar for independent and simultaneous monitoring of CO2 and water vapor (H2O). Triple-pulse IPDA design, development and integration is based on the knowledge gathered from the successful demonstration of the airborne CO2 2-μm double-pulse IPDA lidar. IPDA transmitter enhancements include generating high-energy (80 mJ) and high repetition rate (50Hz) three successive pulses using a single pump pulse. IPDA receiver enhancement include an advanced, low noise (1 fW/Hz1/2) MCT e-APD detection system for improved measurement sensitivity. In place of H2O sensing, the triple-pulse IPDA can be tuned to measure CO2 with two different weighting functions using two on-lines and a common off-line. Modeling of a space-based high-energy 2-µm triple-pulse IPDA lidar was conducted to demonstrate CO2 measurement capability and to evaluate random and systematic errors. Projected performance shows <0.12% random error and <0.07% residual systematic error. These translate to near-optimum 0.5 ppm precision and 0.3 ppm bias in low-tropospheric column CO2 mixing ratio measurements from space for 10 second signal averaging over Railroad Valley reference surface using US Standard atmospheric model. In addition, measurements can be optimized by tuning on-lines based upon ground target scenarios, environment and science objectives. With 10 MHz detection bandwidth, surface ranging with an uncertainty of <3 m can be achieved as demonstrated from earlier airborne flights.

Archaeal diversity and CO2 fixers in carbonate-/siliciclastic-rock groundwater ecosystems

USGS Publications Warehouse

Lazar, Cassandre Sara; Stoll, Wenke; Lehmann, Robert; Herrmann, Martina; Schwab, Valérie F.; Akob, Denise M.; Nawaz, Ali; Wubet, Tesfaye; Buscot, François; Totsche, Kai-Uwe; Küsel, Kirsten

2017-01-01

Groundwater environments provide habitats for diverse microbial communities, and although Archaea usually represent a minor fraction of communities, they are involved in key biogeochemical cycles. We analysed the archaeal diversity within a mixed carbonate-rock/siliciclastic-rock aquifer system, vertically from surface soils to subsurface groundwater including aquifer and aquitard rocks. Archaeal diversity was also characterized along a monitoring well transect that spanned surface land uses from forest/woodland to grassland and cropland. Sequencing of 16S rRNA genes showed that only a few surface soil-inhabiting Archaea were present in the groundwater suggesting a restricted input from the surface. Dominant groups in the groundwater belonged to the marine group I (MG-I) Thaumarchaeota and the Woesearchaeota. Most of the groups detected in the aquitard and aquifer rock samples belonged to either cultured or predicted lithoautotrophs (e.g., Thaumarchaeota or Hadesarchaea). Furthermore, to target autotrophs, a series of 13CO2 stable isotope-probing experiments were conducted using filter pieces obtained after filtration of 10,000 L of groundwater to concentrate cells. These incubations identified the SAGMCG Thaumarchaeota and Bathyarchaeota as groundwater autotrophs. Overall, the results suggest that the majority of Archaea on rocks are fixing CO2, while archaeal autotrophy seems to be limited in the groundwater.

Archaeal Diversity and CO2 Fixers in Carbonate-/Siliciclastic-Rock Groundwater Ecosystems.

PubMed

Lazar, Cassandre Sara; Stoll, Wenke; Lehmann, Robert; Herrmann, Martina; Schwab, Valérie F; Akob, Denise M; Nawaz, Ali; Wubet, Tesfaye; Buscot, François; Totsche, Kai-Uwe; Küsel, Kirsten

2017-01-01

Groundwater environments provide habitats for diverse microbial communities, and although Archaea usually represent a minor fraction of communities, they are involved in key biogeochemical cycles. We analysed the archaeal diversity within a mixed carbonate-rock/siliciclastic-rock aquifer system, vertically from surface soils to subsurface groundwater including aquifer and aquitard rocks. Archaeal diversity was also characterized along a monitoring well transect that spanned surface land uses from forest/woodland to grassland and cropland. Sequencing of 16S rRNA genes showed that only a few surface soil-inhabiting Archaea were present in the groundwater suggesting a restricted input from the surface. Dominant groups in the groundwater belonged to the marine group I (MG-I) Thaumarchaeota and the Woesearchaeota. Most of the groups detected in the aquitard and aquifer rock samples belonged to either cultured or predicted lithoautotrophs (e.g., Thaumarchaeota or Hadesarchaea). Furthermore, to target autotrophs, a series of 13 CO 2 stable isotope-probing experiments were conducted using filter pieces obtained after filtration of 10,000 L of groundwater to concentrate cells. These incubations identified the SAGMCG Thaumarchaeota and Bathyarchaeota as groundwater autotrophs. Overall, the results suggest that the majority of Archaea on rocks are fixing CO 2 , while archaeal autotrophy seems to be limited in the groundwater.

Archaeal Diversity and CO2 Fixers in Carbonate-/Siliciclastic-Rock Groundwater Ecosystems

PubMed Central

Lazar, Cassandre Sara; Stoll, Wenke; Lehmann, Robert; Herrmann, Martina; Schwab, Valérie F.; Akob, Denise M.; Nawaz, Ali; Wubet, Tesfaye; Buscot, François; Totsche, Kai-Uwe

2017-01-01

Groundwater environments provide habitats for diverse microbial communities, and although Archaea usually represent a minor fraction of communities, they are involved in key biogeochemical cycles. We analysed the archaeal diversity within a mixed carbonate-rock/siliciclastic-rock aquifer system, vertically from surface soils to subsurface groundwater including aquifer and aquitard rocks. Archaeal diversity was also characterized along a monitoring well transect that spanned surface land uses from forest/woodland to grassland and cropland. Sequencing of 16S rRNA genes showed that only a few surface soil-inhabiting Archaea were present in the groundwater suggesting a restricted input from the surface. Dominant groups in the groundwater belonged to the marine group I (MG-I) Thaumarchaeota and the Woesearchaeota. Most of the groups detected in the aquitard and aquifer rock samples belonged to either cultured or predicted lithoautotrophs (e.g., Thaumarchaeota or Hadesarchaea). Furthermore, to target autotrophs, a series of 13CO2 stable isotope-probing experiments were conducted using filter pieces obtained after filtration of 10,000 L of groundwater to concentrate cells. These incubations identified the SAGMCG Thaumarchaeota and Bathyarchaeota as groundwater autotrophs. Overall, the results suggest that the majority of Archaea on rocks are fixing CO2, while archaeal autotrophy seems to be limited in the groundwater. PMID:28694737

A first-principles study on the interaction of biogas with noble metal (Rh, Pt, Pd) decorated nitrogen doped graphene as a gas sensor: A DFT study

NASA Astrophysics Data System (ADS)

Zhao, Chunjiang; Wu, Huarui

2018-03-01

Density functional theory calculations are carried out to investigate the adsorption characteristics of methane (CH4), carbon dioxide (CO2), hydrogen (H2), hydrogen sulfide (H2S), nitrogen (N2), and oxygen (O2) on the surface of pyridine-like nitrogen doped graphene (PNG) as well as noble metal (Rh, Pt, Pd) decorated PNG to elaborate their potentials as gas sensors. The adsorption intensities of biogas on noble metal (Rh, Pt, Pd) decorated PNG are in the order of O2> H2S> N2> CH4> CO2> H2, which are corresponded to the order of their sensitivity on surface. Compared with biogas adsorption on pristine PNG, there exist higher adsorption ability, higher charge transfer and higher orbital hybridization upon adsorption on noble metal (Rh, Pt, Pd) decorated PNG. Consequently, the noble metal (Rh, Pt, Pd) decorated PNG can transform the existence of CH4, CO2, H2, H2S, N2, and O2 molecules into electrical signal and they could potentially be used as ideal sensors for detection of biogas in ambient situation.

Catalytic and electrocatalytic oxidation of ethanol over palladium-based nanoalloy catalysts.

PubMed

Yin, Jun; Shan, Shiyao; Ng, Mei Shan; Yang, Lefu; Mott, Derrick; Fang, Weiqin; Kang, Ning; Luo, Jin; Zhong, Chuan-Jian

2013-07-23

The control of the nanoscale composition and structure of alloy catalysts plays an important role in heterogeneous catalysis. This paper describes novel findings of an investigation for Pd-based nanoalloy catalysts (PdCo and PdCu) for ethanol oxidation reaction (EOR) in gas phase and alkaline electrolyte. Although the PdCo catalyst exhibits a mass activity similar to Pd, the PdCu catalyst is shown to display a much higher mass activity than Pd for the electrocatalytic EOR in alkaline electrolyte. This finding is consistent with the finding on the surface enrichment of Pd on the alloyed PdCu surface, in contrast to the surface enrichment of Co in the alloyed PdCo surface. The viability of C-C bond cleavage was also probed for the PdCu catalysts in both gas-phase and electrolyte-phase EOR. In the gas-phase reaction, although the catalytic conversion rate for CO2 product is higher over Pd than PdCu, the nanoalloy PdCu catalyst appears to suppress the formation of acetic acid, which is a significant portion of the product in the case of pure Pd catalyst. In the alkaline electrolyte, CO2 was detected from the gas phase above the electrolyte upon acid treatment following the electrolysis, along with traces of aldehyde and acetic acid. An analysis of the electrochemical properties indicates that the oxophilicity of the base metal alloyed with Pd, in addition to the surface enrichment of metals, may have played an important role in the observed difference of the catalytic and electrocatalytic activities. In comparison with Pd alloyed with Co, the results for Pd alloyed with Cu showed a more significant positive shift of the reduction potential of the oxygenated Pd species on the surface. These findings have important implications for further fine-tuning of the Pd nanoalloys in terms of base metal composition toward highly active and selective catalysts for EOR.

Surface Water pCO2 Variations and Sea-Air CO2 Fluxes During Summer in the Eastern Canadian Arctic

NASA Astrophysics Data System (ADS)

Burgers, T. M.; Miller, L. A.; Thomas, H.; Else, B. G. T.; Gosselin, M.; Papakyriakou, T.

2017-12-01

Based on a 2 year data set, the eastern Canadian Arctic Archipelago and Baffin Bay appear to be a modest summertime sink of atmospheric CO2. We measured surface water CO2 partial pressure (pCO2), salinity, and temperature throughout northern Baffin Bay, Nares Strait, and Lancaster Sound from the CCGS Amundsen during its 2013 and 2014 summer cruises. Surface water pCO2 displayed considerable variability (144-364 μatm) but never exceeded atmospheric concentrations, and average calculated CO2 fluxes in 2013 and 2014 were -12 and -3 mmol C m-2 d-1 (into the ocean), respectively. Ancillary measurements of chlorophyll a reveal low summertime productivity in surface waters. Based on total alkalinity and stable oxygen isotopes (δ18O) data, a strong riverine signal in northern Nares Strait coincided with relatively high surface pCO2, whereas areas of sea-ice melt occur with low surface pCO2. Further assessments, extending the seasonal observation period, are needed to properly constrain both seasonal and annual CO2 fluxes in this region.

Formaldehyde and methanol formation from reaction of carbon monoxide and hydrogen on neutral Fe2S2 clusters in the gas phase.

PubMed

Yin, Shi; Wang, Zhechen; Bernstein, Elliot R

2013-04-07

Reaction of CO with H2 on neutral FemSn clusters in a fast flow reactor is investigated both experimentally and theoretically. Single photon ionization at 118 nm is used to detect neutral cluster distributions through time of flight mass spectrometry. FemSn clusters are generated through laser ablation of a mixed iron-sulfur target in the presence of a pure helium carrier gas. A strong size dependent reactivity of (FeS)m clusters toward CO is characterized. The reaction FeS + CO → Fe + OCS is found for the FeS cluster, and the association product Fe2S2CO is observed for the Fe2S2 cluster. Products Fe2S2(13)COH2 and Fe2S2(13)COH4 are identified for reactions of (13)CO and H2 on Fe2S2 clusters: this suggests that the Fe2S2 cluster has a high catalytic activity for hydrogenation reactions of CO to form formaldehyde and methanol. Density functional theory (DFT) calculations are performed to explore the potential energy surfaces for the two reactions: Fe2S2 + CO + 2H2 → Fe2S2 + CH3OH; and Fe2S2 + CO + H2 → Fe2S2 + CH2O. A barrierless, thermodynamically favorable pathway is obtained for both catalytic processes. Catalytic cycles for formaldehyde and methanol formation from CO and H2 on a Fe2S2 cluster are proposed based on our experimental and theoretical investigations. The various reaction mechanisms explored by DFT are in good agreement with the experimental results. Condensed phase iron sulfide, which contains exposed Fe2S2 units on its surface, is suggested to be a good catalyst for low temperature formaldehyde/methanol synthesis.

3D Interconnected Mesoporous Alumina with Loaded Hemoglobin as a Highly Active Electrochemical Biosensor for H2 O2.

PubMed

Yang, Xuanyu; Cheng, Xiaowei; Song, Hongyuan; Ma, Junhao; Pan, Panpan; Elzatahry, Ahmed A; Su, Jiacan; Deng, Yonghui

2018-06-01

Alumina is one of the most common and stable metal oxides in nature, which has been developed as a novel adsorbent in enrichment of biomolecules due to its excellent affinity to phosphor or amino groups. In this study, ordered mesoporous alumina (OMA) with interconnected mesopores and surface acidic property is synthesized through a solvent evaporation induced co-assembly process using poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymer as a template and aluminium acetylacetonate (Al(acac) 3 ) as the aluminium source. The pore size (12.1-19.7 nm), pore window size (3.5-9.0 nm) and surface acidity (0.092-0.165 mmol g -1 ) can be precisely adjusted. The highly porous structure endows the OMA materials with high hemoglobin (Hb) immobilization capacity (170 mg g -1 ). The obtained Hb@OMA composite is used as an electrocatalyst of biosensor for convienet and fast detection of hydrogen peroxide (H 2 O 2 ) with a low H 2 O 2 detection limit of 1.7 × 10 -8 m and a wide linear range of 2.5 × 10 -8 to 5.0 × 10 -5 m. Moreover, the Hb@OMA sensors show a good performance in real time detection of H 2 O 2 released from Homo sapiens bone osteosarcoma, indicating their potential application in complex biological processes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pluto's surface composition and atmosphere

NASA Astrophysics Data System (ADS)

Young, L. A.; Gladstone, R.; Summers, M. E.; Strobel, D. F.; Kammer, J.; Hinson, D. P.; Grundy, W. M.; Cruikshank, D. P.; Protopapa, S.; Schmitt, B.; Stern, A.; Weaver, H. A., Jr.; Olkin, C.; Ennico Smith, K.

2017-12-01

New Horizons studied Pluto's N2-dominated neutral atmosphere through radio (at 4.2 cm with the REX radio experiment), solar and stellar occultations and airglow (at 52-187 nm with the Alice ultraviolet spectrograph), and imaging (with the LORRI and MVIC visible-wavelength cameras). It studied the plasma environment and solar wind interaction with in situ instruments (PEPPSI and SWAP). Contemporaneous observations of Pluto's atmosphere from Earth included a ground-based stellar occultation and ALMA observations of gaseous CO and HCN. Joint analysis of these datasets reveal a variable boundary layer; a stable lower atmosphere; radiative heating and cooling; haze production and hydrocarbon chemistry; diffusive equilibrium; and slower-than-expected escape. New Horizons studied Pluto's surface composition with the LEISA near-infrared spectral imager from 1.25 to 2.5 micron. Additional compositional information at higher spatial resolution came from the MVIC 4-channel color imager, which included a channel centered at 0.89 micron specifically designed to detect solid CH4. These instruments allow mapping of the volatiles N2, CO, and CH4, the surface expression of the H2O bedrock, and the dark, reddish material presumed to be tholins. These observations reveal a large equatorial basin (informally named Sptunik Planitia), filled with N2 ice with minor amounts of CO and CH4, surrounded by hills of CH4 and H2O ice. Broadly speaking, composition outside of Sptunik Planitia follows latitudinal banding, with dark, mainly volatile free terrains near the equator, with N2, CO, and CH4 at mid-northern latitudes, and mainly CH4 at high northern latitudes. Deviations from these broad trends are seen, and point to complex surface-atmosphere interactions at diurnal, seasonal, perennial, and million-year timescales.

IR reflectance spectroscopy of carbon dioxide clathrate hydrates. Implications for Saturn's icy moons.

NASA Astrophysics Data System (ADS)

Oancea, A.; Grasset, O.; Le Menn, E.; Bezacier, L.; Bollengier, O.; Le Mouélic, S.; Tobie, G.

2012-04-01

A CO2 spectral band was discovered by VIMS on the Saturn's satellites Dione, Hyperion, Iapetus and Phoebe [1]. The band position on the three first satellites corresponds to CO2 trapped in a complex material, but no indication exists whether this latter is water ice or some mineral or complex organic compound [1]. On Phoebe, the CO2 spectral band is consistent with solid CO2 or CO2 molecules trapped in the small cages of a clathrate hydrate structure [2]. It is thought that clathrate hydrates could play a significant role in the chemistry of the solar nebula [3] and in the physical evolution of astrophysical objects [4]. But so far, no clathrate hydrate structure has been observed in astrophysical environments. Moreover, identification of molecules trapped in a clathrate hydrate structure is extremely difficult because of the strong IR vibration modes of the water ice matrix. In this work, experimental IR reflectance spectra for CO2 clathrate hydrates are studied on grains and films. Clathrates are synthesized in a high pressure autoclave at low temperatures. IR spectral analysis is made with a low pressure and low temperature cryostat. These experimental conditions - 80 < T < 110 K, P~10-5 bar - are relevant to icy moons' surfaces. We have observed that the IR reflectance, in the spectral region (3 - 5 μm) characterized by H2O and CO2 high absorption coefficients, is strongly dependent on physical (size, surface) and optical (n and k) properties of the samples. The impact of these parameters on the CO2 clathrate IR reflectance spectrum will be presented. A comparison between the absorption bands of CO2 clathrate hydrates obtained in our lab and CO2 absorption bands as detected by VIMS on the icy satellites of Saturn will be shown. This experimental work confirms that VIMS data are not consistent with the presence of structure I CO2 clathrate hydrates on the surface of the icy moons. Possibility of having metastable structure II still remains unsolved and will be discussed. [1] Dalton et al., Space Sci. Rev. 2010, 153 : 113-154. [2] Cruikshank D.P. et al, Icarus, 2010, 206: 561-572. [3] Mousis O. et al , Ap. J. 2009, 691: 1780-1786. [4] Choukroun M. et al, in Solar System Ices, edited by Castillo-Rogez, J. et al., 2011.

Quantum-state-resolved CO2 scattering dynamics at the gas-liquid interface: dependence on incident angle.

PubMed

Perkins, Bradford G; Nesbitt, David J

2007-08-09

Energy transfer dynamics at the gas-liquid interface have been probed with a supersonic molecular beam of CO2 and a clean perfluorinated-liquid surface in vacuum. High-resolution infrared spectroscopy measures both the rovibrational state populations and the translational distributions for the scattered CO2 flux. The present study investigates collision dynamics as a function of incident angle (thetainc = 0 degrees, 30 degrees, 45 degrees, and 60 degrees), where column-integrated quantum state populations are detected along the specular-scattering direction (i.e., thetascat approximately thetainc). Internal state rovibrational and Doppler translational distributions in the scattered CO2 yield clear evidence for nonstatistical behavior, providing quantum-state-resolved support for microscopic branching of the gas-liquid collision dynamics into multiple channels. Specifically, the data are remarkably well described by a two-temperature model, which can be associated with both a trapping desorption (TD) component emerging at the surface temperature (Trot approximately TS) and an impulsive scattering (IS) component appearing at hyperthermal energies (Trot > TS). The branching ratio between the TD and IS channels is found to depend strongly on thetainc, with the IS component growing dramatically with increasingly steeper angle of incidence.

High CO2/H+ dialysis in the caudal ventrolateral medulla (Loeschcke's area) increases ventilation in wakefulness.

PubMed

da Silva, Glauber S F; Li, Aihua; Nattie, Eugene

2010-04-15

Central chemoreception, the detection of CO(2)/H(+) within the brain and the resultant effect on ventilation, was initially localized at two areas on the ventrolateral medulla, one rostral (rVLM-Mitchell's) the other caudal (cVLM-Loeschcke's), by surface application of acidic solutions in anesthetized animals. Focal dialysis of a high CO(2)/H(+) artificial cerebrospinal fluid (aCSF) that produced a milder local pH change in unanesthetized rats (like that with a approximately 6.6mm Hg increase in arterial P(CO2)) delineated putative chemoreceptor regions for the rVLM at the retrotrapezoid nucleus and the rostral medullary raphe that function predominantly in wakefulness and sleep, respectively. Here we ask if chemoreception in the cVLM can be detected by mild focal stimulation and if it functions in a state dependent manner. At responsive sites just beneath Loeschcke's area, ventilation was increased by, on average, 17% (P<0.01) only in wakefulness. These data support our hypothesis that central chemoreception is a distributed property with some sites functioning in a state dependent manner. Copyright 2010 Elsevier B.V. All rights reserved.

Optical CO2 sensing with ionic liquid doped electrospun nanofibers.

PubMed

Aydogdu, Sibel; Ertekin, Kadriye; Suslu, Aslihan; Ozdemir, Mehtap; Celik, Erdal; Cocen, Umit

2011-03-01

The first use of electrospun nanofibrous materials as highly responsive fluorescence quenching-based optical CO(2) sensors is reported. Poly(methyl methacrylate) and ethyl cellulose were used as polymeric materials. Sensing slides were fabricated by electrospinning technique. A fiber-optic bundle was used for the gas detection. CO(2) sensors based on the change in the fluorescence signal intensity of ion pair form of 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS). The sensor slides showed high sensitivities due to the high surface area-to-volume ratio of the nanofibrous membrane structures. The preliminary results of Stern-Volmer analysis show that the sensitivities of electrospun nanofibrous membranes to detect CO(2) are 24 to 120 fold higher than those of the thin film based sensors. The response times of the sensing reagents were short and the signal changes were fully reversible. The stability of ion pair form of HPTS in the employed matrix materials was excellent and when stored in the ambient air of the laboratory there was no significant drift in signal intensity after 7 months. Our stability tests are still in progress. © Springer Science+Business Media, LLC 2010

Matrix effect of sodium compounds on the determination of metal ions in aqueous solutions by underwater laser-induced breakdown spectroscopy

DOE PAGES

Goueguel, Christian; McIntyre, Dustin L.; Jain, Jinesh; ...

2015-06-30

A significant portion of the carbon sequestration research being performed in the United States involves the risk assessment of injecting large quantities of carbon dioxide into deep saline aquifers. Leakage of CO 2 has the potential to affect the quality of groundwater supplies in case contaminants migrate through underlying conduits. New remote sensing and near-surface monitoring technologies are needed to ensure that injection, abandoned, and monitoring wells are structurally sound, and that CO 2 remains within the geologic storage reservoir. In this paper, we propose underwater laser-induced breakdown spectroscopy (underwater LIBS) as an analytical method for monitoring naturally occurring elementsmore » that can act as tracers to detect a CO 2 leak from storage sites. Laboratory-scale experiments were conducted to measure Sr 2+, Ca 2+, K +, and Li + in bulk solutions to ascertain the analytical performance of underwater LIBS. We compared the effect of NaCl, Na 2CO 3, and Na 2SO 4 on the analytes calibration curves to determine underwater LIBS’ ability to analyze samples of sodium compounds. In all cases, the calibration curves showed a good linearity within 2 orders of magnitude. The limit of detections (LODs) obtained for K + (30±1 ppb) and Li + (60±2 ppb) were in ppb range, while higher LODs were observed for Ca 2+ (0.94±0.14 ppm) and Sr 2+ (2.89±0.11 ppm). Evaluation of the calibration curves for the analytes in mixed solutions showed dependence of the lines’ intensity with the sodium compounds. The intensities increased respectively in the presence of dissolved NaCl and Na 2SO 4, whereas the intensities slightly decreased in the presence of Na 2CO 3. Lastly, the capabilities of underwater LIBS to detect certain elements in the ppb or in the low ppm range make it particularly appealing for in situ monitoring of a CO 2 leak.« less

Matrix effect of sodium compounds on the determination of metal ions in aqueous solutions by underwater laser-induced breakdown spectroscopy

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

Goueguel, Christian; McIntyre, Dustin L.; Jain, Jinesh

A significant portion of the carbon sequestration research being performed in the United States involves the risk assessment of injecting large quantities of carbon dioxide into deep saline aquifers. Leakage of CO 2 has the potential to affect the quality of groundwater supplies in case contaminants migrate through underlying conduits. New remote sensing and near-surface monitoring technologies are needed to ensure that injection, abandoned, and monitoring wells are structurally sound, and that CO 2 remains within the geologic storage reservoir. In this paper, we propose underwater laser-induced breakdown spectroscopy (underwater LIBS) as an analytical method for monitoring naturally occurring elementsmore » that can act as tracers to detect a CO 2 leak from storage sites. Laboratory-scale experiments were conducted to measure Sr 2+, Ca 2+, K +, and Li + in bulk solutions to ascertain the analytical performance of underwater LIBS. We compared the effect of NaCl, Na 2CO 3, and Na 2SO 4 on the analytes calibration curves to determine underwater LIBS’ ability to analyze samples of sodium compounds. In all cases, the calibration curves showed a good linearity within 2 orders of magnitude. The limit of detections (LODs) obtained for K + (30±1 ppb) and Li + (60±2 ppb) were in ppb range, while higher LODs were observed for Ca 2+ (0.94±0.14 ppm) and Sr 2+ (2.89±0.11 ppm). Evaluation of the calibration curves for the analytes in mixed solutions showed dependence of the lines’ intensity with the sodium compounds. The intensities increased respectively in the presence of dissolved NaCl and Na 2SO 4, whereas the intensities slightly decreased in the presence of Na 2CO 3. Lastly, the capabilities of underwater LIBS to detect certain elements in the ppb or in the low ppm range make it particularly appealing for in situ monitoring of a CO 2 leak.« less

DFT studies on H 2O adsorption and its effect on CO oxidation over spinel Co 3O 4 (110) surface

NASA Astrophysics Data System (ADS)

Xu, Xiang Lan; Li, Jun Qian

2011-12-01

Adsorption of H2O and its effect on CO oxidation over spinel Co3O4 (110) surface were studied by density functional theory calculations. H2O is adsorbed favorably at the octahedral cobalt (Cooct) site through O atom on the surface. Hydrogen bonding interaction between 1s orbitals of H atoms in H2O and the 2p orbitals of surface active oxygen sites plays a key role for H2O adsorption. The inhibition effect of H2O adsorption on the CO oxidation over the surfaces is attributed to the competition between H2O and CO molecules for the surface twofold coordinated oxygen site.

Geochemical evidence for a magmatic CO2 degassing event at Mammoth Mountain, California, September-December 1997

USGS Publications Warehouse

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

2000-01-01

Recent time series soil CO2 concentration data from monitoring stations in the vicinity of Mammoth Mountain, California, reveal strong evidence for a magmatic degassing event during the fall of 1997 lasting more than 2 months. Two sensors at Horseshoe Lake first recorded the episode on September 23, 1997, followed 10 days later by a sensor on the north flank of Mammoth Mountain. Direct degassing from shallow intruding magma seems an implausible cause of the degassing event, since the gas released at Horseshoe Lake continued to be cold and barren of other magmatic gases, except for He. We suggest that an increase in compressional strain on the area south of Mammoth Mountain driven by movement of major fault blocks in Long Valley caldera may have triggered an episode of increased degassing by squeezing additional accumulated CO2 from a shallow gas reservoir to the surface along faults and other structures where it could be detected by the CO2 monitoring network. Recharge of the gas reservoir by CO2 emanating from the deep intrusions that probably triggered deep long-period earthquakes may also have contributed to the degassing event. The nature of CO2 discharge at the soil-air interface is influenced by the porous character of High Sierra soils and by meteorological processes. Solar insolation is the primary source of energy for the Earth atmosphere and plays a significant role in most diurnal processes at the Earth surface. Data from this study suggest that external forcing due largely to local orographic winds influences the fine structure of the recorded CO2 signals.

Variability in soil CO2 production and surface CO2 efflux across riparian-hillslope transitions

Treesearch

Vincent Jerald Pacific

2007-01-01

The spatial and temporal controls on soil CO2 production and surface CO2 efflux have been identified as an outstanding gap in our understanding of carbon cycling. I investigated both the spatial and temporal variability of soil CO2 concentrations and surface CO2 efflux across eight topographically distinct riparian-hillslope transitions in the ~300 ha subalpine upper-...

[Research on early fire detection with CO-CO2 FTIR-spectroscopy].

PubMed

Du, Jian-hua; Zhang, Ren-cheng; Huang, Xiang-ying; Gong, Xue; Zhang, Xiao-hua

2007-05-01

A new fire detection method is put forward based on the theory of FTIR spectroscopy through analyzing all kinds of detection methods, in which CO and CO2 are chosen as early fire detection objects, and an early fire experiment system has been set up. The concentration characters of CO and CO2 were obtained through early fire experiments including real alarm sources and nuisance alarm sources. In real alarm sources there are abundant CO and CO2 which change regularly. In nuisance alarm sources there is almost no CO. So it's feasible to reduce the false alarms and increase the sensitivity of early fire detectors through analyzing the concentration characters of CO and CO2.

A Wunda-full world? Carbon dioxide ice deposits on Umbriel and other Uranian moons

NASA Astrophysics Data System (ADS)

Sori, Michael M.; Bapst, Jonathan; Bramson, Ali M.; Byrne, Shane; Landis, Margaret E.

2017-07-01

Carbon dioxide has been detected on the trailing hemispheres of several Uranian satellites, but the exact nature and distribution of the molecules remain unknown. One such satellite, Umbriel, has a prominent high albedo annulus-shaped feature within the 131-km-diameter impact crater Wunda. We hypothesize that this feature is a solid deposit of CO2 ice. We combine thermal and ballistic transport modeling to study the evolution of CO2 molecules on the surface of Umbriel, a high-obliquity (∼98°) body. Considering processes such as sublimation and Jeans escape, we find that CO2 ice migrates to low latitudes on geologically short (100s-1000 s of years) timescales. Crater morphology and location create a local cold trap inside Wunda, and the slopes of crater walls and a central peak explain the deposit's annular shape. The high albedo and thermal inertia of CO2 ice relative to regolith allows deposits 15-m-thick or greater to be stable over the age of the solar system. We conclude that Wunda, located at low latitude (7.9° S) and near the center of the trailing hemisphere where CO2 detections are strongest, likely contains a solid CO2 ice deposit. We discuss prospects for similar CO2 ice deposits on crater floors on the other major Uranian moons, and predict that they are present on Ariel, Titania, and possibly Oberon (but not Miranda or smaller satellites). Such deposits have likely not been observed due to the limited nature of Voyager 2 image coverage.

Measurements of the H2(13)CO ortho/para ratio in cold dark molecular clouds

NASA Technical Reports Server (NTRS)

Minh, Y. C.; Dickens, J. E.; Irvine, W. M.; McGonagle, D.

1995-01-01

H2(13)CO has been detected for the first time toward cold dark molecular clouds using the NRAO 12 m telescope. The H2(13)CO ortho/para abundance ratio R for B335, which we report as R approximately 1.7, suggests equilibrium at the local kinetic temperature and appears to be distinctly different from that for both TMC-1 and L134N, where R is close to or higher than the statistical value 3. Since only B335 among the observed positions includes an imbedded IR source, this difference may result from heating of the grain surfaces, providing the energy necessary for desorption of formaldehyde formed on the grains.

Novel recirculating loop reactor for studies on model catalysts: CO oxidation on Pt/TiO2(110)

NASA Astrophysics Data System (ADS)

Tenney, Samuel A.; Xie, Kangmin; Monnier, John R.; Rodriguez, Abraham; Galhenage, Randima P.; Duke, Audrey S.; Chen, Donna A.

2013-10-01

A novel recirculating loop microreactor coupled to an ultrahigh vacuum (UHV) chamber has been constructed for the kinetic evaluation of model catalysts, which can be fully characterized by UHV surface science techniques. The challenge for this reactor design is to attain sufficient sensitivity to detect reactions on model single-crystal surfaces, which have a low number of active sites compared to conventional catalysts of equivalent mass. To this end, the total dead volume of the reactor system is minimized (32 cm3), and the system is operated in recirculation mode so that product concentrations build up to detectable levels over time. The injection of gas samples into the gas chromatography column and the refilling of the recirculation loop with fresh feed gas are achieved with computer-controlled, automated switching valves. In this manner, product concentrations can be followed over short time intervals (15 min) for extended periods of time (24 h). A proof of principle study in this reactor for CO oxidation at 145-165 °C on Pt clusters supported on a rutile TiO2(110) single crystal yields kinetic parameters that are comparable to those reported in the literature for CO oxidation on Pt clusters on powdered oxide supports, as well as on Pt(100). The calculated activation energy is 16.4 ± 0.7 kcal/mol, the turnover frequency is 0.03-0.06 molecules/(site.s) over the entire temperature range, and the reaction orders in O2 and CO at 160 °C are 0.9 ± 0.2 and -0.82 ± 0.03, respectively.

On-surface Fenton and Fenton-like reactions appraised by paper spray ionization mass spectrometry.

PubMed

Resende, S F; Oliveira, B S; Augusti, R

2018-06-21

On-surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe 2+ / H 2 O 2 ) and Fenton-like (M n+ / H 2 O 2 ; M n+ = Fe 3+ , Co 2+ , Cu 2+ , Mn 2+ ) systems was investigated by using paper spray ionization mass spectrometry (PS-MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS-MS analyzes). The results indicated the following order in the rates of such reactions: Fe 2+ /H 2 O 2 > H 2 O 2 > Cu 2+ /H 2 O 2 > M n+ / H 2 O 2 (M n+ = Fe 3+ , Co 2+ , Mn 2+ ) ~ M n+ (M n+ = Fe 2+ , Fe 3+ , Co 2+ , Cu 2+ , Mn 2 . The superior capability of Fe 2+ /H 2 O 2 in causing the degradation of sildenafil indicates that Fe 2+ efficiently decomposes H 2 O 2 to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H 2 O 2 can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, i. e. Fe 3+ , Co 2+ , Cu 2+ and Mn 2+ . A unique oxidation by-product was detected in the reaction between Fe 2+ /H 2 O 2 with sildenafil and a possible structure for it was proposed based on the MS/MS data. The on-surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS-MS shown to be a convenient platform to promptly monitor on-surface oxidation reactions. This article is protected by copyright. All rights reserved.

Geophysical Methods, Tracer Leakage, and Flow Modeling Studies at the West Pearl Queen Carbon Sequestration/EOR Pilot Site

NASA Astrophysics Data System (ADS)

Bromhal, G. S.; Wilson, T. H.; Wells, A.; Diehl, R.; Smith, D. H.

2003-12-01

Recently, a few thousand tons of CO2 were injected into the West Pearl Queen field, a depleted oil reservoir in southeastern New Mexico, for a pilot carbon sequestration project. Small amounts of 3 different perfluorocarbon tracers were injected with the CO2. Approximately 50 capillary absorption tube samplers (CATS) were located across the field within 2m of the grounds surface to detect the tracers in extremely small (~10-13L) quantities. After only several days, the CATS detected quantities of tracers at distances of up to 350m from the injection well. Greater amounts of tracers were detected in the different directions. The underground transport mechanism(s) are uncertain; however, appearance of tracer in the CATS after only a 6 day period suggests that CO2 movement may have occurred through near-surface processes. Subsequent tracer measurements made over 10 and 54 day time periods revealed continued tracer leakage. To try to understand the tracer information, we conducted lineament interpretations of the area using a black and white aerial photo taken in 1949, digital orthophotos, and Landsat TM imagery. Lineament interpretations revealed distinct northeast and northwest trending lineament sets. These directions coincided roughly with the direction of tracer-leakage into areas northwest and southwest of the injection well. The near-surface geology consists of a few-feet thick veneer of late Pleistocene and Holocene sand dunes covering the middle Pleistocene Mescalero caliche. A survey of the caliche was made using ground penetrating radar (GPR) to attempt to identify any preferential migration pathways. Modeling studies also were performed to identify the potential leakage pathways at the site. Because of the relatively fast appearance of tracers at large distances from the injection well, simple diffusion through the surface layers was ruled out. Wind patterns in the area have also made transport through the atmosphere and back into the ground highly unlikely. Other potential leakage pathways were transport from the well through the saturated zone and diffusion into the unsaturated zone or combined pressure-driven and diffusive flow through the vadose zone. An analysis of these alternatives has been made for this study.

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

Thompson, Christopher J.; Martin, Paul F.; Chen, Jeffrey

A fully automated titration system with infrared detection was developed for investigating interfacial chemistry at high pressures. The apparatus consists of a high-pressure fluid generation and delivery system coupled to a high-pressure cell with infrared optics. A manifold of electronically actuated valves is used to direct pressurized fluids into the cell. Precise reagent additions to the pressurized cell are made with calibrated tubing loops that are filled with reagent and placed in-line with the cell and a syringe pump. The cell’s infrared optics facilitate both transmission and attenuated total reflection (ATR) measurements to monitor bulk-fluid composition and solid-surface phenomena suchmore » as adsorption, desorption, complexation, dissolution, and precipitation. Switching between the two measurement modes is accomplished with moveable mirrors that direct radiation from a Fourier transform infrared spectrometer into the cell along transmission or ATR light paths. The versatility of the high-pressure IR titration system is demonstrated with three case studies. First, we titrated water into supercritical CO2 (scCO2) to generate an infrared calibration curve and determine the solubility of water in CO2 at 50 °C and 90 bar. Next, we characterized the partitioning of water between a montmorillonite clay and scCO2 at 50 °C and 90 bar. Transmission-mode spectra were used to quantify changes in the clay’s sorbed water concentration as a function of scCO2 hydration, and ATR measurements provided insights into competitive residency of water and CO2 on the clay surface and in the interlayer. Finally, we demonstrated how time-dependent studies can be conducted with the system by monitoring the carbonation reaction of forsterite (Mg2SiO4) in water-bearing scCO2 at 50 °C and 90 bar. Immediately after water dissolved in the scCO2, a thin film of adsorbed water formed on the mineral surface, and the film thickness increased with time as the forsterite began to dissolve. However, after approximately 2.5 hours, the trend reversed, and a carbonate precipitate began to form on the forsterite surface, exposing dramatic chemical changes in the thin-water film. Collectively, these applications illustrate how the high-pressure IR titration system can provide molecular-level information about the interactions between variably wet scCO2 and minerals relevant to underground storage of CO2 (geologic carbon sequestration). The apparatus could also be utilized to study high-pressure interfacial chemistry in other areas such as catalysis, polymerization, food processing, and oil and gas recovery.« less

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

Thompson, Christopher J., E-mail: chris.thompson@pnnl.gov; Martin, Paul F.; Chen, Jeffrey

A fully automated titration system with infrared detection was developed for investigating interfacial chemistry at high pressures. The apparatus consists of a high-pressure fluid generation and delivery system coupled to a high-pressure cell with infrared optics. A manifold of electronically actuated valves is used to direct pressurized fluids into the cell. Precise reagent additions to the pressurized cell are made with calibrated tubing loops that are filled with reagent and placed in-line with the cell and a syringe pump. The cell's infrared optics facilitate both transmission and attenuated total reflection (ATR) measurements to monitor bulk-fluid composition and solid-surface phenomena suchmore » as adsorption, desorption, complexation, dissolution, and precipitation. Switching between the two measurement modes is accomplished with moveable mirrors that direct the light path of a Fourier transform infrared spectrometer into the cell along transmission or ATR light paths. The versatility of the high-pressure IR titration system was demonstrated with three case studies. First, we titrated water into supercritical CO{sub 2} (scCO{sub 2}) to generate an infrared calibration curve and determine the solubility of water in CO{sub 2} at 50 °C and 90 bar. Next, we characterized the partitioning of water between a montmorillonite clay and scCO{sub 2} at 50 °C and 90 bar. Transmission-mode spectra were used to quantify changes in the clay's sorbed water concentration as a function of scCO{sub 2} hydration, and ATR measurements provided insights into competitive residency of water and CO{sub 2} on the clay surface and in the interlayer. Finally, we demonstrated how time-dependent studies can be conducted with the system by monitoring the carbonation reaction of forsterite (Mg{sub 2}SiO{sub 4}) in water-bearing scCO{sub 2} at 50 °C and 90 bar. Immediately after water dissolved in the scCO{sub 2}, a thin film of adsorbed water formed on the mineral surface, and the film thickness increased with time as the forsterite began to dissolve. However, after approximately 2.5 h, the trend reversed, and a carbonate precipitate began to form on the forsterite surface, exposing dramatic chemical changes in the thin-water film. Collectively, these applications illustrate how the high-pressure IR titration system can provide molecular-level information about the interactions between variably wet scCO{sub 2} and minerals relevant to underground storage of CO{sub 2} (geologic carbon sequestration). The apparatus could also be utilized to study high-pressure interfacial chemistry in other areas such as catalysis, polymerization, food processing, and oil and gas recovery.« less

Giant galaxy growing from recycled gas: ALMA maps the circumgalactic molecular medium of the Spiderweb in [C I

NASA Astrophysics Data System (ADS)

Emonts, B. H. C.; Lehnert, M. D.; Dannerbauer, H.; De Breuck, C.; Villar-Martín, M.; Miley, G. K.; Allison, J. R.; Gullberg, B.; Hatch, N. A.; Guillard, P.; Mao, M. Y.; Norris, R. P.

2018-06-01

The circumgalactic medium (CGM) of the massive Spiderweb Galaxy, a conglomerate of merging proto-cluster galaxies at z = 2.2, forms an enriched interface where feedback and recycling act on accreted gas. This is shown by observations of [C I], CO(1-0), and CO(4-3) performed with the Atacama Large Millimeter Array and Australia Telescope Compact Array. [C I] and CO(4-3) are detected across ˜50 kpc, following the distribution of previously detected low-surface-brightness CO(1-0) across the CGM. This confirms our previous results on the presence of a cold molecular halo. The central radio galaxy MRC 1138-262 shows a very high global L^'_CO(4-3)/L^'_CO(1-0) ˜ 1, suggesting that mechanisms other than FUV-heating by star formation prevail at the heart of the Spiderweb Galaxy. Contrary, the CGM has L^'_CO(4-3)/L^'_CO(1-0) and L^'_[C I]/L^'_CO(1-0) similar to the ISM of five galaxies in the wider proto-cluster, and its carbon abundance, X_[C I]/X_H_2, resembles that of the Milky Way and star-forming galaxies. The molecular CGM is thus metal-rich and not diffuse, confirming a link between the cold gas and in situ star formation. Thus, the Spiderweb Galaxy grows not directly through accretion of gas from the cosmic web, but from recycled gas in the CGM.

Sensor systems for the Altair Lunar Lander:

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

Mariella, R

The Altair Lunar Lander will enable astronauts to learn to live and work on the moon for extended periods of time, providing the experience needed to expand human exploration farther into the solar system. My overriding recommendation: Use independent and complementary [sometimes referred to as 'orthogonal'] techniques to disambiguate confounding/interfering signals. E.g.: a mass spectrometer ['MS'], which currently serves as a Majority Constituent Analyzer ['MCA'] can be very valuable in detecting the presence of a gaseous specie, so long as it falls on a mass-to-charge ratio ['m/z'] that is not already occupied by a majority constituent of cabin air. Considermore » the toxic gas, CO. Both N{sub 2} and CO have parent peaks of m/z = 28, and CO{sub 2} has a fragment peak at m/z = 28 [and at 16 and 12], so the N{sub 2} and CO{sub 2} m/z=28 signals could mask low, but potentially-dangerous levels of CO. However there are numerous surface-sensitive CO detectors, as well as tunable-diode-laser-based CO sensors that could provide independent monitoring of CO. Also, by appending a gas chromatograph ['GC'] as the front-end sample processer, prior to the inlet of the MS, one can rely upon the GC to separate CO from N{sub 2} and CO{sub 2}, providing the crew with another CO monitor. If the Altair Lunar Lander is able to include a Raman-based MCA for N{sub 2}, O{sub 2}, H{sub 2}O, and CO{sub 2}, then each type of MCA would have cross-references, providing more confidence in the ongoing performance of each technique, and decreasing the risk that one instrument might fail to perform properly, without being noticed. See, also Dr. Pete Snyder's work, which states 'An orthogonal technologies sensor system appears to be attractive for a high confidence detection of presence and temporal characterization of bioaerosols.' Another recommendation: Use data fusion for event detection to decrease uncertainty: tie together the outputs from multiple sensing modalities - eNose, solid-state sensors, GC-IMS, GC-MS - via nonlinear algorithms, such as an 'artificial neural net.' MA Ryan at the JPL and Henry Abarbanel at UCSD are possible candidates to implement such an approach.« less

Interactions between iron and organic matter may influence the fate of permafrost carbon in the Arctic

NASA Astrophysics Data System (ADS)

Cory, R. M.; Trusiak, A.; Ward, C.; Kling, G. W.; Tfaily, M.; Paša-Tolić, L.; Noel, V.; Bargar, J.

2017-12-01

The ongoing thawing of permafrost soils is the only environmental change that allows tremendous stores of organic carbon (C) to be converted into carbon dioxide (CO2) on decadal time scales, thus providing a positive and accelerating feedback to global warming. Evidence suggests that iron enhances abiotic reactions that convert dissolved organic matter (DOM) to CO2 in dark soils and in sunlit surface waters depending on its redox state and association with DOM (i.e., iron-DOM complexation). However, the complexation of iron in surface waters and soils remains too poorly understood to predict how iron influences the rates of oxidation of DOM to CO2. To address this knowledge gap, we characterized iron-DOM complexation in iron-rich soil and surface waters of the Arctic, in combination with measurements of DOM oxidation to CO2. These waters contain high concentrations of dissolved iron and DOM (up to 1 and 2 mM, respectively), and low concentrations of other potential ligands for iron such as sulfide, carbonate, chloride, or bromide. Ultra-high resolution mass spectrometry (FT-ICR MS) was used to identify ligands for iron within the DOM pool, and synchrotron based X-ray analysis (XAS and EXAFS) was used to assess iron's oxidation state, to detect iron complexation, and to constrain the chemical composition of the complexes. Across a natural gradient of dissolved iron and DOM concentrations, many potential ligands were identified within DOM that are expected to complex with iron (e.g., aromatic acids). EXAFS showed substantial complexation of reduced ferrous iron (Fe(II)) to DOM in arctic soil waters, on the basis of comparison to Fe(II)-DOM reference spectra. Identification of iron complexed to DOM in soil waters is consistent with strongly co-varying iron and DOM concentrations in arctic soil and surface waters, and supports our hypothesis that complexation of iron by DOM influences dark and light redox reactions that oxidize DOM to CO2. Understanding the molecular controls on the biogeochemical reactions that convert permafrost carbon to CO2 is critical for understanding the role of the Arctic in current and future climate change.

Rational Design of Bi Nanoparticles for Efficient Electrochemical CO 2 Reduction: The Elucidation of Size and Surface Condition Effects

DOE PAGES

Zhang, Zhiyong; Chi, Miaofang; Veith, Gabriel M.; ...

2016-08-08

Here we report an efficient electrochemical conversion of CO 2 to CO on surface-activated bismuth nanoparticles (NPs) in acetonitrile (MeCN) under ambient conditions, with the assistance of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]). Through the comparison between electrodeposited Bi films (Bi-ED) and different types of Bi NPs, we, for the first time, demonstrate the effects of catalyst’s size and surface condition on organic phase electrochemical CO 2 reduction. Our study reveals that the surface inhibiting layer (hydrophobic surfactants and Bi 3+ species) formed during the synthesis and purification process hinders the CO 2 reduction, leading to a 20% drop in Faradaic efficiency formore » CO evolution (FE CO). Bi particle size showed a significant effect on FE CO when the surface of Bi was air-oxidized, but this effect of size on FE CO became negligible on surface-activated Bi NPs. After the surface activation (hydrazine treatment) that effectively removed the native inhibiting layer, activated 36-nm Bi NPs exhibited an almost-quantitative conversion of CO 2 to CO (96.1% FE CO), and a mass activity for CO evolution (MA CO) of 15.6 mA mg –1, which is three-fold higher than the conventional Bi-ED, at ₋2.0 V (vs Ag/AgCl). Ultimately, this work elucidates the importance of the surface activation for an efficient electrochemical CO 2 conversion on metal NPs and paves the way for understanding the CO 2 electrochemical reduction mechanism in nonaqueous media.« less

CO line emission from galaxies in the Epoch of Reionization

NASA Astrophysics Data System (ADS)

Vallini, L.; Pallottini, A.; Ferrara, A.; Gallerani, S.; Sobacchi, E.; Behrens, C.

2018-01-01

We study the CO line luminosity (LCO), the shape of the CO spectral line energy distribution (SLED), and the value of the CO-to-H2 conversion factor in galaxies in the Epoch of Reionization (EoR). For this aim, we construct a model that simultaneously takes into account the radiative transfer and the clumpy structure of giant molecular clouds (GMCs) where the CO lines are excited. We then use it to post-process state-of-the-art zoomed, high resolution (30 pc), cosmological simulation of a main-sequence (M* ≈ 1010 M⊙, SFR ≈ 100 M⊙ yr- 1) galaxy, 'Althæa', at z ≈ 6. We find that the CO emission traces the inner molecular disc (r ≈ 0.5 kpc) of Althæa with the peak of the CO surface brightness co-located with that of the [C II] 158 μm emission. Its LCO(1-0) = 104.85 L⊙ is comparable to that observed in local galaxies with similar stellar mass. The high (Σgas ≈ 220 M⊙ pc- 2) gas surface density in Althæa, its large Mach number (M ≈ 30) and the warm kinetic temperature (Tk ≈ 45 K) of GMCs yield a CO SLED peaked at the CO(7-6) transition, i.e. at relatively high-J and a CO-to-H2 conversion factor α _CO≈ 1.5 M_{⊙} (K km s^{-1} pc^2)^{-1} lower than that of the Milky Way. The Atacama Large Millimeter/submillimeter Array observing time required to detect (resolve) at 5σ the CO(7-6) line from galaxies similar to Althæa is ≈13 h (≈38 h).

Application of Relaxed Eddy Accumulation (REA) method to estimate CO2 and CH4 surface fluxes in the city of Krakow, southern Poland.

NASA Astrophysics Data System (ADS)

Zimnoch, Miroslaw; Gorczyca, Zbigniew; Pieniazek, Katarzyna; Jasek, Alina; Chmura, Lukasz; Rozanski, Kazimierz

2013-04-01

There is a growing interest in the recent years in studies aimed at quantifying carbon cycling in urban centres. Worldwide migration of human population from rural to urban areas and corresponding growth of extensive urban agglomerations and megacities leads to intensification of anthropogenic emissions of carbon and strong disruption of natural carbon cycle on these areas. Therefore, a deeper understanding of the carbon "metabolism" of such regions is required. Apart of better quantification of surface carbon fluxes, also a thorough understanding of the functioning of biosphere under strong anthropogenic influence is needed. Nowadays, covariance methods are widely applied for studying gas exchange between the atmosphere and the Earth's surface. Relaxed Eddy Accumulation method (REA), combined with the CO2 and CH4 CRDS analyser allows simultaneous measurements of surface fluxes of carbon dioxide and methane within the chosen footprint of the detection system, thus making possible thorough characterisation of the overall exchange of those gases between the atmosphere and the urban surface across diverse spatial and temporal scales. Here we present preliminary results of the study aimed at quantifying surface fluxes of CO2 and CH4 in Krakow, southern Poland. The REA system for CO2 and CH4 flux measurements has been installed on top of a 20m high tower mounted on the roof of the faculty building, close to the city centre of Krakow. The sensors were installed ca 42 m above the local ground. Gill Windmaster-Pro sonic anemometer was coupled with self-made system, designed by the Poznan University of Life Sciences, Poland, for collecting air samples in two pairs of 10-liter Tedlar bags, and with Picarro G2101-i CRDS analyser. The air was collected in 30-min intervals. The CO2 and CH4 mixing ratios in these cumulative downdraft and updraft air samples were determined by the CRDS analyser after each sampling interval. Based on the measured mixing ratios difference and the vertical wind component, the variability of the mean surface fluxes of CO2 and CH4 was quantified. In case of CO2 flux, a typical diurnal pattern with the maximum values of around 30 mmol m-2 h-1 occurring during night hours and the minimum values, around -40 mmol m-2 h-1, occurring early afternoon was observed during sunny days ("plus" and "minus" signs mark upward and downward fluxes, respectively). In addition, some events with much higher fluxes (up to 100 mmol m-2 h-1) were observed, mainly during rush hours. Temporal variability of methane flux turned out to be much higher than that observed for CO2. During summer, it varied from approximately -100 to +500 μmol m-2 h-1, with the mean value of around +100 μmol m-2 h-1 and maximum values occurring predominantly during daytime. In addition to flux measurements, an attempt was made to characterize also the isotopic signature of carbon in the CO2 flux components measured with the aid of REA method. The results showed that the precision of δ13CO2 measurements performed with Picarro analyser was not sufficient to differentiate the isotopic signatures of upward and downward CO2 fluxes. Acknowledgement: This work is supported by the Ministry of Science and Higher Education (project No. 817.N-COST/2010/0 and the statutory funds of the AGH University of Science and Technology, project no. 11.11.220.01).

Confinement of surface state electrons in self-organized Co islands on Au(111)

NASA Astrophysics Data System (ADS)

Schouteden, Koen; Lijnen, Erwin; Janssens, Ewald; Ceulemans, Arnout; Chibotaru, Liviu F.; Lievens, Peter; Van Haesendonck, Chris

2008-04-01

We report on detailed low temperature scanning tunneling spectroscopy measurements performed on nanoscale Co islands on Au(111) films. At low coverages, Co islands self-organize in arrays of mono- and bilayer nanoscale structures that often have an hexagonal shape. The process of self-organization is induced by the Au(111) 'herringbone' reconstruction. By means of mapping of the local density of states with lock-in detection, electron standing wave patterns are resolved on top of the atomically flat Co islands. The surface state electrons are observed to be strongly confined laterally inside the Co nanosized islands, with their wavefunctions reflecting the symmetry of the islands. To complement the experimental work, particle-in-a-box calculations were performed. The calculations are based on a newly developed variational method that can be applied to '2D boxes' of arbitrary polygonal shape. The experimental patterns are found to fit nicely to the calculated wavefunctions for a box having a symmetry corresponding to the experimental island symmetry. The small size of the Co islands under study (down to 7.7 nm2) is observed to induce a strong discretization of the energy levels, with very large energy separations between the eigenstates up to several 100 meV. The observed standing wave patterns are identified either as individual eigenstates or as a 'mixture' of two or more energetically close-lying eigenstates of the cobalt island. Additionally, the Co surface state appears not to be limited to mono- and bilayer islands, but this state remains observable for multilayered islands up to five monolayers of Co.

Hydrogeologic Modeling for Monitoring, Reporting and Verification of Geologic Sequestration

NASA Astrophysics Data System (ADS)

Kolian, M.; De Figueiredo, M.; Lisa, B.

2011-12-01

In December 2010, EPA finalized Subpart RR of the Greenhouse Gas (GHG) Reporting Program, which requires facilities that conduct geologic sequestration (GS) of carbon dioxide (CO2) to report GHG data to EPA annually. The GHG Reporting Program requires reporting of GHGs and other relevant information from certain source categories in the United States, and information obtained through Subpart RR will inform Agency decisions under the Clean Air Act related to the use of carbon dioxide capture and sequestration for mitigating GHGs. This paper examines hydrogeologic modeling necessities and opportunities in the context of Subpart RR. Under Subpart RR, facilities that conduct GS by injecting CO2 for long-term containment in subsurface geologic formations are required to develop and implement an EPA-approved site-specific monitoring, reporting, and verification (MRV) plan; and report basic information on CO2 received for injection, annual monitoring activities and the amount of CO2 geologically sequestered using a mass balance approach. The major components of the MRV plan include: identification of potential surface leakage pathways for CO2 and the likelihood, magnitude, and timing, of surface leakage of CO2 through these pathways; delineation of the monitoring areas; strategy for detecting and quantifying any surface leakage of CO2; and the strategy for establishing the expected baselines for monitoring CO2 surface leakage. Hydrogeologic modeling is an integral aspect of the design of an MRV plan. In order to prepare an adequate monitoring program that addresses site specific risks over the full life of the project the MRV plan must reflect the full spatial extent of the free phase CO2 over time. Facilities delineate the maximum area that the CO2 plume is predicted to cover and how monitoring can be phased in over this area. The Maximum Monitoring Area (MMA) includes the extent of the free phase CO2 plume over the lifetime of the project plus a buffer zone of one-half mile. The Active Monitoring Area (AMA) is the area that will be monitored over a specified time interval chosen by the reporter, which must be greater than one year. All of the area in the MMA will eventually be covered by one or more AMAs. This allows operators to phase in monitoring so that during any given time interval, only that part of the MMA in which surface leakage might occur needs to be monitored. EPA designed the MRV plan approach to be site-specific, flexible, and adaptive to future technology developments. This approach allows the reporter to leverage the site characterization, modeling, and monitoring approaches (e.g. monitoring of injection pressures, injection well integrity, groundwater quality and geochemistry, and CO2 plume location, etc.) developed for their Underground Injection Control (UIC) permit. UIC requirements provide the foundation for the safe sequestration of CO2 by helping to ensure that injected fluids remain isolated in the subsurface and away from underground sources of drinking water, thereby serving to reduce the risk of CO2 leakage to the atmosphere.

Chemical states of surface oxygen during CO oxidation on Pt(1 1 0) surface revealed by ambient pressure XPS

DOE PAGES

Yu, Youngseok; Koh, Yoobin Esther; Lim, Hojoon; ...

2017-10-20

Here, the study of CO oxidation on Pt(110) surface is revisited using ambient pressure x-ray photoemission spectroscopy. When the surface temperature reaches the activation temperature for CO oxidation under elevated pressure conditions, both the α-phase of PtO 2 oxide and chemisorbed oxygen are formed simultaneously on the surface. Due to the exothermic nature of CO oxidation, the temperature of the Pt surface increases as CO oxidation takes place. As the CO/O 2 ratio increases, the production of CO 2 increases continuously and the surface temperature also increases. Interestingly, within the diffusion limited regions, the amount of surface oxide changes littlemore » while the chemisorbed oxygen is reduced.« less

Chemical states of surface oxygen during CO oxidation on Pt(1 1 0) surface revealed by ambient pressure XPS

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

Yu, Youngseok; Koh, Yoobin Esther; Lim, Hojoon

Here, the study of CO oxidation on Pt(110) surface is revisited using ambient pressure x-ray photoemission spectroscopy. When the surface temperature reaches the activation temperature for CO oxidation under elevated pressure conditions, both the α-phase of PtO 2 oxide and chemisorbed oxygen are formed simultaneously on the surface. Due to the exothermic nature of CO oxidation, the temperature of the Pt surface increases as CO oxidation takes place. As the CO/O 2 ratio increases, the production of CO 2 increases continuously and the surface temperature also increases. Interestingly, within the diffusion limited regions, the amount of surface oxide changes littlemore » while the chemisorbed oxygen is reduced.« less

A facile one-pot preparation of Co3O4/g-C3N4 heterojunctions with excellent electrocatalytic activity for the detection of environmental phenolic hormones

NASA Astrophysics Data System (ADS)

Sun, Yanjuan; Jiang, Jizhou; Liu, Yi; Wu, Shengli; Zou, Jing

2018-02-01

The Co3O4/g-C3N4 heterojunctions were prepared by a facile one-pot thermal decomposition technique. Compared with g-C3N4, it was found that Co3O4/g-C3N4 heterojunctions possessed a higher Brunner-Emmet-Teller (BET) surface area, which was beneficial to the diffusion of aim molecules on the electrode surfaces. And the optimal Co3O4/g-C3N4 heterojunctions exhibited a narrower band gap and a higher donor density, resulting in an excellent electrocatalytic activity for environmental phenolic hormones. Moreover, the Co3O4/g-C3N4 heterojunctions were used for the electrochemical sensing of environmental phenolic hormones such as bisphenol A, pentachlorophenol, p-nitrophenol and octylphenol. All detection ranges reached three orders of magnitude, showing a lower limit of detection of 10-9 mol L-1. So, sensitivity and accurate determination of environmental phenolic hormones in real water samples may use this Co3O4/g-C3N4 heterojunctions modified electrode.

Monitoring Conformance and Containment for Geological Carbon Storage: Can Technology Meet Policy and Public Requirements?

NASA Astrophysics Data System (ADS)

Lawton, D. C.; Osadetz, K.

2014-12-01

The Province of Alberta, Canada identified carbon capture and storage (CCS) as a key element of its 2008 Climate Change strategy. The target is a reduction in CO2 emissions of 139 Mt/year by 2050. To encourage uptake of CCS by industry, the province has provided partial funding to two demonstration scale projects, namely the Quest Project by Shell and partners (CCS), and the Alberta Carbon Trunk Line Project (pipeline and CO2-EOR). Important to commercial scale implementation of CCS will be the requirement to prove conformance and containment of the CO2 plume injected during the lifetime of the CCS project. This will be a challenge for monitoring programs. The Containment and Monitoring Institute (CaMI) is developing a Field Research Station (FRS) to calibrate various monitoring technologies for CO2 detection thresholds at relatively shallow depths. The objective being assessed with the FRS is sensitivity for early detection of loss of containment from a deeper CO2 storage project. In this project, two injection wells will be drilled to sandstone reservoir targets at depths of 300 m and 700 m. Up to four observation wells will be drilled with monitoring instruments installed. Time-lapse surface and borehole monitoring surveys will be undertaken to evaluate the movement and fate of the CO2 plume. These will include seismic, microseismic, cross well, electrical resistivity, electromagnetic, gravity, geodetic and geomechanical surveys. Initial baseline seismic data from the FRS will presented.

A SERS biosensor with magnetic substrate CoFe2O4@Ag for sensitive detection of Hg2+

NASA Astrophysics Data System (ADS)

Yang, Xia; He, Yi; Wang, Xueling; Yuan, Ruo

2017-09-01

Mercuric ion (Hg2+) is one toxic metal ion existed in aquatic ecosystems which would seriously damage human central nervous system and other organs. So developing an approach to sensitively detect Hg2+ in our living environment is urgent and important. In this work, a novel surface enhancement Raman spectrum(SERS) sensor is fabricated for high selective and ultrasensitive detection of Hg2+ in aqueous solution, based on a stable thymine-Hg2+-thymine (T-Hg2+-T) structure and the π-π interaction between single-stranded DNA (ssDNA) and single walled carbon nanotubes (SWCNTs). Herein, SWCNTs act as Raman labels to produce characteristic Raman peaks which can be a beacon to quantitative detect Hg2+. In the presence of Hg2+, the ssDNA can capture Hg2+ forming T-Hg2+-T structure, which makes SWCNTs leave the hot spots of the SERS-based biosensor. With this design, the Raman intensity of SWCNTs decreased with the increasing concentration of Hg2+. At the same time, CoFe2O4@Ag as active SERS substrates can effectively enhance sensitivity and uniformity of the biosensor through aggregation by magnet. Under optimal conditions, this proposed biosensor can detect Hg2+ at a range from 1 pM to 100 nM with a detection limit of 0.84 pM. With the advantages of good sensitivity, selectivity, simplicity and rapidity, the biosensor is potentially suitable for monitoring of Hg2+ in environmental applications.

Amyloid Precursor-like Protein 2 Association with HLA Class I Molecules

PubMed Central

Tuli, Amit; Sharma, Mahak; Wang, Xiaojian; Simone, Laura C.; Capek, Haley L.; Cate, Steven; Hildebrand, William H.; Naslavsky, Naava; Caplan, Steve; Solheim, Joyce C.

2009-01-01

Amyloid precursor-like protein 2 (APLP2) is a ubiquitously expressed protein. The previously demonstrated functions for APLP2 include binding to the mouse major histocompatibility complex (MHC) class I molecule H-2Kd and down regulating its cell surface expression. In this study, we have investigated the interaction of APLP2 with the human leukocyte antigen (HLA) class I molecule in human tumor cell lines. APLP2 was readily detected in pancreatic, breast, and prostate tumor lines, although it was found only in very low amounts in lymphoma cell lines. In a pancreatic tumor cell line, HLA class I was extensively co-localized with APLP2 in vesicular compartments following endocytosis of HLA class I molecules. In pancreatic, breast, and prostate tumor lines, APLP2 was bound to the HLA class I molecule. APLP2 was found to bind to HLA-A24, and more strongly to HLA-A2. Increased expression of APLP2 resulted in reduced surface expression of HLA-A2 and HLA-A24. Overall, these studies demonstrate that APLP2 binds to the HLA class I molecule, co-localizes with it in intracellular vesicles, and reduces the level of HLA class I molecule cell surface expression. PMID:19184004

Adding a dimension to the infrared spectra of interfaces using heterodyne detected 2D sum-frequency generation (HD 2D SFG) spectroscopy

PubMed Central

Xiong, Wei; Laaser, Jennifer E.; Mehlenbacher, Randy D.; Zanni, Martin T.

2011-01-01

In the last ten years, two-dimensional infrared spectroscopy has become an important technique for studying molecular structures and dynamics. We report the implementation of heterodyne detected two-dimensional sum-frequency generation (HD 2D SFG) spectroscopy, which is the analog of 2D infrared (2D IR) spectroscopy, but is selective to noncentrosymmetric systems such as interfaces. We implement the technique using mid-IR pulse shaping, which enables rapid scanning, phase cycling, and automatic phasing. Absorptive spectra are obtained, that have the highest frequency resolution possible, from which we extract the rephasing and nonrephasing signals that are sometimes preferred. Using this technique, we measure the vibrational mode of CO adsorbed on a polycrystalline Pt surface. The 2D spectrum reveals a significant inhomogenous contribution to the spectral line shape, which is quantified by simulations. This observation indicates that the surface conformation and environment of CO molecules is more complicated than the simple “atop” configuration assumed in previous work. Our method can be straightforwardly incorporated into many existing SFG spectrometers. The technique enables one to quantify inhomogeneity, vibrational couplings, spectral diffusion, chemical exchange, and many other properties analogous to 2D IR spectroscopy, but specifically for interfaces. PMID:22143772

Adding a dimension to the infrared spectra of interfaces using heterodyne detected 2D sum-frequency generation (HD 2D SFG) spectroscopy.

PubMed

Xiong, Wei; Laaser, Jennifer E; Mehlenbacher, Randy D; Zanni, Martin T

2011-12-27

In the last ten years, two-dimensional infrared spectroscopy has become an important technique for studying molecular structures and dynamics. We report the implementation of heterodyne detected two-dimensional sum-frequency generation (HD 2D SFG) spectroscopy, which is the analog of 2D infrared (2D IR) spectroscopy, but is selective to noncentrosymmetric systems such as interfaces. We implement the technique using mid-IR pulse shaping, which enables rapid scanning, phase cycling, and automatic phasing. Absorptive spectra are obtained, that have the highest frequency resolution possible, from which we extract the rephasing and nonrephasing signals that are sometimes preferred. Using this technique, we measure the vibrational mode of CO adsorbed on a polycrystalline Pt surface. The 2D spectrum reveals a significant inhomogenous contribution to the spectral line shape, which is quantified by simulations. This observation indicates that the surface conformation and environment of CO molecules is more complicated than the simple "atop" configuration assumed in previous work. Our method can be straightforwardly incorporated into many existing SFG spectrometers. The technique enables one to quantify inhomogeneity, vibrational couplings, spectral diffusion, chemical exchange, and many other properties analogous to 2D IR spectroscopy, but specifically for interfaces.

Ultrasensitive Surface-Enhanced Raman Spectroscopy Detection Based on Amorphous Molybdenum Oxide Quantum Dots.

PubMed

Li, Hao; Xu, Qun; Wang, Xuzhe; Liu, Wei

2018-06-07

Surface-enhanced Raman spectroscopy (SERS) based on plasmonic semiconductive material has been proved to be an efficient tool to detect trace of substances, while the relatively weak plasmon resonance compared with noble metal materials restricts its practical application. Herein, for the first time a facile method to fabricate amorphous H x MoO 3 quantum dots with tunable plasmon resonance is developed by a controlled oxidization route. The as-prepared amorphous H x MoO 3 quantum dots show tunable plasmon resonance in the region of visible and near-infrared light. Moreover, the tunability induced by SC CO 2 is analyzed by a molecule kinetic theory combined with a molecular thermodynamic model. More importantly, the ultrahigh enhancement factor of amorphous H x MoO 3 quantum dots detecting on methyl blue can be up to 9.5 × 10 5 with expending the limit of detection to 10 -9 m. Such a remarkable porperty can also be found in this H x MoO 3 -based sensor with Rh6G and RhB as probe molecules, suggesting that the amorphous H x MoO 3 quantum dot is an efficient candidate for SERS on molecule detection in high precision. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of Fe loadings on desulfurization performance of activated carbon treated by nitric acid.

PubMed

Guo, Jia-Xiu; Shu, Song; Liu, Xiao-Li; Wang, Xue-Jiao; Yin, Hua-Qiang; Chu, Ying-Hao

2017-02-01

A series of Fe supported on activated carbon treated by nitric acid are prepared by incipient wetness impregnation with ultrasonic assistance and characterized by N 2 adsorption-desorption, X-ray diffraction, Fourier transform infrared spectrum and X-ray photoelectron spectroscopy. It has shown that Fe loadings significantly influence the desulfurization activity. Fe/NAC5 exhibits an excellent removal ability of SO 2 , corresponding to breakthrough sulfur capacity of 323 mg/g. With the increasing Fe loadings, the generated Fe 3 O 4 and Fe 2 SiO 4 increase, but Fe 2 (SO 4 ) 3 is observed after desulfurization. Fe/NAC1 has a Brunauer-Emmett-Teller (BET) surface area of 925 m 2 /g with micropore surface area of 843 m 2 /g and total pore volume of 0.562 cm 3 /g including a micropore volume of 0.300 cm 3 /g. With the increasing Fe loadings, BET surface area and micropore volume decrease, and those of Fe/NAC10 decrease to 706 m 2 /g and 0.249 cm 3 /g. The Fe loadings influence the pore-size distribution, and SO 2 adsorption mainly reacts in micropores at about 0.70 nm. C=O and C-O are observed for all samples before SO 2 removal. After desulfurization, the C-O stretching is still detected, but the C=O stretching vibration of carbonyl groups disappears. The stretching of S-O or S=O in sulfate is observed at 592 cm -1 for the used sample, proving that the existence of [Formula: see text].

Solubility of C-O-H volatiles in graphite-saturated martian basalts and application to martian atmospheric evolution

NASA Astrophysics Data System (ADS)

Stanley, B. D.; Hirschmann, M. M.; Withers, A. C.

2012-12-01

The modern martian atmosphere is thin, leading to surface conditions too cold to support liquid water. Yet, there is evidence of liquid surface water early in martian history that is commonly thought to require a thick CO2 atmosphere. Our previous work follows the analysis developed by Holloway and co-workers (Holloway et al. 1992; Holloway 1998), which predicts a linear relationship between CO2 and oxygen fugacity (fO2) in graphite-saturated silicate melts. At low oxygen fugacity, the solubility of CO2 in silicate melts is therefore very low. Such low calculated solubilities under reducing conditions lead to small fluxes of CO2 associated with martian magmatism, and therefore production of a thick volcanogenic CO2 atmosphere could require a prohibitively large volume of mantle-derived magma. The key assumption in these previous calculations is that the carbonate ion is the chief soluble C-O-H species. The results of the calculations would not be affected appreciably if molecular CO2, rather than carbonate ion, were an important species, but could be entirely different if there were other appreciable C-species such as CO, carbonyl (C=O) complexes, carbide (Si-C), or CH4. Clearly, graphite-saturated experiments are required to explore how much volcanogenic C may be degassed by reduced martian lavas. A series of piston-cylinder experiments were performed on synthetic martian starting materials over a range of oxygen fugacities (IW+2.3 to IW-0.9), and at pressures of 1-3 GPa and temperatures of 1340-1600 °C in Pt-graphite double capsules. CO2 contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and range from 0.0026-0.50 wt%. CO2 solubilities change by one order of magnitude with an order of magnitude change in oxygen fugacity, as predicted by previous work. Secondary ion mass spectrometry (SIMS) determinations of C contents in glasses range from 0.0131-0.2626 wt%. C contents determined by SIMS are consistently higher than CO2 contents determined by FTIR. This difference, termed excess C, is attributed to the presence of other reduced C-species, such as carbonyls and amides (which have C=O and N-H bonds), detected using FTIR in reduced graphite-saturated martian basalts. An atmosphere produced by degassing of magmas similar to this study would be richer in C-O-H species than previously modeled using only CO2 and could create a much warmer climate that stabilizes liquid water on the ancient martian surface.

Measurement of Circumstellar Disk Sizes in the Upper Scorpius OB Association with ALMA

NASA Astrophysics Data System (ADS)

Barenfeld, Scott A.; Carpenter, John M.; Sargent, Anneila I.; Isella, Andrea; Ricci, Luca

2017-12-01

We present detailed modeling of the spatial distributions of gas and dust in 57 circumstellar disks in the Upper Scorpius OB Association observed with ALMA at submillimeter wavelengths. We fit power-law models to the dust surface density and CO J = 3–2 surface brightness to measure the radial extent of dust and gas in these disks. We found that these disks are extremely compact: the 25 highest signal-to-noise disks have a median dust outer radius of 21 au, assuming an {R}-1 dust surface density profile. Our lack of CO detections in the majority of our sample is consistent with these small disk sizes assuming the dust and CO share the same spatial distribution. Of seven disks in our sample with well-constrained dust and CO radii, four appear to be more extended in CO, although this may simply be due to the higher optical depth of the CO. Comparison of the Upper Sco results with recent analyses of disks in Taurus, Ophiuchus, and Lupus suggests that the dust disks in Upper Sco may be approximately three times smaller in size than their younger counterparts, although we caution that a more uniform analysis of the data across all regions is needed. We discuss the implications of these results for disk evolution.

Effects of hydration and oxygen vacancy on CO2 adsorption and activation on beta-Ga2O3(100).

PubMed

Pan, Yun-xiang; Liu, Chang-jun; Mei, Donghai; Ge, Qingfeng

2010-04-20

The effects of hydration and oxygen vacancy on CO(2) adsorption on the beta-Ga(2)O(3)(100) surface have been studied using density functional theory slab calculations. Adsorbed CO(2) is activated on the dry perfect beta-Ga(2)O(3)(100) surface, resulting in a carbonate species. This adsorption is slightly endothermic, with an adsorption energy of 0.07 eV. Water is preferably adsorbed molecularly on the dry perfect beta-Ga(2)O(3)(100) surface with an adsorption energy of -0.56 eV, producing a hydrated perfect beta-Ga(2)O(3)(100) surface. Adsorption of CO(2) on the hydrated surface as a carbonate species is also endothermic, with an adsorption energy of 0.14 eV, indicating a slightly repulsive interaction when H(2)O and CO(2) are coadsorbed. The carbonate species on the hydrated perfect surface can be protonated by the coadsorbed H(2)O to a bicarbonate species, making the CO(2) adsorption exothermic, with an adsorption energy of -0.13 eV. The effect of defects on CO(2) adsorption and activation has been examined by creating an oxygen vacancy on the dry beta-Ga(2)O(3)(100) surface. The formation of an oxygen vacancy is endothermic, by 0.34 eV, with respect to a free O(2) molecule in the gas phase. Presence of the oxygen vacancy promoted the adsorption and activation of CO(2). In the most stable CO(2) adsorption configuration on the dry defective beta-Ga(2)O(3)(100) surface with an oxygen vacancy, one of the oxygen atoms of the adsorbed CO(2) occupies the oxygen vacancy site, and the CO(2) adsorption energy is -0.31 eV. Water favors dissociative adsorption at the oxygen vacancy site on the defective surface. This process is spontaneous, with a reaction energy of -0.62 eV. These results indicate that, when water and CO(2) are present in the adsorption system simultaneously, water will compete with CO(2) for the oxygen vacancy sites and impact CO(2) adsorption and conversion negatively.

Infrared Spectral Studies of the Thermally-Driven Chemistry Present on Icy Satellites

NASA Technical Reports Server (NTRS)

Loeffler, Mark J.; Hudson, Reggie L.

2012-01-01

Remote sensing of Jupiters icy satellites has revealed that even though their surfaces arc composed mostly of water ice, molecules such as SO2, CO2, H2O2. O2, and O3 also are present. On Europa, a high radiation flux is believed to play a role in the formation of many of the minor species detected, and numerous laboratory studies have been devoted to explore this hypothesis. In this presentation we will discuss some of our recent research on another alteration pathway, thermally-driven chemical reactions, which are also important for understanding the chemical evolution of Europa's surface and sub-surface ices. We will focus on the infrared spectra of and reactions between H2O, SO2 and H2O2, at 80 - 130 K.

Sensitive and selective detection of trivalent chromium using Hyper Rayleigh Scattering with 5,5'-dithio-bis-(2-nitrobenzoic acid)-modified gold nanoparticles.

PubMed

Hughes, Shantelle I; Dasary, Samuel S R; Singh, Anant K; Glenn, Zachery; Jamison, Hakim; Ray, Paresh C; Yu, Hongtao

2013-03-01

Hyper Rayleigh Scattering (HRS) and absorption spectral assays using surface-modified gold nanoparticles (AuNP) have been developed for sensitive and selective detection of trivalent chromium (Cr 3+ ) from other metal ions including hexavalent chromium (as Cr 2 O 7 2- ). Gold nanoparticles of 13 nm, covalently attached with 5,5'-dithio- bis -(2-nitrobenzoic acid) (AuNP-DTNBA), is used as a probe for both the absorption and HRS assays. AuNP-DTNBA is able to detect Cr 3+ at 20 ppb level at pH 6.0 using absorption spectral change of the AuNP-DTNBA. Visible color change can be observed when mixed with 250 ppb of Cr 3+ , while there is no color change when mixed with 2 ppm level of some of the most common metal ions such as Cr 2 O 7 2- , Hg 2+ , Ba 2+ , Fe 3+ , Pb 2+ , Na + , Zn 2+ , Cd 2+ , Co 2+ , Mn 2+ , Ca 2+ , and Ni 2+ . However, a color change is observed when mixed with Ni 2+ , Zn 2+ , and Cd 2+ at a concentration higher than 2 ppm. The detection limit for the HRS assay is on a remarkable 25 ppt level, and there is no detectable HRS signal at 2 ppm level for Cr 2 O 7 2- , Hg 2+ , Ba 2+ , Fe 3+ , Pb 2+ , Na + , Zn 2+ , Cd 2+ , Co 2+ , Mn 2+ , Ca 2+ , and Ni 2+ .

Detection of chemical agent aerosols

NASA Astrophysics Data System (ADS)

Fox, Jay A.; Ahl, Jeffrey L.; D'Amico, Francis M.; Vanderbeek, Richard G.; Moon, Raphael; Swim, Cynthia R.

1999-05-01

One of the major threats presented by a chemical agent attack is that of a munition exploding overhead and 'raining' aerosols which can contaminate surfaces when they impact. Since contact with these surfaces can be fatal, it is imperative to know when such an attack has taken place and the likely threat density and location. We present the results of an experiment designed to show the utility of a CO2 lidar in detecting such an attack. Testing occurred at Dugway Proving Grounds, Utah and involved the simulation of an explosive airburst chemical attack. Explosions occurred at a height of 30 m and liquid droplets from two chemicals, PEG-200 (polyethylene glycol 200) and TEP (triethylphosphate), were expelled and fell to the ground. The munition was the U.S. Army M9 Simulator, Projectile, Airburst, Liquid (SPAL) system that is designed for chemical warfare training exercises. The instrument that was used to detect the presence of the aerosols was the Laser Standoff Chemical Detector (LSCD) which is a light detection and ranging (LIDAR) system that utilizes a rapidly tunable, pulsed CO2 laser. The LIDAR scanned a horizontal path approximately 5 - 8 m above the ground in order to measure the concentration of liquid deposition. The LIDAR data were later correlated with card data to determine how well the system could predict the location and quantity of liquid deposition on the ground.

Damage evaluation for crops exposed to a simulated leakage of geologically stored CO2 using hyperspectral imaging technology

NASA Astrophysics Data System (ADS)

Burud, Ingunn; Moni, Christophe; Flø, Andreas; Rolstad Denby, Cecilie; Rasse, Daniel

2013-04-01

Facilities for the geological storage of carbon dioxide (CO2) as part of carbon capture and storage (CCS) schemes will be designed to prevent any leakage from the defined 'storage complex'. However, even though the risk is of low probability, the precautionary principle requires that near surface environments that might be at risk be thoroughly monitored to detect a leak, were it to happen. Among all currently proposed monitoring methods, only hyperspectral imaging of vegetation stress response allows one to scan large areas rapidly and in detail. Until now, however, only a handful of studies have been carried out on using this novel technology. The aim of the present communication was to characterize the impacts that a simulated CO2 leak might have on the hyperspectral signature of a Norwegian oats crop. In order to test the effects of different intensity of leakage, a CO2 exposure field experiment was designed to create a longitudinal CO2 gradient. For this purpose a gas supply pipe was inserted at one end of a 6m by 3m experimental plot at the base of a 45 cm thick layer of sand buried 40 cm below the surface under a silt loam plough layer. CO2 was then injected at a rate of 2l.min-1 just after the oats had germinated at the end of June, and Facilities for the geological storage of carbon dioxide (CO2) as part of carbon capture and storage (CCS) schemes will be designed to prevent any leakage from the defined 'storage complex'. However, even though the risk is of low probability, the precautionary principle requires that near surface environments that might be at risk be thoroughly monitored to detect a leak, were it to happen. Among all currently proposed monitoring methods, only hyperspectral imaging of vegetation stress response allows one to scan large areas rapidly and in detail. Until now, however, only a handful of studies have been carried out on using this novel technology. The aim of the present communication was to characterize the impacts that a simulated CO2 leak might have on the hyperspectral signature of a Norwegian oats crop. In order to test the effects of different intensity of leakage, a CO2 exposure field experiment was designed to create a longitudinal CO2 gradient. For this purpose a gas supply pipe was inserted at one end of a 6m by 3m experimental plot at the base of a 45 cm thick layer of sand buried 40 cm below the surface under a silt loam plough layer. CO2 was then injected at a rate of 2l.min-1 just after the oats had germinated at the end of June, and continued until it was harvested at the end of August. Then soil CO2 fluxes were recorded at the surface using a (60 x 60 cm) grid sampling pattern. Hyperspectral images of the experimental plot were taken at different dates during the gassing period using a SPECIM camera with 800 spectral bands, covering the wavelength range 400 - 1000 nm. The change in the reflectance spectra were characterized over time within the plot by the computation of various hyperspectral vegetation indices for small discretized spatial units (i.e. 10 cm by 10 cm square). The results showed that one month after injection, reduced plant growth, yellowing of the leaves and purple discoloration of the stems were observed just above the injection points were high CO2 fluxes had been identified. These high CO2 flux zones were further associated with an increase of the reflectance that occurred in the red region of the spectra indicating a decrease of the chlorophyll content in the plants. To conclude, plant health, as indicated by the hyperspectral signature, was closely related to the leakage pattern, indicating that hyperspectral imaging could be used to identify a CO2 seepage in an agricultural field. Acknowledgments This work is part of the RISCS project (Research into Impacts and Safety in CO2 Storage), funded by the EC 7th Framework Programme and by industry partners ENEL I&I, Statoil, Vattenfall AB, E.ON and RWE. R&D partners are BGS, CERTH, IMARES, OGS, PML, SINTEF, University of Nottingham, Sapienza Università di Roma, Quintessa, CO2 GeoNet, Bioforsk, BGR and ZERO. For more information please go to the website (www.riscs-co2.eu) or contact the project coordinator David Jones (e-mail: dgj@bgs.ac.uk tel. +44(0)115-936-3576).

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.

Monitoring of leaked CO2 through sediment, water column and atmosphere in sub-seabed CCS experiment

NASA Astrophysics Data System (ADS)

Shitashima, K.; Sakamoto, A.; Maea, Y.

2013-12-01

CO2 capture and storage in sub-seabed geological formations (sub-seabed CCS) is currently being studied as a feasible option to mitigate the accumulation of anthropogenic CO2 in the atmosphere. In implementing sub-seabed CCS, detecting and monitoring the impact of the sequestered CO2 on the ocean environment is highly important. The first controlled CO2 release experiment, entitled 'Quantifying and Monitoring Potential Ecosystem Impacts of Geological Carbon Storage (QICS)', took place in Ardmucknish Bay, Oban, in May-July 2012. We applied the in-situ pH/pCO2/ORP sensor to the QICS experiment for detection and monitoring of leaked CO2, and carried out several observations. The on-line sensor that was connected by 400m of RS422 cable was deployed close to the CO2 leakage (bubbling) point, and the fluctuations of pH, pCO2 and ORP were monitored in real-time in a observation van on land. Three sets of off-line sensors were also placed on seafloor in respective points (release point, and two low impacted regions at 25m and 75m distant) for three months. The long-term monitoring of pH in sediment at 50cm depth under the seafloor was conducted. The spear type electrode was stabbed into sediment by diver near the CO2 leakage point. Wide-area mapping surveys of pH, pCO2 and ORP in seawater around the leakage point were carried out by AUV (REMUS-100) that some chemical sensors were installed in. The AUV cruised along the grid line in two layers of 4m and 2m above the seafloor during both of periods of low tide and high tide. Atmospheric CO2 in sea surface above the leakage point was observed by the LI-COR CO2 Analyzer. The analyzer was attached to the bow of ship, and the ship navigated a wide-area along a grid observation line during both of periods of low tide and high tide.

Extensive Viable Middle East Respiratory Syndrome (MERS) Coronavirus Contamination in Air and Surrounding Environment in MERS Isolation Wards.

PubMed

Kim, Sung-Han; Chang, So Young; Sung, Minki; Park, Ji Hoon; Bin Kim, Hong; Lee, Heeyoung; Choi, Jae-Phil; Choi, Won Suk; Min, Ji-Young

2016-08-01

The largest outbreak of Middle East respiratory syndrome coronavirus (MERS-CoV) outside the Middle East occurred in South Korea in 2015 and resulted in 186 laboratory-confirmed infections, including 36 (19%) deaths. Some hospitals were considered epicenters of infection and voluntarily shut down most of their operations after nearly half of all transmissions occurred in hospital settings. However, the ways that MERS-CoV is transmitted in healthcare settings are not well defined. We explored the possible contribution of contaminated hospital air and surfaces to MERS transmission by collecting air and swabbing environmental surfaces in 2 hospitals treating MERS-CoV patients. The samples were tested by viral culture with reverse transcription polymerase chain reaction (RT-PCR) and immunofluorescence assay (IFA) using MERS-CoV Spike antibody, and electron microscopy (EM). The presence of MERS-CoV was confirmed by RT-PCR of viral cultures of 4 of 7 air samples from 2 patients' rooms, 1 patient's restroom, and 1 common corridor. In addition, MERS-CoV was detected in 15 of 68 surface swabs by viral cultures. IFA on the cultures of the air and swab samples revealed the presence of MERS-CoV. EM images also revealed intact particles of MERS-CoV in viral cultures of the air and swab samples. These data provide experimental evidence for extensive viable MERS-CoV contamination of the air and surrounding materials in MERS outbreak units. Thus, our findings call for epidemiologic investigation of the possible scenarios for contact and airborne transmission, and raise concern regarding the adequacy of current infection control procedures. © The Author 2016. Published by Oxford University Press for the Infectious Diseases Society of America. All rights reserved. For permissions, e-mail journals.permissions@oup.com.

Investigation of Potassium Feldspar Reactivity in Wet Supercritical CO2 by In Situ Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Thompson, C.; Widener, C.; Schaef, T.; Loring, J.; McGrail, B. P.

2014-12-01

Capture and subsequent storage of CO2 in deep geologic reservoirs is progressively being considered as a viable approach to reduce anthropogenic greenhouse gas emissions. In the long term, injected CO2 may become permanently entrapped as silicate minerals react with CO2 enriched fluids to form stable carbonate minerals. Potassium feldspars are highly abundant in the earth's crust and are present in the caprocks and storage formations of many target reservoirs. While the dissolution kinetics and carbonation reactions of feldspars have been well studied in the aqueous phase, comparatively little work has focused on K-feldspar reactivity in the CO2-rich fluid. In this study, we used in situ infrared spectroscopy to investigate the carbonation reactions of natural microcline samples. Experiments were carried out at 50 °C and 91 bar by circulating dry or wet supercritical CO2 (scCO2) past a thin film of powdered sample. Water concentrations ranged from 0% to 125% relative to saturation, and transmission-mode absorbance spectra were recorded as a function of time for 48 hours. No discernible reaction was detected when the samples were exposed to anhydrous scCO2. However, in fully water-saturated scCO2, a thin film of liquid-like water was observed on the samples' surfaces, and up to 0.6% of the microcline was converted to a carbonate phase. Potassium carbonate is the most likely reaction product, but minor amounts of sodium carbonate and siderite may also have formed from minor sample impurities. The extent of reaction appears to be related to the thickness of the water film and is likely a consequence of the film's ability to solvate and transport ions in the vicinity of the mineral surface. Other features observed in the spectra correspond to microcline dissolution and precipitation of amorphous silica. Implications about the role of water in these reactions and the relative effectiveness of alkali feldspars for mineral trapping of CO2 will be discussed.

Spectroscopy from Space

NASA Astrophysics Data System (ADS)

Clark, R. N.; Swayze, G. A.; Carlson, R.; Grundy, W.; Noll, K.

2014-01-01

This chapter reviews detection of materials on solid and liquid (lakes and ocean) surfaces in the solar system using ultraviolet to infrared spectroscopy from space, or near space (high altitude aircraft on the Earth), or in the case of remote objects, earth-based and earth-orbiting telescopes. Point spectrometers and imaging spectrometers have been probing the surfaces of our solar system for decades. Spacecraft carrying imaging spectrometers are currently in orbit around Mercury, Venus, Earth, Mars, and Saturn, and systems have recently visited Jupiter, comets, asteroids, and one spectrometer-carrying spacecraft is on its way to Pluto. Together these systems are providing a wealth of data that will enable a better understanding of the composition of condensed matter bodies in the solar system. Minerals, ices, liquids, and other materials have been detected and mapped on the Earth and all planets and/or their satellites where the surface can be observed from space, with the exception of Venus whose thick atmosphere limits surface observation. Basaltic minerals (e.g., pyroxene and olivine) have been detected with spectroscopy on the Earth, Moon, Mars and some asteroids. The greatest mineralogic diversity seen from space is observed on the Earth and Mars. The Earth, with oceans, active tectonic and hydrologic cycles, and biological processes, displays the greatest material diversity including the detection of amorphous and crystalline inorganic materials, organic compounds, water and water ice. Water ice is a very common mineral throughout the Solar System and has been unambiguously detected or inferred in every planet and/or their moon(s) where good spectroscopic data has been obtained. In addition to water ice, other molecular solids have been observed in the solar system using spectroscopic methods. Solid carbon dioxide is found on all systems beyond the Earth except Pluto, although CO2 sometimes appears to be trapped in other solids rather than as an ice on some objects. The largest deposits of carbon dioxide ice are found on Mars. Sulfur dioxide ice is found in the Jupiter system. Nitrogen and methane ices are common beyond the Uranian system. Saturn's moon Titan probably has the most complex active extra-terrestrial surface chemistry involving organic compounds. Some of the observed or inferred compounds include ices of benzene (C6H6), cyanoacetylene (HC3N), toluene (C7H8), cyanogen (C2N2), acetonitrile (CH3CN), water (H2O), carbon dioxide (CO2), and ammonia (NH3). Confirming compounds on Titan is hampered by its thick smoggy atmosphere, where in relative terms the atmospheric interferences that hamper surface characterization lie between that of Venus and Earth. In this chapter we exclude discussion of the planets Jupiter, Saturn, Uranus, and Neptune because their thick atmospheres preclude observing the surface, even if surfaces exist. However, we do discuss spectroscopic observations on a number of the extra-terrestrial satellite bodies. Ammonia was predicted on many icy moons but is notably absent among the definitively detected ices with possible exceptions on Charon and possible trace amounts on some of the Saturnian satellites. Comets, storehouses of many compounds that could exist as ices in their nuclei, have only had small amounts of water ice definitively detected on their surfaces from spectroscopy. Only two asteroids have had a direct detection of surface water ice, although its presence can be inferred in others.

Replenishment of fish populations is threatened by ocean acidification

PubMed Central

Munday, Philip L.; Dixson, Danielle L.; McCormick, Mark I.; Meekan, Mark; Ferrari, Maud C. O.; Chivers, Douglas P.

2010-01-01

There is increasing concern that ocean acidification, caused by the uptake of additional CO2 at the ocean surface, could affect the functioning of marine ecosystems; however, the mechanisms by which population declines will occur have not been identified, especially for noncalcifying species such as fishes. Here, we use a combination of laboratory and field-based experiments to show that levels of dissolved CO2 predicted to occur in the ocean this century alter the behavior of larval fish and dramatically decrease their survival during recruitment to adult populations. Altered behavior of larvae was detected at 700 ppm CO2, with many individuals becoming attracted to the smell of predators. At 850 ppm CO2, the ability to sense predators was completely impaired. Larvae exposed to elevated CO2 were more active and exhibited riskier behavior in natural coral-reef habitat. As a result, they had 5–9 times higher mortality from predation than current-day controls, with mortality increasing with CO2 concentration. Our results show that additional CO2 absorbed into the ocean will reduce recruitment success and have far-reaching consequences for the sustainability of fish populations. PMID:20615968

Hyperspectral Geobotanical Remote Sensing for Monitoring and Verifying CO 2 Containment Final Report CRADA No. TC-2036-02

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

Pickles, W. L.; Ebrom, D. A.

This collaborative effort was in support of the CO 2 Capture Project (CCP), to develop techniques that integrate overhead images of plant species, plant health, geological formations, soil types, aquatic, and human use spatial patterns for detection and discrimination of any CO 2 releases from underground storage formations. The goal of this work was to demonstrate advanced hyperspectral geobotanical remote sensing methods to assess potential leakage of CO 2 from underground storage. The timeframes and scales relevant to the long-term storage of CO 2 in the subsurface make remote sensing methods attractive. Moreover, it has been shown that individual fieldmore » measurements of gas composition are subject to variability on extremely small temporal and spatial scales. The ability to verify ultimate reservoir integrity and to place individual surface measurements into context will be crucial to successful long-term monitoring and verification activities. The desired results were to produce a defined and tested procedure that could be easily used for long-term monitoring of possible CO 2 leakage from underground CO 2 sequestration sites. This testing standard will be utilized on behalf of the oil industry.« less

30 s Response Time of K+ Ion-Selective Hydrogels Functionalized with 18-Crown-6 Ether Based on QCM Sensor.

PubMed

Zhang, Zhenxiao; Dou, Qian; Gao, Hongkai; Bai, Bing; Zhang, Yongmei; Hu, Debo; Yetisen, Ali K; Butt, Haider; Yang, Xiaoxia; Li, Congju; Dai, Qing

2018-03-01

Potassium detection is critical in monitoring imbalances in electrolytes and physiological status. The development of rapid and robust potassium sensors is desirable in clinical chemistry and point-of-care applications. In this study, composite supramolecular hydrogels are investigated: polyethylene glycol methacrylate and acrylamide copolymer (P(PEGMA-co-AM)) are functionalized with 18-crown-6 ether by employing surface initiated polymerization. Real-time potassium ion monitoring is realized by combining these compounds with quartz crystal microbalance. The device demonstrates a rapid response time of ≈30 s and a concentration detection range from 0.5 to 7.0 × 10 -3 m. These hydrogels also exhibit high reusability and K + ion selectivity relative to other cations in biofluids such as Na + , NH 4 + , Mg 2+ , and Ca 2+ . These results provide a new approach for sensing alkali metal ions using P(PEGMA-co-AM) hydrogels. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thrombospondin-4 reduces binding affinity of [3H]-gabapentin to calcium-channel α2δ-1-subunit but does not interact with α2δ-1 on the cell-surface when co-expressed

PubMed Central

Lana, Beatrice; Page, Karen M.; Kadurin, Ivan; Ho, Shuxian; Nieto-Rostro, Manuela; Dolphin, Annette C.

2016-01-01

The α2δ proteins are auxiliary subunits of voltage-gated calcium channels, and influence their trafficking and biophysical properties. The α2δ ligand gabapentin interacts with α2δ-1, and inhibits calcium channel trafficking. However, α2-1 has also been proposed to play a synaptogenic role, independent of calcium channel function. In this regard, α2δ-1 was identified as a ligand of thrombospondins, with the interaction involving the thrombospondin synaptogenic domain and the α2δ-1 von-Willebrand-factor domain. Co-immunoprecipitation between α2δ-1 and the synaptogenic domain of thrombospondin-2 was prevented by gabapentin. We therefore examined whether interaction of thrombospondin with α2δ-1 might reciprocally influence 3H-gabapentin binding. We concentrated on thrombospondin-4, because, like α2δ-1, it is upregulated in neuropathic pain models. We found that in membranes from cells co-transfected with α2δ-1 and thrombospondin-4, there was a Mg2+ -dependent reduction in affinity of 3H-gabapentin binding to α2δ-1. This effect was lost for α2δ-1 with mutations in the von-Willebrand-factor-A domain. However, the effect on 3H-gabapentin binding was not reproduced by the synaptogenic EGF-domain of thrombospondin-4. Partial co-immunoprecipitation could be demonstrated between thrombospondin-4 and α2δ-1 when co-transfected, but there was no co-immunoprecipitation with thrombospondin-4-EGF domain. Furthermore, we could not detect any association between these two proteins on the cell-surface, indicating the demonstrated interaction occurs intracellularly. PMID:27076051

The planning of a passive seismic experiment: the Ketzin case

NASA Astrophysics Data System (ADS)

Rossi, G.; Petronio, L.

2009-04-01

In the last years, it has been recognized the importance of using microseismic activity data to gain information on the state and dynamics of a reservoir, notwithstanding the difficulties of recording, localizing the events, interpret them correctly, in terms of developing fractures, or thermal effects. The increasing number of CO2 storage experiments, with the necessity of providing efficient, economic, and long-term monitoring methods, both in the injection and post-injection phases, further encourage the development and improvement of recording and processing techniques. Microseismic signals are typically recorded with downhole sensors. Monitoring with surface sensors is problematic due to increased noise levels and signal attenuation particularly in the near surface. The actual detection distance depends on background noise conditions, seismic attenuation and the microseismic source strength. In the frame of the European project Co2ReMoVe and of the European Network of Excellence Co2GeoNet, a passive seismic experiment was planned in the Ketzin site for geological storage of CO2, a former gas store near Potsdam, object of the CO2SINK European project and inserted also in the European project Co2ReMoVe. Aim of the survey is to complement the CO2-SINK active seismic downhole experiments, adding precious information on the microseismicity induced by stress field changes at the reservoir level and in the overburden, due to the CO2 injection. The baseline survey was done in May 2008 by the Istituto Nazionale di Oceanografia e di Geofisica Sperimentale-OGS (Italy), with the support of the Deutsches GeoForschungsZentrum-GFZ (Germany) and the collaboration of the Institut für Geowissenschaftliche Gemeinschaftsaufgaben-GGA (Germany), shortly before the starting of the CO2 injection (June 30th 2008). A continuous monitoring (about 5 days) was performed by 2 downhole 3C geophones, and 3 surface 3C geophones located around the wells. This paper, based on the analysis of the baseline data, is focused on the design and planning of the next seismic passive surveys, optimizing the recording geometry and instrumentation, to record the microseismic events that could be induced by the redistribution of the stresses following the injection, and help the understanding of the injected CO2 behaviour.

ALMA Resolves the Molecular Gas in a Young Low-metallicity Starburst Galaxy at z = 1.7

NASA Astrophysics Data System (ADS)

González-López, Jorge; Barrientos, L. Felipe; Gladders, M. D.; Wuyts, Eva; Rigby, Jane; Sharon, Keren; Aravena, Manuel; Bayliss, Matthew B.; Ibar, Eduardo

2017-09-01

We present Atacama Large Millimeter/submillimeter Array observations of CO lines and dust continuum emission of the source RCSGA 032727-132609, a young z = 1.7 low-metallicity starburst galaxy. The CO(3-2) and CO(6-5) lines and continuum at rest-frame 450 μm are detected and show a resolved structure in the image plane. We use the corresponding lensing model to obtain a source plane reconstruction of the detected emissions revealing an intrinsic flux density of {S}450μ {{m}}={23.5}-8.1+26.8 μJy and intrinsic CO luminosities {L}{CO(3-2)}{\\prime }={2.90}-0.23+0.21 × {10}8 {{K}} {km} {{{s}}}-1 {{pc}}2 and {L}{CO(6-5)}{\\prime }={8.0}-1.3+1.4× {10}7 {{K}} {km} {{{s}}}-1 {{pc}}2. We used the resolved properties in the source plane to obtain molecular gas and star formation rate surface densities of {{{Σ }}}{{H}2}={16.2}-3.5+5.8 {M}⊙ {{pc}}-2 and {{{Σ }}}{SFR}={0.54}-0.27+0.89 {M}⊙ {{yr}}-1 {{kpc}}-2, respectively. The intrinsic properties of RCSGA 032727-132609 show an enhanced star formation activity compared to local spiral galaxies with similar molecular gas densities, supporting the ongoing merger-starburst phase scenario. RCSGA 032727-132609 also appears to be a low-density starburst galaxy similar to local blue compact dwarf galaxies, which have been suggested as local analogs to high-redshift low-metallicity starburst systems. Finally, the CO excitation level in the galaxy is consistent with having the peak at J˜ 5, with a higher excitation concentrated in the star-forming clumps.

The CarbonTracker Data Assimilation System for CO2 and δ13C (CTDAS-C13 v1.0): retrieving information on land-atmosphere exchange processes

NASA Astrophysics Data System (ADS)

van der Velde, Ivar R.; Miller, John B.; van der Molen, Michiel K.; Tans, Pieter P.; Vaughn, Bruce H.; White, James W. C.; Schaefer, Kevin; Peters, Wouter

2018-01-01

To improve our understanding of the global carbon balance and its representation in terrestrial biosphere models, we present here a first dual-species application of the CarbonTracker Data Assimilation System (CTDAS). The system's modular design allows for assimilating multiple atmospheric trace gases simultaneously to infer exchange fluxes at the Earth surface. In the prototype discussed here, we interpret signals recorded in observed carbon dioxide (CO2) along with observed ratios of its stable isotopologues 13CO2/12CO2 (δ13C). The latter is in particular a valuable tracer to untangle CO2 exchange from land and oceans. Potentially, it can also be used as a proxy for continent-wide drought stress in plants, largely because the ratio of 13CO2 and 12CO2 molecules removed from the atmosphere by plants is dependent on moisture conditions.The dual-species CTDAS system varies the net exchange fluxes of both 13CO2 and CO2 in ocean and terrestrial biosphere models to create an ensemble of 13CO2 and CO2 fluxes that propagates through an atmospheric transport model. Based on differences between observed and simulated 13CO2 and CO2 mole fractions (and thus δ13C) our Bayesian minimization approach solves for weekly adjustments to both net fluxes and isotopic terrestrial discrimination that minimizes the difference between observed and estimated mole fractions.With this system, we are able to estimate changes in terrestrial δ13C exchange on seasonal and continental scales in the Northern Hemisphere where the observational network is most dense. Our results indicate a decrease in stomatal conductance on a continent-wide scale during a severe drought. These changes could only be detected after applying combined atmospheric CO2 and δ13C constraints as done in this work. The additional constraints on surface CO2 exchange from δ13C observations neither affected the estimated carbon fluxes nor compromised our ability to match observed CO2 variations. The prototype presented here can be of great benefit not only to study the global carbon balance but also to potentially function as a data-driven diagnostic to assess multiple leaf-level exchange parameterizations in carbon-climate models that influence the CO2, water, isotope, and energy balance.

CO2 hydrogenation on a metal hydride surface.

PubMed

Kato, Shunsuke; Borgschulte, Andreas; Ferri, Davide; Bielmann, Michael; Crivello, Jean-Claude; Wiedenmann, Daniel; Parlinska-Wojtan, Magdalena; Rossbach, Peggy; Lu, Ye; Remhof, Arndt; Züttel, Andreas

2012-04-28

The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface. This journal is © the Owner Societies 2012

Plasmonics-based detection of H(2) and CO: discrimination between reducing gases facilitated by material control.

PubMed

Dharmalingam, Gnanaprakash; Joy, Nicholas A; Grisafe, Benjamin; Carpenter, Michael A

2012-01-01

Monitoring emissions in high-temperature-combustion applications is very important for regulating the discharge of gases such as NO(2) and CO as well as unburnt fuel into the environment. This work reports the detection of H(2) and CO gases by employing a metal-metal oxide nanocomposite (gold-yttria stabilized zirconia (Au-YSZ)) film fabricated through layer-by-layer physical vapor deposition (PVD). The change in the peak position of the localized surface plasmon resonance (LSPR) was monitored as a function of time and gas concentration. The responses of the films were preferential towards H(2), as observed from the results of exposing the films to the gases at temperatures of 500 °C in a background of dry air. Characterization of the samples by XRD and SEM enabled the correlation of material properties with the differences in the CO- and H(2)-induced LSPR peak shifts, including the relative desensitization towards NO(2). Sensing characteristics of films with varying support thicknesses and metal-particle diameters have been studied, and the results are presented. A comparison has been made to films fabricated through co-sputtered PVD, and the calibration curves of the sensing response show a preferential response towards H(2). The distinction between H(2) and CO responses is also seen through the use of principal-component analysis (PCA). Such material arrangements, which can be tuned for their selectivity by changing certain parameters such as particle size, support thickness, etc., have direct applications within optical chemical sensors for turbine engines, solid-oxide fuel cells, and other high-temperature applications.

Limits, complementarity and improvement of Advanced SAR Interferometry monitoring of anthropogenic subsidence/uplift due to long term CO2 storage

NASA Astrophysics Data System (ADS)

de Michele, M.; Raucoules, D.; Rohmer, J.; Loschetter, A.; Raffard, D.; Le Gallo, Y.

2013-12-01

A prerequisite to the large scale industrial development of CO2 Capture and geological Storage is the demonstration that the storage is both efficient and safe. In this context, precise uplift/subsidence monitoring techniques constitute a key component of any CO2 storage risk management. Space-borne Differential SAR (Synthetic Aperture Radar) interferometry is a promising monitoring technique. It can provide valuable information on vertical positions of a set of scatterer undergoing surface deformation induced by volumetric changes through time and space caused by CO2 injection in deep aquifers. To what extent ? To date, InSAR techniques have been successfully used in a variety of case-studies involving the measure of surface deformation caused by subsurface fluid withdrawal / injection. For instance, groundwater flow characterization in complex aquifers systems, oil / gas field characterization, verification of enhanced oil recovery efficiency, monitoring of seasonal gas storage. The successful use of InSAR is strictly related to the favourable scattering conditions in terms of spatial distribution of targets and their temporal stability. In arid regions, natural radar scatterers density can be very high, exceeding 1,000 per square km. But future onshore industrial-scale CO2 storage sites are planned in more complex land-covers such as agricultural or vegetated terrains. Those terrains are characterized by poor to moderate radar scatterers density, which decrease the detection limits of the space-borne interferometric technique. The present study discusses the limits and constraints of advanced InSAR techniques applied to deformation measurements associated with CO2 injection/storage into deep aquifers in the presence of agricultural and vegetated land-covers. We explore different options to enhance the measurement performances of InSAR techniques. As a first option, we propose to optimize the deployment of a network of 'artificial' scatterers, i.e. corner reflectors (artificial devices installed on ground to provide high backscatter to the radar signal) to complement the existing 'natural' network. The methodology is iterative and adaptive to the spatial and temporal extent of the detectable deforming region. We take into account the need of a change in sensors characteristics (for a very long term monitoring 10-50 years) that could result in a need of re-organisation of the network. Our discussion is supported by the estimates of the expected spatio-temporal evolution of surface vertical displacements caused by CO2 injection at depth by combining the approximate analytical solutions for pressure build-up during CO2 injection in deep aquifers and the poro-elastic behaviour of the reservoir under injection. As second option, we then review different advanced InSAR algorithms that could improve the displacement measurements using natural scatterers over vegetated areas.

Photocatalytic CO2 reduction over SrTiO3: Correlation between surface structure and activity

NASA Astrophysics Data System (ADS)

Luo, Chao; Zhao, Jie; Li, Yingxuan; Zhao, Wen; Zeng, Yubin; Wang, Chuanyi

2018-07-01

Perovskite oxide SrTiO3 is a promising semiconductor photocatalyst for CO2 reduction, which has two possible chemical surfaces-TiO2-terminated and SrO-terminated surfaces. Up to now, the effect of chemical surface and its modification on CO2 adsorption, activation and sequential photocatalytic reduction is not established. In the work, SrTiO3, surface-Ti-rich SrTiO3 and Sr(OH)2-decorated SrTiO3 were prepared and their structural, surface, and optical properties and photocatalytic activity were explored. It is found that the absorption edge of surface-Ti-rich SrTiO3 shifted toward visible-light region as compared with that of the other two photocatalysts, which is attributed to the decreased Ti 3d ground-state level at the surface. Bicarbonate- (HCO3-) and bidentate carbonate-like (b-CO3=) species are the main species for CO2 adsorption on the surface-Ti-rich SrTiO3, whereas, besides HCO3- and b-CO3=, plenty of monodentate carbonate-like species (m-CO3=) that has relatively low reactivity is present on the SrTiO3 and Sr(OH)2-decorated photocatalysts. As a result, the surface-Ti-rich SrTiO3 exhibits the highest activity for CO2 reduction. Furthermore, although Sr(OH)2-decoration and SrO-terminated surfaces facilitate CO2 fixing, the produced surface species are attached to the weakly active Sr ions, giving rise to the lower reactivity. The present work might supply a guide for designing highly active perovskite-type semiconductors for photocatalysis.

Use of PIXE-PIGE under variable incident angle for ancient glass corrosion measurements

NASA Astrophysics Data System (ADS)

Weber, G.; Strivay, D.; Martinot, L.; Garnir, H. P.

2002-04-01

Although glass is usually considered as a very stable archaeological material, it can undergo severe degradation. Soda-lime glass, the most common glass throughout ancient times, is particularly sensitive to this problem. The glass surface absorbs moisture from its environment and the contact with CO 2 causes Na 2O and NaOH to convert to Na 2CO 3, which is extremely hygroscopic. The subsequent unstable glass layer can be leached out and causes decomposition of the glass. The non-destructive PIGE-PIXE method of investigation allows detection of this phenomenon even if no visible effect appears. The variable incident angle method is able to discern the depth of the degradation. One aim of such studies is the possible dating or at least fake detecting of archaeological materials. Furthermore, even objects of large size can be investigated with the atmospheric PIGE-PIXE set-up. Some examples of measurements on ancient glass are given.

Redox polymer and probe DNA tethered to gold electrodes for enzyme-amplified amperometric detection of DNA hybridization.

PubMed

Kavanagh, Paul; Leech, Dónal

2006-04-15

The detection of nucleic acids based upon recognition surfaces formed by co-immobilization of a redox polymer mediator and DNA probe sequences on gold electrodes is described. The recognition surface consists of a redox polymer, [Os(2,2'-bipyridine)2(polyvinylimidazole)(10)Cl](+/2+), and a model single DNA strand cross-linked and tethered to a gold electrode via an anchoring self-assembled monolayer (SAM) of cysteamine. Hybridization between the immobilized probe DNA of the recognition surface and a biotin-conjugated target DNA sequence (designed from the ssrA gene of Listeria monocytogenes), followed by addition of an enzyme (glucose oxidase)-avidin conjugate, results in electrical contact between the enzyme and the mediating redox polymer. In the presence of glucose, the current generated due to the catalytic oxidation of glucose to gluconolactone is measured, and a response is obtained that is binding-dependent. The tethering of the probe DNA and redox polymer to the SAM improves the stability of the surface to assay conditions of rigorous washing and high salt concentration (1 M). These conditions eliminate nonspecific interaction of both the target DNA and the enzyme-avidin conjugate with the recognition surfaces. The sensor response increases linearly with increasing concentration of target DNA in the range of 1 x 10(-9) to 2 x 10(-6) M. The detection limit is approximately 1.4 fmol, (corresponding to 0.2 nM of target DNA). Regeneration of the recognition surface is possible by treatment with 0.25 M NaOH solution. After rehybridization of the regenerated surface with the target DNA sequence, >95% of the current is recovered, indicating that the redox polymer and probe DNA are strongly bound to the surface. These results demonstrate the utility of the proposed approach.

DFT insight into the effect of potassium on the adsorption, activation and dissociation of CO2 over Fe-based catalysts.

PubMed

Nie, Xiaowa; Meng, Linlin; Wang, Haozhi; Chen, Yonggang; Guo, Xinwen; Song, Chunshan

2018-05-30

Catalytic conversion of CO2 including hydrogenation has attracted great attention as a method for chemical fixation of CO2 in combination with other techniques such as CO2 capture and storage. Potassium is a well-known promotor for many industrial catalytic processes such as in Fischer-Tropsch synthesis. In this work, we performed density functional theory (DFT) calculations to investigate the effect of potassium on the adsorption, activation, and dissociation of CO2 over Fe(100), Fe5C2(510) and Fe3O4(111) surfaces. The function of K was analyzed in terms of electronic interactions between co-adsorbed CO2 and K-surfaces which showed conspicuous promotion in the presence of K of the adsorption and activation of CO2. The adsorption strength of CO2 on these surfaces ranks as oct2-Fe3O4(111) > Fe(100) > Fe5C2(510). Generally, we observed a direct proportional correlation between the adsorption strength and the charges on the adsorbates. Adding K on the catalyst surface also reduces the kinetic barrier for CO2 dissociation. CO2 dissociation is more facile to occur on Fe(100) and Fe5C2(510) in the presence of K whereas the Fe3O4(111) surfaces impede CO2 dissociation regardless of the existence of K. Instead, a stable CO3- species is formed upon CO2 adsorption on Fe3O4(111) which will be directly hydrogenated when sufficient H* are available on the surface. Our results highlight the origin of the promotion effect of potassium and provide insight for the future design of K-promoted Fe-based catalysts for CO2 hydrogenation.

Huygens Gas Chromatograph Mass Spectrometer Results from Titan

NASA Technical Reports Server (NTRS)

Niemann, Hasso

2008-01-01

The Huygens Probe executed a successful entry, descent and impact on the Saturnian moon of Titan on January 14, 2005. Gas Chromatograph Mass Spectrometer (GCMS) instrument conducted isotopic and compositional measurements throughout the two and one half hour descent from 146 km altitude, and on the surface for 69 minutes until loss of signal from the orbiting Cassini spacecraft. The GCMS incorporated a quadrupole mass filter with a secondary electron multiplier detection system. The gas sampling system provided continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact. Data products from the GCMS included altitude profiles of the major atmospheric constituents dinitrogen (N2) and methane (CH4), isotope ratios of N-14/N-15, C-12/C-13, and D/H, mole fractions of radiogenic argon (Ar-40)and primordial argon Ar-36), and upper limits on the mole fractions of neon, krypton and xenon, which were found to be below the detection limit of the instrument or absent. Surface measurements confirmed the presence of ethane (C2H6) and cyanogen (C2N2). Later data products include the instrument response to surface outgassing of C2N2, C2H6, acetylene (C2H2),and carbon dioxide (CO2). More recent results include the detection of benzene (C6H6) and height profiles of molecular hydrogen (H2). Numerous other trace species evaporating from the surface were also identified using the GCMS data.

Limits on the UV Photodecomposition of Carbonates on Mars

NASA Technical Reports Server (NTRS)

Quinn, Richard; Zent, Aaron P.; McKay, Christopher P.; DeVincenzi, Donald L. (Technical Monitor)

2002-01-01

The effect of UV (ultraviolet) light on the stability of calcium carbonate in a simulated martian atmosphere was experimentally investigated. Sample cells containing C-13 labeled calcite were irradiated with a Xe arc lamp in 10 mbar of simulated martian atmosphere and a quadrupole mass spectrometer was used to monitor the headspace gases for the production of (13)CO2. We found no experimental evidence of the UV photodecomposition of calcium carbonate in a simulated martian atmosphere. Extrapolating the lower limit of detection of our experimental system to an upper limit of carbonate decomposition on Mars yields a quantum efficiency of 3.5 x 10(exp -8) molecules/photon over the wavelength interval of 190-390 nm and a maximum UV photodecomposition rate of 1.2 x 10(exp -13) kg m(exp -2) s(exp -1) from a calcite surface. The maximum loss of bulk calcite due to this process would be 2.5 nm yr(exp -1). However, calcite is expected to be thermodynamically stable on the surface of Mars and potential UV photodecomposition reaction mechanisms indicate that while calcium carbonate may decompose under vacuum, it would be stable in a CO2 atmosphere. Given the expected stability of carbonate on Mars and our inability to detect carbonate decomposition, we conclude that it is unlikely that the apparent absence of carbonate on the martian surface is due to UV photo decomposition of calcite in the current environment.

Synthesis and detection the oxidization of Co cores of Co@SiO2 core-shell nanoparticles by in situ XRD and EXAFS.

PubMed

Zhang, Kunhao; Zhao, Ziyan; Wu, Zhonghua; Zhou, Ying

2015-01-01

In this paper, the Co@SiO2 core-shell nanoparticles were prepared by the sol-gel method. The oxidization of Co core nanoparticles was studied by the synchrotron radiation-based techniques including in situ X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) up to 800°C in air and N2 protection conditions, respectively. It was found that the oxidization of Co cores is undergoing three steps regardless of being in air or in N2 protection condition. In the first step ranging from room temperature to 200°C, the Co cores were dominated by Co(0) state as well as small amount of Co(2+) ions. When temperature was above 300°C, the interface between Co cores and SiO2 shells was gradually oxidized into Co(2+), and the CoO layer was observed. As the temperature increasing to 800°C, the Co cores were oxidized to Co3O4 or Co3O4/CoO. Nevertheless, the oxidization kinetics of Co cores is different for the Co@SiO2 in air and N2 gas conditions. Generally, the O2 in the air could get through the SiO2 shells easily onto the Co core surface and induce the oxidization of the Co cores due to the mesoporous nature of the SiO2 shells. However, in N2 gas condition, the O atoms can only be from the SiO2 shells, so the diffusion effect of O atoms in the interface between Co core and SiO2 shell plays a key role.

Fast synthesis of porous NiCo2O4 hollow nanospheres for a high-sensitivity non-enzymatic glucose sensor

NASA Astrophysics Data System (ADS)

Huang, Wei; Cao, Yang; Chen, Yong; Peng, Juan; Lai, Xiaoyong; Tu, Jinchun

2017-02-01

In this paper, we report the fast synthesis of porous NiCo2O4 hollow nanospheres via a polycrystalline Cu2O-templated route based on the elaborately designed "coordinating etching and precipitating" process. The composition and morphology of the porous NiCo2O4 hollow nanospheres were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The electron-transfer capability and electrocatalytic activity of the materials were investigated by electrochemical impedance spectroscopy and cyclic voltammetry. NiCo2O4 was endowed with superior electron-transfer capability, large surface area, and abundant intrinsic redox couples of Ni2+/Ni3+ and Co2+/Co3+ ions; thus, the modified electrode exhibited excellent glucose-sensing properties, with a high sensitivity of 1917 μA·mM-1·cm-2 at a low concentration, a good linear range from 0.01 mM to 0.30 mM and from 0.30 mM to 2.24 mM, and a low detection limit of 0.6 μM (S/N = 3).

Surface Modification of SiO2 Microchannels with Biocompatible Polymer Using Supercritical Carbon Dioxide

NASA Astrophysics Data System (ADS)

Saito, Tatsuro; Momose, Takeshi; Hoshi, Toru; Takai, Madoka; Ishihara, Kazuhiko; Shimogaki, Yukihiro

2010-11-01

The surface of 500-mm-long microchannels in SiO2 microchips was modified using supercritical CO2 (scCO2) and a biocompatible polymer was coated on it to confer biocompatibility to the SiO2 surface. In this method, the SiO2 surface of a microchannel was coated with poly(ethylene glycol monomethacrylate) (PEGMA) as the biocompatible polymer using allyltriethoxysilane (ATES) as the anchor material in scCO2 as the reactive medium. Results were compared with those using the conventional wet method. The surface of a microchannel could not be modified by the wet method owing to the surface tension and viscosity of the liquid, but it was modified uniformly by the scCO2 method probably owing to the near-zero surface tension, low viscosity, and high diffusivity of scCO2. The effect of the surface modification by the scCO2 method to prevent the adsorption of protein was as high as that of the modification by the wet method. Modified microchips can be used in biochemical and medical analyses.

Dynamic interaction of CO/H 2O mixtures with gold nanocrystals: Real-time imaging and local chemical probing

NASA Astrophysics Data System (ADS)

Visart de Bocarmé, Thierry; Chau, Thoi-Dai; Kruse, Norbert

2006-09-01

The dynamic interaction of pure gold nanocrystals ("tips") with H 2O/CO gas mixtures was studied by means of video-field ion microscopy (FIM). While imaging with nano-scale resolution selected areas of the equivalent of ˜200 atomic Au sites were analysed for their chemical composition using short field pulses and injecting respective ions into a time-of-flight mass spectrometer (pulsed field desorption mass spectrometry, PFDMS). At room temperature the exposure of a clean Au sample to water gas at 10 -4 Pa, in the presence of an electric field of ˜10 V/nm, led to water adsorption and formation of bright patterns in FIM. Additional exposure to CO gas at 5 × 10 -3 Pa led to the removal of the water layer. This was associated with the occurrence of bright wave fronts which ignited simultaneously in several regions of the Au surface with no preference for a certain crystallographic surface plane. In some cases wave fronts were seen to collide resulting in more complicated patterns such as concentric rings. Surface areas free of water appeared with low brightness. The phenomena were completely reversible. PFDMS demonstrated water ions to be responsible for image formation. Surface hydroxyl was also detected mass spectrometrically and respective ion intensities decreased during the titration with CO. The results suggest that gold nanocrystals, in the absence of oxidic support materials, may be active in the reaction between water and CO at temperatures as low as 300 K and in the presence of an electric field of ˜10 V/nm.

Roles of reaction kinetics of CO 2 on a PrBaCo 2O 5.5+δ surfaces

DOE PAGES

Xu, Xing; Mace, Brennan; Enriquez, Erik; ...

2017-08-18

A symmetric PBCO/YSZ/PBCO cell (where PBCO refers to PrBaCo 2O 5.5+δ, and YSZ to yttria stabilized zirconia) was designed and fabricated for the investigation of the catalytic nature and reaction kinetics of CO 2 on PBCO surfaces. The electrochemical impedance spectroscopy was employed to probe the CO 2 reaction behavior on the PBCO electrode. The symmetric equivalent circuit cell characterization reveals that the surface resistance of CO 2 on PBCO is only 30.2 Ω cm 2 and the maximum surface exchange coefficient k chem is 2.0 × 10 -4 cm s -1 at 1147 K, suggesting that PBCO can bemore » an excellent candidate for CO 2 reduction.« less

Transversely Excited Atmospheric CO2 Laser-Induced Plasma Spectroscopy for the Detection of Heavy Metals in Soil

NASA Astrophysics Data System (ADS)

Khumaeni, A.; Sugito, H.; Setia Budi, W.; Yoyo Wardaya, A.

2018-01-01

A rapid detection of heavy metals in soil was presented by the metal-assisted gas plasma method using specific characteristics of a pulsed, transversely excited atmospheric (TEA) CO2 laser. The soil particles were placed in a hole made of acrylic plate. The sample was covered by a to prevent the soil particles from being blown off. The mesh also functioned to initiate a luminous plasma. When a TEA CO2 laser (1500 mJ, 200 ns) was focused on the soil sample, passing through the metal mesh, some of the laser energy was used to generate the gas plasma on the mesh surface, and the remaining laser energy was employed to ablate the soil particles. The fine, ablated soil particles moved into the gas plasma region to be dissociated and excited. Using this technique, analysis can be made with reduced sample pretreatment, and therefore a rapid analysis can be performed efficiently. The results proved that the signal to noise ratio (S/N) of the emission spectral lines is much better for the case of the present method (mesh method) compared to the case of standard laser-induced breakdown spectroscopy using the pellet method. Rapid detection of heavy metal elements in soil has been successfully carried out. The detection limits of Cu and Hg in soil were estimated to be 3 and 10 mg/kg, respectively. The present method has good potential for rapid and sensitive detection of heavy metals in soil samples.

Atomic layer deposition to prevent metal transfer from implants: An X-ray fluorescence study

NASA Astrophysics Data System (ADS)

Bilo, Fabjola; Borgese, Laura; Prost, Josef; Rauwolf, Mirjam; Turyanskaya, Anna; Wobrauschek, Peter; Kregsamer, Peter; Streli, Christina; Pazzaglia, Ugo; Depero, Laura E.

2015-12-01

We show that Atomic Layer Deposition is a suitable coating technique to prevent metal diffusion from medical implants. The metal distribution in animal bone tissue with inserted bare and coated Co-Cr alloys was evaluated by means of micro X-ray fluorescence mapping. In the uncoated implant, the migration of Co and Cr particles from the bare alloy in the biological tissues is observed just after one month and the number of particles significantly increases after two months. In contrast, no metal diffusion was detected in the implant coated with TiO2. Instead, a gradient distribution of the metals was found, from the alloy surface going into the tissue. No significant change was detected after two months of aging. As expected, the thicker is the TiO2 layer, the lower is the metal migration.

Selective divalent cobalt ions detection using Ag2O3-ZnO nanocones by ICP-OES method for environmental remediation.

PubMed

Rahman, Mohammed M; Khan, Sher Bahadar; Marwani, Hadi M; Asiri, Abdullah M

2014-01-01

Here, we have synthesized Ag2O3-ZnO nanocones (NCs) by a wet-chemical route using reducing agents at low temperature. The structural, optical and morphological properties of Ag2O3-ZnO NCs were investigated by several conventional techniques such as powder XRD, XPS, FESEM, XEDS, FTIR and UV/vis. spectroscopy. The analytical parameters of prepared NCs were also calculated for a selective detection of divalent cobalt [Co(II)] prior to its determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). The selectivity of NCs toward various metal ions, including Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ni(II), and Zn(II) was studied. Results of the selectivity study demonstrated that Ag2O3-ZnO NC phase was the most selective towards Co(II) ion. The uptake capacity for Co(II) ion was experimentally calculated to be ∼76.69 mgg-1. Moreover, adsorption isotherm data provided that the adsorption process was mainly monolayer on homogeneous adsorbent surfaces of Ag2O3-ZnO NCs. Kinetic study revealed that the adsorption of Co(II) on Ag2O3-ZnO NCs phase followed the pseudo-second-order kinetic model. In addition, thermodynamic results provided that the adsorption mechanism of Co(II) ions on Ag2O3-ZnO NCs was a spontaneous process and thermodynamically favorable. Finally, the proposed method was validated by applying it to real environmental water samples with reasonable results.

Selective Divalent Cobalt Ions Detection Using Ag2O3-ZnO Nanocones by ICP-OES Method for Environmental Remediation

PubMed Central

Rahman, Mohammed M.; Khan, Sher Bahadar; Marwani, Hadi M.; Asiri, Abdullah M.

2014-01-01

Here, we have synthesized Ag2O3-ZnO nanocones (NCs) by a wet-chemical route using reducing agents at low temperature. The structural, optical and morphological properties of Ag2O3-ZnO NCs were investigated by several conventional techniques such as powder XRD, XPS, FESEM, XEDS, FTIR and UV/vis. spectroscopy. The analytical parameters of prepared NCs were also calculated for a selective detection of divalent cobalt [Co(II)] prior to its determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). The selectivity of NCs toward various metal ions, including Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ni(II), and Zn(II) was studied. Results of the selectivity study demonstrated that Ag2O3-ZnO NC phase was the most selective towards Co(II) ion. The uptake capacity for Co(II) ion was experimentally calculated to be ∼76.69 mgg−1. Moreover, adsorption isotherm data provided that the adsorption process was mainly monolayer on homogeneous adsorbent surfaces of Ag2O3-ZnO NCs. Kinetic study revealed that the adsorption of Co(II) on Ag2O3-ZnO NCs phase followed the pseudo-second-order kinetic model. In addition, thermodynamic results provided that the adsorption mechanism of Co(II) ions on Ag2O3-ZnO NCs was a spontaneous process and thermodynamically favorable. Finally, the proposed method was validated by applying it to real environmental water samples with reasonable results. PMID:25464507

Critical Role of Water and Oxygen Defects in C-O Scission during CO2 Reduction on Zn2GeO4(010).

PubMed

Yang, Jing; Li, Yanlu; Zhao, Xian; Fan, Weiliu

2018-03-27

Exploration of catalyst structure and environmental sensitivity for C-O bond scission is essential for improving the conversion efficiency because of the inertness of CO 2 . We performed density functional theory calculations to understand the influence of the properties of adsorbed water and the reciprocal action with oxygen vacancy on the CO 2 dissociation mechanism on Zn 2 GeO 4 (010). When a perfect surface was hydrated, the introduction of H 2 O was predicted to promote the scission step by two modes based on its appearance, with the greatest enhancement from dissociative adsorbed H 2 O. The dissociative H 2 O lowers the barrier and reaction energy of CO 2 dissociation through hydrogen bonding to preactivate the C-O bond and assisted scission via a COOH intermediate. The perfect surface with bidentate-binding H 2 O was energetically more favorable for CO 2 dissociation than the surface with monodentate-binding H 2 O. Direct dissociation was energetically favored by the former, whereas monodentate H 2 O facilitated the H-assisted pathway. The defective surface exhibited a higher reactivity for CO 2 decomposition than the perfect surface because the generation of oxygen vacancies could disperse the product location. When the defective surface was hydrated, the reciprocal action for vacancy and surface H 2 O on CO 2 dissociation was related to the vacancy type. The presence of H 2 O substantially decreased the reaction energy for the direct dissociation of CO 2 on O 2c1 - and O 3c2 -defect surfaces, which converts the endoergic reaction to an exoergic reaction. However, the increased decomposition barrier made the step kinetically unfavorable and reduced the reaction rate. When H 2 O was present on the O 2c2 -defect surface, both the barrier and reaction energy for direct dissociation were invariable. This result indicated that the introduction of H 2 O had little effect on the kinetics and thermodynamics. Moreover, the H-assisted pathway was suppressed on all hydrated defect surfaces. These results provide a theoretical perspective for the design of highly efficient catalysts.

Driving CO2 to a Quasi-Condensed Phase at the Interface between a Nanoparticle Surface and a Metal-Organic Framework at 1 bar and 298 K.

PubMed

Lee, Hiang Kwee; Lee, Yih Hong; Morabito, Joseph V; Liu, Yejing; Koh, Charlynn Sher Lin; Phang, In Yee; Pedireddy, Srikanth; Han, Xuemei; Chou, Lien-Yang; Tsung, Chia-Kuang; Ling, Xing Yi

2017-08-23

We demonstrate a molecular-level observation of driving CO 2 molecules into a quasi-condensed phase on the solid surface of metal nanoparticles (NP) under ambient conditions of 1 bar and 298 K. This is achieved via a CO 2 accumulation in the interface between a metal-organic framework (MOF) and a metal NP surface formed by coating NPs with a MOF. Using real-time surface-enhanced Raman scattering spectroscopy, a >18-fold enhancement of surface coverage of CO 2 is observed at the interface. The high surface concentration leads CO 2 molecules to be in close proximity with the probe molecules on the metal surface (4-methylbenzenethiol), and transforms CO 2 molecules into a bent conformation without the formation of chemical bonds. Such linear-to-bent transition of CO 2 is unprecedented at ambient conditions in the absence of chemical bond formation, and is commonly observed only in pressurized systems (>10 5 bar). The molecular-level observation of a quasi-condensed phase induced by MOF coating could impact the future design of hybrid materials in diverse applications, including catalytic CO 2 conversion and ambient solid-gas operation.

Facile synthesis of electrospun MFe2O4 (M = Co, Ni, Cu, Mn) spinel nanofibers with excellent electrocatalytic properties for oxygen evolution and hydrogen peroxide reduction.

PubMed

Li, Mian; Xiong, Yueping; Liu, Xiaotian; Bo, Xiangjie; Zhang, Yufan; Han, Ce; Guo, Liping

2015-05-21

Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m(2) g(-1)) than those of the CoFe2O4 NPs (5.93 m(2) g(-1))) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media.

Adsorption and reaction of CO and H2O on WC(0001) surface: A first-principles investigation

NASA Astrophysics Data System (ADS)

Tong, Yu-Jhe; Wu, Shiuan-Yau; Chen, Hsin-Tsung

2018-01-01

We have performed a spin-polarized density functional theory (DFT) study for understanding the detailed reaction mechanism of CO and H2O on WC (0001) surface. The adsorption properties and vibrational frequencies of H2O, OH, O, H, CO and CO2 on the WC (0001) surface were illustrated. These results are well in consistent with the experimental observations studied by temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). Based on the adsorption results, potential energy profiles of H2O and OH dehydrogenation and HCO, COH, COOH, and CO2 formation on the WC (0001) surface were predicted. The calculation results demonstrated that the WC (0001) surface as Fe (110) surface exhibits significantly reaction activity toward the dehydrogenation of H2O and OH but less activity toward the formation of HCO, COH, COOH and CO2 compared to the Cu (111) and Pt (111) surfaces.

The Joint Airport Weather Studies Project - Current analysis highlights in the aviation safety context

NASA Technical Reports Server (NTRS)

Mccarthy, J.

1984-01-01

The principal objective of the Joint Airport Weather Studies Project was to obtain high-resolution velocity, turbulence, and thermodynamic data on a convective outflow called a microburst, an intense downdraft and resulting horizontal outflow near the surface. Data collection occurred during the summer of 1982 near Denver, CO. Data sensors included three pulsed-microwave Doppler and two pulsed CO2 lidar radars, along with 27 Portable Automated Mesonet surface weather stations, the FAA's low-level-wind-shear alert system (LLWSAS), and five instrumented research aircraft. Convective storms occurred on 75 of 91 operational days, with Doppler data being collected on at least 70 microbursts. Analyses reported included a thorough examination of microburst-climatology statistics, the capability of the LLWSAS to detect adequately and accurately the presence of low-altitude wind shear danger to aircraft, the capability of a terminal Doppler radar system development to provide improved wind-shear detection and warning, and progress toward improved wind-shear training for pilots.

High Chemical Activity of a Perovskite Surface: Reaction of CO with Sr3Ru2O7

NASA Astrophysics Data System (ADS)

Stöger, Bernhard; Hieckel, Marcel; Mittendorfer, Florian; Wang, Zhiming; Fobes, David; Peng, Jin; Mao, Zhiqiang; Schmid, Michael; Redinger, Josef; Diebold, Ulrike

2014-09-01

Adsorption of CO at the Sr3Ru2O7(001) surface was studied with low-temperature scanning tunneling microscopy (STM) and density functional theory. In situ cleaved single crystals terminate in an almost perfect SrO surface. At 78 K, CO first populates impurities and then adsorbs above the apical surface O with a binding energy Eads=-0.7 eV. Above 100 K, this physisorbed CO replaces the surface O, forming a bent CO2 with the C end bound to the Ru underneath. The resulting metal carboxylate (Ru-COO) can be desorbed by STM manipulation. A low activation (0.2 eV) and high binding (-2.2 eV) energy confirm a strong reaction between CO and regular surface sites of Sr3Ru2O7; likely, this reaction causes the "UHV aging effect" reported for this and other perovskite oxides.

Characterization and corrosion behaviour of CoNi alloys obtained by mechanical alloying

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

Olvera, S.; Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química-Física Aplicada, 28049 Madrid; Sánchez-Marcos, J.

2014-07-01

CoNi alloys including Co{sub 30}Ni{sub 70}, Co{sub 50}Ni{sub 50} and Co{sub 70}Ni{sub 30} were prepared via mechanical alloying using Co and Ni powders. The crystallinity and short-range order were studied using X-ray diffraction and X-ray absorption spectroscopy. The results show that the milling process increases the number of vacancies, especially around the Co atoms, while the milling time decreases the crystalline size and enhances the crystallinity. X-ray photoelectron spectroscopy was used to characterise the chemical composition of the samples surface. The magnetic properties were analysed using zero-field cooling, field cooling and a magnetic hysteresis loops. The magnetic saturation moment ismore » approximately 1.05 μ{sub B}/atom; this value decreases with the mechanical alloying time, and it is proportional to the cobalt concentration. The polarization and impedance curves in different media (NaCl, H{sub 2}SO{sub 4} and NaOH) showed similar corrosion resistance values. The corrosion resistance increased in the order NaCl, H{sub 2}SO{sub 4} and NaOH. A good passivation layer was formed in NaOH due to the cobalt and nickel oxides on the particle surfaces. - Highlights: • Ni{sub x}Co{sub 100-x} alloys were synthesized by mechanical alloying • Milling time decrease size and enhances crystallinity. • Oxygen is not present in a significant percentage in bulk but is detected on the surface. • Magnetic saturation moment is 1.05 mB/atom and decrease with mechanical allowing time • Corrosion resistance is higher in NaOH than in NaCl or HCl solutions.« less

Analysis of non-phthalates plasticizers on porous graphitic carbon by supercritical fluid chromatography using evaporative light scattering detection.

PubMed

Vaccher, Claude; Decaudin, Bertrand; Sautou, Valérie; Lecoeur, Marie

2014-09-12

The analysis of several plasticizers, widely used in the production of medical devices, was investigated on porous graphitic carbon (PGC) stationary phase in supercritical fluid chromatography (SFC) with an evaporative light scattering detector (ELSD). Due to strong interaction of compounds with the PGC support, solvents of strong eluotropic strength were added to the CO2 supercritical fluid. The effect of alkyl chain (pentane, hexane, heptane) and chlorinated (CH2Cl2, CHCl3, CCl4) solvents was studied on the retention and on the ELSD detection of plasticizers. A co-solvent mixture composed of CHCl3/heptane, eluted under gradient mode, allowed a significant improvement of the ELSD response compared to the use of each solvent individually. Then, a central composite design (CCD) was implemented to optimize both the separation and the detection of plasticizers. The parameters involved were the outlet pressure, the gradient slope, the co-solvent composition and the drift tube temperature of the ELSD. After optimization, baseline separation of plasticizers was achieved in 7min and best signal-to-noise ratios were obtained with outlet pressure and drift tube temperature of ELSD set at 200bar and 31°C, respectively. The co-solvent mixture was also composed of CHCl3/heptane (35/65 v/v) and a gradient from 15 to 60% of co-solvent in 2.2min was employed. The results demonstrated that CCD is a powerful tool for the optimization of SFC/ELSD method and the response surface model analysis can provide statistical understandings of the significant factors required to achieve optimal separation and ELSD sensitivity. Copyright © 2014 Elsevier B.V. All rights reserved.

Surface chemistry of carbon dioxide revisited

NASA Astrophysics Data System (ADS)

Taifan, William; Boily, Jean-François; Baltrusaitis, Jonas

2016-12-01

This review discusses modern developments in CO2 surface chemistry by focusing on the work published since the original review by H.J. Freund and M.W. Roberts two decades ago (Surface Science Reports 25 (1996) 225-273). It includes relevant fundamentals pertaining to the topics covered in that earlier review, such as conventional metal and metal oxide surfaces and CO2 interactions thereon. While UHV spectroscopy has routinely been applied for CO2 gas-solid interface analysis, the present work goes further by describing surface-CO2 interactions under elevated CO2 pressure on non-oxide surfaces, such as zeolites, sulfides, carbides and nitrides. Furthermore, it describes additional salient in situ techniques relevant to the resolution of the interfacial chemistry of CO2, notably infrared spectroscopy and state-of-the-art theoretical methods, currently used in the resolution of solid and soluble carbonate species in liquid-water vapor, liquid-solid and liquid-liquid interfaces. These techniques are directly relevant to fundamental, natural and technological settings, such as heterogeneous and environmental catalysis and CO2 sequestration.

CO2 adsorption-assisted CH4 desorption on carbon models of coal surface: A DFT study

NASA Astrophysics Data System (ADS)

Xu, He; Chu, Wei; Huang, Xia; Sun, Wenjing; Jiang, Chengfa; Liu, Zhongqing

2016-07-01

Injection of CO2 into coal is known to improve the yields of coal-bed methane gas. However, the technology of CO2 injection-enhanced coal-bed methane (CO2-ECBM) recovery is still in its infancy with an unclear mechanism. Density functional theory (DFT) calculations were performed to elucidate the mechanism of CO2 adsorption-assisted CH4 desorption (AAD). To simulate coal surfaces, different six-ring aromatic clusters (2 × 2, 3 × 3, 4 × 4, 5 × 5, 6 × 6, and 7 × 7) were used as simplified graphene (Gr) carbon models. The adsorption and desorption of CH4 and/or CO2 on these carbon models were assessed. The results showed that a six-ring aromatic cluster model (4 × 4) can simulate the coal surface with limited approximation. The adsorption of CO2 onto these carbon models was more stable than that in the case of CH4. Further, the adsorption energies of single CH4 and CO2 in the more stable site were -15.58 and -18.16 kJ/mol, respectively. When two molecules (CO2 and CH4) interact with the surface, CO2 compels CH4 to adsorb onto the less stable site, with a resulting significant decrease in the adsorption energy of CH4 onto the surface of the carbon model with pre-adsorbed CO2. The Mulliken charges and electrostatic potentials of CH4 and CO2 adsorbed onto the surface of the carbon model were compared to determine their respective adsorption activities and changes. At the molecular level, our results showed that the adsorption of the injected CO2 promoted the desorption of CH4, the underlying mechanism of CO2-ECBM.

Application of Geochemical Parameters for the Early Detection of CO2 Leakage from Sequestration Sites into Groundwater

NASA Astrophysics Data System (ADS)

Kharaka, Y. K.; Beers, S.; Thordsen, J.; Thomas, B.; Campbell, P.; Herkelrath, W. N.; Abedini, A. A.

2011-12-01

Geologically sequestered CO2 is buoyant, has a low viscosity and, when dissolved in brine, becomes reactive to minerals and well pipes. These properties of CO2 may cause it to leak upward, possibly contaminating underground sources of drinking water. We have participated in several multi-laboratory field experiments to investigate the chemical and isotopic parameters that are applicable to monitoring the flow of injected CO2 into deep saline aquifers and into potable shallow groundwater. Geochemical results from the deep SECARB Phase III tests at Cranfield oil field, Mississippi, and from the Frio Brine I and II pilots located in the S. Liberty oil field, Dayton, Texas, proved powerful tools in: 1- Tracking the successful injection and flow of CO2 into the injection sandstones; 2- showing major changes in the chemical (pH, alkalinity, and major divalent cations) and isotopic (δ13C values of CO2, and δ18O values of CO2 and brine) compositions of formation water; 3-. showing mobilization of metals, including Fe Mn and Pb, and organic compounds , including DOC, BTEX, PAHs, and phenols following CO2 injection; and 4- showing that some of the CO2 injected into the Frio "C" sandstone was detected in the overlying "B" sandstone that is separated from it by 15 m of shale and siltstone. Rapid, significant and systematic changes were also observed in the isotopic and chemical compositions of shallow groundwater at the Zero Emissions Research and Technology (ZERT) site located in Bozeman, Montana, in response to four yearly injections of variable amounts of CO2 gas through a slotted pipe placed horizontally at a depth of ~2 m below ground level. The observed changes, included the lowering of groundwater pH from ~7.0 to values as low as 5.6, increases in the alkalinity from about 400 mg/L as HCO3 to values of up to 1330 mg/L, increases in the electrical conductance from ~600 μS/cm to up to 1800 μS/cm, as well as increases in the concentrations of cations and metals following CO2 injection. Geochemical modeling, sequential extractions of cations from the ZERT-aquifer sediments, and controlled laboratory CO2-groundwater-sediment interactions demonstrated that calcite dissolution and ion exchange on organic material and inorganic mineral surfaces are responsible for the observed chemical changes. Results from both the deep and shallow field tests show that geochemical methods have highly sensitive chemical and isotopic tracers that are needed at CO2 injection sites to monitor injection performance and for early detection of any CO2 and brine leakages.

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.

Dissecting the steps of CO2 reduction: 1. The interaction of CO and CO2 with γ-Al2O3: an in situ FTIR study

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

Szanyi, Janos; Kwak, Ja Hun

2014-08-07

The adsorption of CO2 and CO was investigated on a pure γ-Al2O3 support material that has been used for the preparation of Pd and Ru catalysts for the catalytic reduction of CO2. The adsorption of CO2 resulted in the formation of carbonates, bicarbonates and linearly adsorbed CO2 species. The amount and the nature of the adsorbed species were dependent on the annealing temperature of the alumina support. On γ-Al2O3 annealed at 473 K mostly bicarbonates formed, while no adsorbed CO2 was seen on this highly hydroxylated surface. With increasing calcinations temperature, i.e., increasing extent of dehydroxylation, the amounts of bothmore » surface nitrates and linear adsorbed CO2 increased, but still the most abundant surface species were bicarbonates. Surface carbonates and adsorbed CO2 can readily be removed from the alumina surface, while bicarbonates are stable to elevated temperatures. The interaction of CO with γ-Al2O3 is much weaker than that of CO2. At room temperatures CO adsorbs only on Lewis acid sites, and can be readily removed by evacuation. At 100 K CO can probe different defect sites on the alumina surface (both Lewis acid sites and surface hydroxyls). Under no conditions we have observed the formation of any carbonates or bicarbonates upon the interaction of CO with the pure alumina support. In co-adsorption experiments CO competes for adsorption sites with the linearly adsorbed CO2 on the 773 K-annealed γ-Al2O3 surface; but it does not result in the desorption of CO2, rather in the increase of weakly-held carbonate production. After the removal of adsorbed CO, CO2 moves back to its original adsorption sites, i.e., Lewis acidic Al3+ centers. The exposure of a CO2-saturated γ-Al2O3 to H2O did not affect any of the adsorbed surface species. The findings of this study will be used to rationalize the results of our ongoing in situ and in operando studies on the reduction of CO2 on supported Pd and Ru catalysts. Acknowledgements: We gratefully acknowledge the US Department of Energy Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for the support of this work. The synthesis and catalyst pre-treatment portion of the work described in this manuscript was supported by a Laboratory Directed Research and Development (LDRD) project at the Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute. J.H.K. also acknowledges the support of this work by the 2013 Research Fund of UNIST (Ulsan National Institute of Science and Technology, Ulsan, Korea).« less

Surface and interlayer base-characters in lepidocrocite titanate: The adsorption and intercalation of fatty acid

NASA Astrophysics Data System (ADS)

Maluangnont, Tosapol; Arsa, Pornanan; Limsakul, Kanokporn; Juntarachairot, Songsit; Sangsan, Saithong; Gotoh, Kazuma; Sooknoi, Tawan

2016-06-01

While layered double hydroxides (LDHs) with positively-charged sheets are well known as basic materials, layered metal oxides having negatively-charged sheets are not generally recognized so. In this article, the surface and interlayer base-characters of O2- sites in layered metal oxides have been demonstrated, taking lepidocrocite titanate K0.8Zn0.4Ti1.6O4 as an example. The low basicity (0.04 mmol CO2/g) and low desorption temperature (50-300 °C) shown by CO2- TPD suggests that O2- sites at the external surfaces is weakly basic, while those at the interlayer space are mostly inaccessible to CO2. The liquid-phase adsorption study, however, revealed the uptake as much as 37% by mass of the bulky palmitic acid (C16 acid). The accompanying expansion of the interlayer space by ~0.1 nm was detected by PXRD and TEM. In an opposite manner to the external surfaces, the interlayer O2- sites can deprotonate palmitic acid, forming the salt (i.e., potassium palmitate) occluded between the sheets. Two types of basic sites are proposed based on ultrafast 1H MAS NMR and FTIR results. The interlayer basic sites in lepidocrocite titanate leads to an application of this material as a selective and stable two-dimensional (2D) basic catalyst, as demonstrated by the ketonization of palmitic acid into palmitone (C31 ketone). Tuning of the catalytic activity by varying the type of metal (Zn, Mg, and Li) substituting at TiIV sites was also illustrated.

Efficient Gas-Sensing for Formaldehyde with 3D Hierarchical Co3O4 Derived from Co5-Based MOF Microcrystals.

PubMed

Zhou, Wei; Wu, Ya-Pan; Zhao, Jun; Dong, Wen-Wen; Qiao, Xiu-Qing; Hou, Dong-Fang; Bu, Xianhui; Li, Dong-Sheng

2017-11-20

Detecting formaldehyde at low operating temperature and maintaining long-term stability are of great significance. In this work, a hierarchical Co 3 O 4 nanostructure has been fabricated by calcining Co 5 -based metal-organic framework (MOF) microcrystals. Co 3 O 4 -350 particles were used for efficient gas-sensing for the detecting of formaldehyde vapor at lower working temperature (170 °C), low detection limit of 10 ppm, and long-term stability (30 days), which not only is the optimal value among all reported pure Co 3 O 4 sensing materials for the detection of formaldehyde but also is superior to that of majority of Co 3 O 4 -based composites. Such extraordinarily efficient properties might be resulted from hierarchically structures, larger surface area and unique pore structure. This strategy is further confirmed that MOFs, especially Co-clusters MOFs, could be used as precursor to synthesize 3D nanostructure metal oxide materials with high-performance, which possess high porosity and more active sites and shorter ionic diffusion lengths.

Effects of the PPy layer thickness on Co-PPy composite films

NASA Astrophysics Data System (ADS)

Haciismailoglu, Murside

2015-11-01

Co-PPy composite films were electrodeposited on ITO substrate from two different solutions potentiostatically. Firstly, the PPy layers with the thicknesses changing from 20 to 5000 nm were produced on ITO. Then Co was electrodeposited on these PPy/ITO substrates with a charge density of 1000 mC cm-2. The electrochemical properties were investigated by the current density-time transients and the variation of the elapsed time for the Co deposition depending on the PPy layer thickness. X-ray photoelectron (XPS) spectra indicated the presence of both Co metal and its oxides on the surface. The weak reflections of the Co3O4, CoO and hcp Co were detected by the X-ray diffraction (XRD) technique. According to scanning electron microscopy (SEM) images, the thickness of the PPy layer strongly affects the Co nucleation. The composite films with the PPy layer thinner than 200 nm and thicker than 2000 nm have an isotropic magnetic behavior due to the symmetrical crystal field. The composite films with the PPy layer thicknesses between 200 and 2000 nm have an anisotropic magnetic behavior attributable to the deterioration of this symmetrical crystal field by the PPy bubbles on the surface. All films are hard magnetic material, since the coercivities are larger than 125 Oe.

The Effect of CO2 Pressure on Chromia Scale Microstructure at 750°C

NASA Astrophysics Data System (ADS)

Pint, B. A.; Unocic, K. A.

2018-06-01

To understand and model performance in supercritical CO2 (sCO2) for high-efficiency, concentrating solar power (CSP) and fossil energy power cycles, reaction rates are compared at 750°C in 0.1 MPa CO2 and 30 MPa sCO2 as well as laboratory air as a baseline on structural materials such as Ni-based alloy 625. Due to the thin reaction products formed even after 5000 h, scanning transmission electron microscopy was used to study the Cr-rich surface oxide scale. The scales formed in CO2 and sCO2 had a much finer grain size with more voids observed in CO2. However, the observations on alloy 625 were complicated by Mo and Nb-rich precipitates in the adjacent substrate and Al internal oxidation. To simplify the system, a binary Ni-22Cr alloy was exposed for 1000 h in similar environments. After exposure in sCO2, there was an indication of carbon segregation detected on the Cr2O3 grain boundaries. After exposure in air, metallic Ni precipitates were observed in the scale that were not observed in the scale formed on alloy 625. The scale formed in air on a second Ni-22Cr model alloy with Mn and Si additions did not contain Ni precipitates, suggesting caution when drawing conclusions from model alloys.

Salivary protein adsorption and Streptococccus gordonii adhesion to dental material surfaces.

PubMed

Schweikl, Helmut; Hiller, Karl-Anton; Carl, Ulrich; Schweiger, Rainer; Eidt, Andreas; Ruhl, Stefan; Müller, Rainer; Schmalz, Gottfried

2013-10-01

The initial adhesion of microorganisms to clinically used dental biomaterials is influenced by physico-chemical parameters like hydrophobicity and pre-adsorption of salivary proteins. Here, polymethyl methacrylate (PMMA), polyethylene (PE), polytetrafluoroethylene (PTFE), silicone (Mucopren soft), silorane-based (Filtek Silorane) and methacrylate-based (Tetric EvoCeram) dental composites, a conventional glassionomer cement as well as cobalt-chromium-molybdenum (Co28Cr6Mo) and titanium (Ti6Al4V) were tested for adsorption of salivary proteins and adhesion of Streptococcus gordonii DL1. Wettability of material surfaces precoated with salivary proteins or left in phosphate-buffered saline was determined by the measurement of water contact angles. Amounts of adsorbed proteins were determined directly on material surfaces after biotinylation of amino groups and detection by horseradish peroxidase-conjugated avidin-D. The same technique was used to analyze for the binding of biotinylated bacteria to material surfaces. The highest amount of proteins (0.18μg/cm(2)) adsorbed to hydrophobic PTFE samples, and the lowest amount (0.025μg/cm(2)) was detected on silicone. The highest number of S. gordonii (3.2×10(4)CFU/mm(2)) adhered to the hydrophilic glassionomer cement surface coated with salivary proteins, and the lowest number (4×10(3)CFU/mm(2)) was found on the hydrophobic silorane-based composite. Hydrophobicity of pure material surfaces and the number of attached microorganisms were weakly negatively correlated. No such correlation between hydrophobicity and the number of bacteria was detected when surfaces were coated with salivary proteins. Functional groups added by the adsorption of specific salivary proteins to material surfaces are more relevant for initial bacterial adhesion than hydrophobicity as a physical property. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Precursory diffuse CO2 emission signature of the 2011 El Hierro submarine eruption, Canary Islands

NASA Astrophysics Data System (ADS)

Pérez, N. M.; Padilla, G. D.; Padrón, E.; Hernández, P. A.; Melián, G. V.; Barrancos, J.; Dionis, S.; Rodríguez, F.; Nolasco, D.; Calvo, D.; Hernández, I.; Peraza, M. D.

2012-04-01

El Hierro is the youngest and southernmost island of the Canarian archipelago and represents the summit of a volcanic shield elevating from the surrounding seafloor at depth of 4000 m to up to 1501 m above sea level. The island is believed to be near the present hotspot location in the Canaries with the oldest subaerial rocks dated at 1.12 Ma. The subaerial parts of the El Hierro rift zones (NE, NW and S Ridges) are characterized by tightly aligned dyke complexes with clusters of cinder cones as their surface expressions. Since 16 July, an anomalous seismicity at El Hierro Island was recorded by IGN seismic network. Volcanic tremor started at 05:15 on 10 October, followed on the afternoon of 12 October by a green discolouration of seawater, strong bubbling and degassing, and abundant bombs on a decimetre scale found floating on the ocean surface offshore, southwest of La Restinga village, indicating the occurrence of a submarine volcanic eruption at approximately 2 km far the coast line of La Restinga. Further episodes have occurred during November, December 2011 and January 2012, with turbulent water, foam rings, and volcanic material again reaching the sea surface. In order to improve the volcanic surveillance program of El Hierro Island and to provide a multidisciplinary approach, a continuous geochemical station to measure CO2 efflux was installed on September 2003 in Llanos de Guillen, the interception center of the three volcanic-rift zones of the island, with the aim of detecting changes in the diffuse emission of CO2 related to the seismic or volcanic activity. The station measures on an hourly basis the CO2 and H2S efflux, the CO2 and H2S air concentrations, the soil water content and temperature and the atmospheric parameters: wind speed and direction, air temperature and humidity and barometric pressure. The meteorological parameters together with the air CO2 concentration are measured 1 m above the ground and the soil water content and soil temperature are measured 40-cm deep, and recorded contemporaneously with CO2 efflux. Although time series of CO2 efflux showed background (4-5 g m-2 d-1) values before the July 16, when the seismic unrest started, and still August 30, some significant increases up to 10 g m-2 d-1 was measured prior the occurrence of peaks on the seismic energy release. Since the end of August, coinciding with a migration of the hypocenters of the seismic activity toward the south part of the island, the CO2 efflux time series started a relatively constant increase during 1 month, reaching a maximum of 19 g m-2 d-1 one week before the occurrence of the submarine volcanic eruption. Since October 5 till present, including the whole eruptive period, the CO2 efflux time series have shown a general decrease trend but with some significant emission peaks prior the occurrence of important seismic energy release episodes. This station has revealed as an important observation point to evaluate the volcanic activity of El Hierro Island since diffuse degassing of carbon dioxide seems to be associated with fluid pressure fluctuations in the volcanic system. These results demonstrated the potential of applying continuous monitoring of soil CO2 efflux to improve and optimize the detection of early warning signals of future volcanic unrest episodes at El Hierro.

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

Structural, electronic and optical properties of CO adsorbed on the defective anatase TiO2 (101) surface; a DFT study

NASA Astrophysics Data System (ADS)

Rafique, Muhammad; Shuai, Yong; Hassan, Muhammad

2017-08-01

This paper illustrates the study of stable structural, electronic and optical properties of carbon mono oxide (CO) molecule adsorbed on pure anatase TiO2 (101) surface and CO molecule adsorbed on defective anatase TiO2 (101) surface containing oxygen (O) atom subsurface vacancy using first-principles study calculations based on density functional theory (DFT) method. A foreign molecule CO was added in the interstitial space of anatase TiO2 (101) surface. It was observed that, adsorption of CO molecule is not favorable on pure anatase TiO2 (101) surface, however adsorption process is improved when subsurface contains O atom vacancy defect. In case of anatase TiO2 (101) surface containing subsurface vacancy, adsorption process is exothermic, resulting in stable structures. The adsorption energies calculated for CO molecules adsorbed at O2c site, at defect site and at Ti5c site of anatase surface containing subsurface O vacancy are 0.16 eV (at O2c), 0.32 eV (at defect site) and 0.43 eV (at Ti5c) site. DOS and PDOS plots are calculated for all the structures. Results indicated that CO molecule adsorption introduces surface states at the Fermi energy level (EF) as shown in partial density of states (PDOS) plots. The dielectric matrix and absorption coefficient (α) for defective anatase TiO2 (101) surface, CO adsorbed at O2c site, at defect site and at Ti5C site of anatase TiO2 (101) surface containing O atom subsurface vacancy has been calculated within the random phase approximation (RPA) using VASP (Vienna ab-initio simulation package) code. It was observed that upon CO adsorption at defective anatase surface, real and imaginary dielectric function peaks were shifted towards lower energy level and a small absorption peak was observed at 1.1 eV energy level which is not present in case of defective anatase (101) surface. CO adsorption produces a red shift in the absorption spectrum of anatase TiO2 (101) surface containing subsurface O atom vacancy.

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.

Blind Geothermal System Exploration in Active Volcanic Environments; Multi-phase Geophysical and Geochemical Surveys in Overt and Subtle Volcanic Systems, Hawai’i and Maui

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

Fercho, Steven; Owens, Lara; Walsh, Patrick

2015-08-01

Suites of new geophysical and geochemical exploration surveys were conducted to provide evidence for geothermal resource at the Haleakala Southwest Rift Zone (HSWRZ) on Maui Island, Hawai’i. Ground-based gravity (~400 stations) coupled with heli-bourne magnetics (~1500 line kilometers) define both deep and shallow fractures/faults, while also delineating potentially widespread subsurface hydrothermal alteration on the lower flanks (below approximately 1800 feet a.s.l.). Multi-level, upward continuation calculations and 2-D gravity and magnetic modeling provide information on source depths, but lack of lithologic information leaves ambiguity in the estimates. Additionally, several well-defined gravity lows (possibly vent zones) lie coincident with magnetic highs suggestingmore » the presence of dike intrusions at depth which may represent a potentially young source of heat. Soil CO2 fluxes were measured along transects across geophysically-defined faults and fractures as well as young cinder cones along the HSWRZ. This survey generally did not detect CO2 levels above background, with the exception of a weak anomalous flux signal over one young cinder cone. The general lack of observed CO2 flux signals on the HSWRZ is likely due to a combination of lower magmatic CO2 fluxes and relatively high biogenic surface CO2 fluxes which mix with the magmatic signal. Similar surveys at the Puna geothermal field on the Kilauea Lower East Rift Zone (KLERZ) also showed a lack of surface CO2 flux signals, however aqueous geochemistry indicated contribution of magmatic CO2 and He to shallow groundwater here. As magma has been intercepted in geothermal drilling at the Puna field, the lack of measured surface CO2 flux indicative of upflow of magmatic fluids here is likely due to effective “scrubbing” by high groundwater and a mature hydrothermal system. Dissolved inorganic carbon (DIC) concentrations, δ13C compositions and 3He/4He values were sampled at Maui from several shallow groundwater samples indicating only minor additions of magmatic CO2 and He to the groundwater system, although much less than observed near Puna. The much reduced DIC and He abundances at Maui, along with a lack of hotsprings and hydrothermal alteration, as observed near Puna, does not strongly support a deeper hydrothermal system within the HSWRZ.« less

Nocturnal accumulation of CO2 underneath a tropical forest canopy along a topographical gradient.

PubMed

de Araújo, Alessandro C; Kruijt, Bart; Nobre, Antonio D; Dolman, Albertus J; Waterloo, Maarten J; Moors, Eddy J; de Souza, Juliana S

2008-09-01

Flux measurements of carbon dioxide and water vapor above tropical rain forests are often difficult to interpret because the terrain is usually complex. This complexity induces heterogeneity in the surface but also affects lateral movement of carbon dioxide (CO2) not readily detected by the eddy covariance systems. This study describes such variability using measurements of CO2 along vertical profiles and along a toposequence in a tropical rain forest near Manaus, Brazil. Seasonal and diurnal variation was recorded, with atmospheric CO2 concentration maxima around dawn, generally higher CO2 build-up in the dry season and stronger daytime CO2 drawdown in the wet season. This variation was reflected all along the toposequence, but the slope and valley bottom accumulated clearly more CO2 than the plateaus, depending on atmospheric stability. Particularly during stable nights, accumulation was along lines of equal altitude, suggesting that large amounts of CO2 are stored in the valleys of the landscape. Flushing of this store only occurs during mid-morning, when stored CO2 may well be partly transported back to the plateaus. It is clear that, for proper interpretation of tower fluxes in such complex and actively respiring terrain, the horizontal variability of storage needs to be taken into account not only during the night but also during the mornings.

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 .

A Chemoreceptor That Detects Molecular Carbon Dioxide*

PubMed Central

Smith, Ewan St. John; Martinez-Velazquez, Luis; Ringstad, Niels

2013-01-01

Animals from diverse phyla possess neurons that are activated by the product of aerobic respiration, CO2. It has long been thought that such neurons primarily detect the CO2 metabolites protons and bicarbonate. We have determined the chemical tuning of isolated CO2 chemosensory BAG neurons of the nematode Caenorhabditis elegans. We show that BAG neurons are principally tuned to detect molecular CO2, although they can be activated by acid stimuli. One component of the BAG transduction pathway, the receptor-type guanylate cyclase GCY-9, suffices to confer cellular sensitivity to both molecular CO2 and acid, indicating that it is a bifunctional chemoreceptor. We speculate that in other animals, receptors similarly capable of detecting molecular CO2 might mediate effects of CO2 on neural circuits and behavior. PMID:24240097

Simulating CO2 Leakage and Seepage From Geologic Carbon Sequestration Sites: Implications for Near-Surface Monitoring

NASA Astrophysics Data System (ADS)

Oldenburg, C. M.; Lewicki, J. L.; Zhang, Y.

2003-12-01

The injection of CO2 into deep geologic formations for the purpose of carbon sequestration entails risk that CO2 will leak upward from the target formation and ultimately seep out of the ground surface. We have developed a coupled subsurface and atmospheric surface layer modeling capability based on TOUGH2 to simulate CO2 leakage and seepage. Simulation results for representative subsurface and surface layer conditions are used to specify the requirements of potential near-surface monitoring strategies relevant to both health, safety, and environmental risk assessment as well as sequestration verification. The coupled model makes use of the standard multicomponent and multiphase framework of TOUGH2 and extends the model domain to include an atmospheric surface layer. In the atmospheric surface layer, we assume a logarithmic velocity profile for the time-averaged wind and make use of Pasquill-Gifford and Smagorinski dispersion coefficients to model surface layer dispersion. Results for the unsaturated zone and surface layer show that the vadose zone pore space can become filled with pure CO2 even for small leakage fluxes, but that CO2 concentrations above the ground surface are very low due to the strong effects of dispersion caused by surface winds. Ecological processes such as plant photosynthesis and root respiration, as well as biodegradation in soils, strongly affect near-surface CO2 concentrations and fluxes. The challenge for geologic carbon sequestration verification is to discern the leakage and seepage signal from the ecological signal. Our simulations point to the importance of subsurface monitoring and the need for geochemical (e.g., isotopic) analyses to distinguish leaking injected fossil CO2 from natural ecological CO2. This work was supported by the Office of Science, U.S. Department of Energy under contract No. DE-AC03-76SF00098.

Soil degassing at the Los Humeros geothermal field (Mexico)

NASA Astrophysics Data System (ADS)

Peiffer, Loïc; Carrasco-Núñez, Gerardo; Mazot, Agnès; Villanueva-Estrada, Ruth Esther; Inguaggiato, Claudio; Bernard Romero, Rubén; Rocha Miller, Roberto; Hernández Rojas, Javier

2018-05-01

The Los Humeros geothermal field is the third most important producer of geothermal electricity (70 MW) in Mexico. Geothermal fluids are hosted in fractured andesitic lavas and mostly consist of high enthalpy steam with limited water content (vapor fraction > 0.9). Despite the high reservoir temperature ( 300-400 °C), thermal manifestations at the surface are scarce and locally appear as steaming grounds, weak steam vents and advanced argillic alteration. Geothermal fluid upflow from the reservoir towards the surface is limited by welded ignimbrite deposits that act as a low-permeability barrier. In this study, we present the first measurements of CO2, CH4 and H2S degassing rates from the soil performed at Los Humeros. Flux measurements were complemented with δ13C composition of degassing CO2 and soil temperatures to discuss gas origin and thermal anomalies. We measured high soil degassing rates (up to 7530 g m-2 d-1 CO2, 33 g m-2 d-1 CH4 and 22 g m-2 d-1 H2S) in three localized areas (Humeros North - HN, Humeros South - HS and Xalapazco - XA) as well as high soil temperatures reaching the boiling temperature at the local altitude (90.6 °C). The particular location of these three areas suggests that the steam-dominated reservoir degases to the surface through permeable faults crossing the ignimbritic deposits. The remaining surveyed areas are characterized by weak CO2 fluxes (≤44 g m-2 d-1), non-detectable CH4 and H2S fluxes, and lower soil temperatures (5-21 °C). The compositions in δ13CCO2 from HN-HS-XA areas (δ13CCO2 = -7.94 to -2.73‰) reflect a magmatic source with some possible contribution from the sedimentary basement, as well as fractionation induced by boiling and CO2 dissolution in shallow water bodies. We also discuss the processes causing the spread in CO2/CH4 flux ratios. Finally, we estimate the heat output from the three high degassing areas to a value of 16.4 MWt.

Leaf Area Influence on Surface Layer in a Deciduous Forest. Part 2; Detecting Leaf Area and Surface Resistance During Transition Seasons

NASA Technical Reports Server (NTRS)

Sakai, Ricardo K.; Fitzjarrald, David R.; Moore, Kathleen E.; Sicker, John W.; Munger, Willian J.; Goulden, Michael L.; Wofsy, Steven C.

1996-01-01

Temperate deciduous forest exhibit dramatic seasonal changes in surface exchange properties following on the seasonal changes in leaf area index. The canopy resistance to water vapor transport r(sub c) decreased abruptly at leaf emergence in each year but then also continued to decrease slowly during the remaining growing season due to slowly increasing LAI. Canopy resistance and PAR-albedo (albedo from photosynthetically active radiation) began to increase about one month before leaf fall with the diminishment of CO2 gradient above the canopy as well. At this time evaporation begun to be controlled as if the canopy were leafless.

The Functionality of Surface Hydroxy Groups on the Selectivity and Activity of Carbon Dioxide Reduction over Cuprous Oxide in Aqueous Solutions.

PubMed

Yang, Piaoping; Zhao, Zhi-Jian; Chang, Xiaoxia; Mu, Rentao; Zha, Shenjun; Zhang, Gong; Gong, Jinlong

2018-06-25

Carbon dioxide (CO 2 ) reduction in aqueous solutions is an attractive strategy for carbon capture and utilization. Cuprous oxide (Cu 2 O) is a promising catalyst for CO 2 reduction as it can convert CO 2 into valuable hydrocarbons and suppress the side hydrogen evolution reaction (HER). However, the nature of the active sites in Cu 2 O remains under debate because of the complex surface structure of Cu 2 O under reducing conditions, leading to limited guidance in designing improved Cu 2 O catalysts. This paper describes the functionality of surface-bonded hydroxy groups on partially reduced Cu 2 O(111) for the CO 2 reduction reaction (CO 2 RR) by combined density functional theory (DFT) calculations and experimental studies. We find that the surface hydroxy groups play a crucial role in the CO 2 RR and HER, and a moderate coverage of hydroxy groups is optimal for promotion of the CO 2 RR and suppression of the HER simultaneously. Electronic structure analysis indicates that the charge transfer from hydroxy groups to coordination-unsaturated Cu (Cu CUS ) sites stabilizes surface-adsorbed COOH*, which is a key intermediate during the CO 2 RR. Moreover, the CO 2 RR was evaluated over Cu 2 O octahedral catalysts with {111} facets and different surface coverages of hydroxy groups, which demonstrates that Cu 2 O octahedra with moderate coverage of hydroxy groups can indeed enhance the CO 2 RR and suppress the HER. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monte Carlo Simulation of Callisto's Exosphere

NASA Astrophysics Data System (ADS)

Vorburger, Audrey; Wurz, Peter; Galli, André; Mousis, Olivier; Barabash, Stas; Lammer, Helmut

2014-05-01

Whereas Callisto's surface has been mapped as early as in 1980 by the two Voyager missions, Callisto's tenuous atmosphere, also called an exosphere, was not directly observed until the Galileo mission in 1999. The Galileo Near-Infrared Mapping Spectrometer detected a CO2 signal up to 100 km above the surface [Carlson, Science, 1999]. Radio occultation measurements, also conducted by Galileo, led to the detection of an ionosphere with inferred densities much higher than can be explained by the measured CO2 exosphere, though [Kliore et al., J. Geophys. Res, 2002]. Insight about Callisto's exosphere is expected to be boosted by the Neutral Ion Mass Spectrometer (NIM) of the Particle Environment Package (PEP) on board the planned JUpiter ICy moons Explorer (JUICE) mission, which will conduct the first-ever direct sampling of the exospheres of Europa, Ganymede, and Callisto. To ensure that NIM's mass resolution and mass range will be sufficient for NIM to detect most expected species in Callisto's exosphere, we model said exosphere ab initio. Since Callisto is thought to consist to about equal parts of both icy and rocky components [Showman and Malhotra, Science, 1999], we model particle release from an icy as well as from a mineral surface separately. For the ice component, we investigate two different compositions, for reducing and oxidising conditions, which find analogy in the initial gas phase conditions in the solar nebula [Mousis et al., Planet. Space Sci., submitted]. For the non-ice material, the mineral surface, we investigate surfaces with compositions similar to CI chondrites and L/LL type chondrites, both of which have been suggested to represent Callisto's non-ice material best [Kuskov and Kronrod, Icarus, 2005 and Moore et al., Cambridge University Press, 2004]. For all mentioned materials, we compute density profiles for particles released by either surface sublimation or ion induced sputtering up to an altitude of 100'000 km. Our results show that close to the surface the sublimated particles dominate the day-side exosphere, however, their density profiles (with the exception of H and H2) decrease much more rapidly with altitude than those of the sputtered particles, thus, the latter particles start to dominate at altitudes above ~1000 km. Since the JUICE flybys are as low as 200 km above Callisto's surface, NIM is expected to register both the sublimated as well as sputtered particle populations. Our simulations show that NIM's sensitivity is high enough to allow the detection of particles sputtered from the icy as well as the mineral surfaces, and to distinguish between the different composition models.

Screen-Printed Carbon Electrodes Modified with Cobalt Phthalocyanine for Selective Sulfur Detection in Cosmetic Products

PubMed Central

Chen, Pei-Yen; Luo, Chin-Hsiang; Chen, Mei-Chin; Tsai, Feng-Jie; Chang, Nai-Fang; Shih, Ying

2011-01-01

Cobalt phthalocyanine (CoPc) films were deposited on the surface of a screen-printed carbon electrode using a simple drop coating method. The cyclic voltammogram of the resulting CoPc modified screen-printed electrode (CoPc/SPE) prepared under optimum conditions shows a well-behaved redox couple due to the (CoI/CoII) system. The CoPc/SPE surface demonstrates excellent electrochemical activity towards the oxidation of sulfur in a 0.01 mol·L−1 NaOH. A linear calibration curve with the detection limit (DL, S/N = 3) of 0.325 mg·L−1 was achieved by CoPc/SPE coupled with flow injection analysis of the sulfur concentration ranging from 4 to 1120 mg·L−1. The precision of the system response was evaluated (3.60% and 3.52% RSD for 12 repeated injections), in the range of 64 and 480 mg·L−1 sulfur. The applicability of the method was successfully demonstrated in a real sample analysis of sulfur in anti-acne creams, and good recovery was obtained. The CoPc/SPE displayed several advantages in sulfur determination including easy fabrication, high stability, and low cost. PMID:21747708

Combination of first-principles molecular dynamics and XANES simulations for LiCoO2-electrolyte interfacial reactions in a lithium-ion battery

NASA Astrophysics Data System (ADS)

Tamura, Tomoyuki; Kohyama, Masanori; Ogata, Shuji

2017-07-01

We performed a first-principles molecular dynamics (FPMD) simulation of the interfacial reactions between a LiCoO2 electrode and a liquid ethylene carbonate (EC) electrolyte. For configurations during the FPMD simulation, we also performed first-principles Co K-edge x-ray absorption near-edge structure (XANES) simulations, which can properly reproduce the bulk and surface spectra of LiCoO2. We observed strong absorption of an EC molecule on the LiCoO2 {110} surface, involving ring opening of the molecule, bond formation between oxygen atoms in the molecule and surface Co ions, and emission of one surface Li ion, while all the surface Co ions remain Co3 +. The surface Co ions having the bond with an oxygen atom in the molecule showed remarkable changes in simulated K-edge spectra which are similar to those of the in situ observation under electrolyte soaking [D. Takamatsu et al., Angew. Chem., Int. Ed. 51, 11597 (2012), 10.1002/anie.201203910]. Thus, the local environmental changes of surface Co ions due to the reactions with an EC molecule can explain the experimental spectrum changes.

Comparison of Surface and Column Variations of CO2 Over Urban Areas for Future Active Remote CO2 Sensors

NASA Technical Reports Server (NTRS)

Choi, Yonghoon; Yang, Melissa; Kooi, Susan; Browell, Edward

2015-01-01

High resolution in-situ CO2 measurements were recorded onboard the NASA P-3B during the DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) Field Campaign, to investigate the ability of space-based observations to accurately assess near surface conditions related to air quality. This campaign includes, Washington DC/Baltimore, MD (July 2011), San Joaquin Valley, CA (January - February 2013), Houston, TX (September 2013), and Denver, CO (July-August 2014). Each of these campaigns consisted of missed approaches and approximately two hundred vertical soundings of CO2 within the lower troposphere (surface to about 5 km). In this study, surface (0 - 1 km) and column-averaged (0 - 3.5 km) CO2 mixing ratio values from the vertical soundings in the four geographically different urban areas are used to investigate the temporal and spatial variability of CO2 within the different urban atmospheric emission environments. Tracers such as CO, CH2O, NOx, and NMHCs are used to identify the source of CO2 variations in the urban sites. Additionally, we apply nominal CO2 column weighting functions for potential future active remote CO2 sensors operating in the 1.57-microns and 2.05-microns measurement regions to convert the in situ CO2 vertical mixing ratio profiles to variations in CO2 column optical depths, which is what the active remote sensors actually measure. Using statistics calculated from the optical depths at each urban site measured during the DISCOVER-AQ field campaign and for each nominal weighting function, we investigate the natural variability of CO2 columns in the lower troposphere; relate the CO2 column variability to the urban surface emissions; and show the measurement requirements for the future ASCENDS (Active Sensing of CO2 Emissions over Nights, Days, and Seasons) in the continental U.S. urban areas.

Rapid identification of macro nutrients in pharmaceutical medicine using laser-induced plasma spectroscopy

NASA Astrophysics Data System (ADS)

Khumaeni, Ali; Sugito, Heri; Yoyo Wardaya, Asep; Setia Budi, Wahyu

2018-05-01

Identification of macro nutrients in medicine is really necessary for healthy purpose. In this study, identification of macro elements in pharmaceutical products was carried out by laser-induced plasma spectroscopy (LIPS). A comparative study was made by employing different types of laser, namely an Nd:YAG laser and a pulse TEA CO2 laser. Experimentally, the laser beam was directed and focused by a convex lens on a mineral supplement tablet. A luminous plasma was induced on the tablet’s surface. Sharp and high-intensity emission spectra of macro elements including Ca and Mg were detected both in LIBS using Nd:YAG and pulse CO2 lasers. However, the intensities of Ca and Mg spectra are much higher for the LIBS using CO2 laser. Based on the analysis, the plasma temperature plays important role in the spectra. Namely, the plasma induced by a TEA CO2 laser is much higher than that of Nd:YAG laser; the plasma temperature for the case of TEA CO2 laser and Nd:YAG laser were 6400 K and 4500 K, respectively.

Detecting fossil fuel emissions patterns from subcontinental regions using North American in situ CO2 measurements.

PubMed

Shiga, Yoichi P; Michalak, Anna M; Gourdji, Sharon M; Mueller, Kim L; Yadav, Vineet

2014-06-28

The ability to monitor fossil fuel carbon dioxide (FFCO 2 ) emissions from subcontinental regions using atmospheric CO 2 observations remains an important but unrealized goal. Here we explore a necessary but not sufficient component of this goal, namely, the basic question of the detectability of FFCO 2 emissions from subcontinental regions. Detectability is evaluated by examining the degree to which FFCO 2 emissions patterns from specific regions are needed to explain the variability observed in high-frequency atmospheric CO 2 observations. Analyses using a CO 2 monitoring network of 35 continuous measurement towers over North America show that FFCO 2 emissions are difficult to detect during nonwinter months. We find that the compounding effects of the seasonality of atmospheric transport patterns and the biospheric CO 2 flux signal dramatically hamper the detectability of FFCO 2 emissions. Results from several synthetic data case studies highlight the need for advancements in data coverage and transport model accuracy if the goal of atmospheric measurement-based FFCO 2 emissions detection and estimation is to be achieved beyond urban scales. Poor detectability of fossil fuel CO 2 emissions from subcontinental regionsDetectability assessed via attribution of emissions patterns in atmospheric dataLoss in detectability due to transport modeling errors and biospheric signal.

Multi-shelled ZnCo2O4 yolk-shell spheres for high-performance acetone gas sensor

NASA Astrophysics Data System (ADS)

Xiong, Ya; Zhu, Zongye; Ding, Degong; Lu, Wenbo; Xue, Qingzhong

2018-06-01

In the present study, multi-shelled ZnCo2O4 yolk-shell spheres have been successfully prepared by using carbonaceous microspheres as templates. It is found that the multi-shelled ZnCo2O4 yolk-shell spheres based sensor shows optimal sensing performances (response value of 38.2, response/recovery time of 19 s/71 s) toward 500 ppm acetone at 200 °C. In addition, this sensor exhibits a low detection limit of 0.5 ppm acetone (response value of 1.36) and a good selectivity toward hydrogen, methane, ethanol, ammonia and carbon dioxide. Furthermore, it is demonstrated that acetone gas response of multi-shelled ZnCo2O4 yolk-shell spheres is significantly better than that of ZnCo2O4 nanotubes and ZnCo2O4 nanosheets. High acetone response of the multi-shelled ZnCo2O4 yolk-shell spheres is attributed to the enhanced gas accessibility of the multi-shell morphology caused by the small crystalline size and high specific surface area while the short response/recovery time is mainly related to the rapid gas diffusion determined by the highly porous structure. Our work puts forward an exciting opportunity in designing various yolk-shelled structures for multipurpose applications.

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.

Design of a perfluorocarbon tracer based monitoring network to support monitoring verification and accounting of sequestered CO2

NASA Astrophysics Data System (ADS)

Watson, T.; Sullivan, T.

2013-05-01

The levels of CO2 in the atmosphere have been growing since the beginning of the industrial revolution. The current level is 391 ppm. If there are no efforts to mitigate CO2 emissions, the levels will rise to 750 ppm by 2100. Geologic carbon sequestration is one strategy that may be used to begin to reduce emissions. Sequestration will not be effective unless reservoir leak rates are significantly less than 1%. There must be rigorous monitoring protocols in place to ensure sequestration projects meet regulatory and environmental goals. Monitoring for CO2 leakage directly is difficult because of the large background levels and variability of CO2 in the atmosphere. Using tracers to tag the sequestered CO2 can mitigate some of the difficulties of direct measurement but a tracer monitoring network and the levels of tagging need to be carefully designed. Simple diffusion and dispersion models are used to predict the surface and atmospheric concentrations that would be seen by a network monitoring a sequestration site. Levels of tracer necessary to detect leaks from 0.01 to 1% are presented and suggestions for effective monitoring and protection of global tracer utility are presented.

Spatial and temporal variability of seawater pCO2 within the Canadian Arctic Archipelago and Baffin Bay during the summer and autumn 2011

NASA Astrophysics Data System (ADS)

Geilfus, N.-X.; Pind, M. L.; Else, B. G. T.; Galley, R. J.; Miller, L. A.; Thomas, H.; Gosselin, M.; Rysgaard, S.; Wang, F.; Papakyriakou, T. N.

2018-03-01

The partial pressure of CO2 in surface water (pCO2sw) measured within the Canadian Arctic Archipelago (CAA) and Baffin Bay was highly variable with values ranging from strongly undersaturated (118 μatm) to slightly supersaturated (419 μatm) with respect to the atmospheric levels ( 386 μatm) during summer and autumn 2011. During summer, melting sea ice contributed to cold and fresh surface water and enhanced the ice-edge bloom, resulting in strong pCO2sw undersaturation. Coronation Gulf was the only area with supersaturated pCO2sw, likely due to warm CO2-enriched freshwater input from the Coppermine River. During autumn, the entire CAA (including Coronation Gulf) was undersaturated, despite generally increasing pCO2sw. Coronation Gulf was the one place where pCO2sw decreased, likely due to seasonal reduction in discharge from the Coppermine River and the decreasing sea surface temperature. The seasonal summer-to-autumn increase in pCO2sw across the archipelago is attributed in part to the continuous uptake of atmospheric CO2 through both summer and autumn and to the seasonal deepening of the surface mixed layer, bringing CO2-rich waters to the surface. These observations demonstrate how freshwater from sea ice melt and rivers affect pCO2sw differently. The general pCO2sw undersaturation during summer-autumn 2011 throughout the CAA and Baffin Bay give an estimated net oceanic sink for atmospheric CO2 over the study period of 11.4 mmol CO2 m-2 d-1, assuming no sea-air CO2 flux exchange across the sea-ice covered areas.

Coupling molecular catalysts with nanostructured surfaces for efficient solar fuel production

NASA Astrophysics Data System (ADS)

Jin, Tong

Solar fuel generation via carbon dioxide (CO2) reduction is a promising approach to meet the increasing global demand for energy and to minimize the impact of energy consumption on climate change. However, CO2 is thermodynamically stable; its activation often requires the use of appropriate catalysts. In particular, molecular catalysts with well-defined structures and tunability have shown excellent activity in photochemical CO2 reduction. These homogenous catalysts, however, suffer from poor stability under photochemical conditions and difficulty in recycling from the reaction media. Heterogenized molecular catalysts, particularly those prepared by coupling molecular catalysts with solid-state surfaces, have attracted more attention in recent years as potential solutions to address the issues associated with molecular catalysts. In this work, solar CO2 reduction is investigated using systems coupling molecular catalysts with robust nanostructured surfaces. In Chapter 2, heterogenization of macrocyclic cobalt(III) and nickel (II) complexes on mesoporous silica surface was achieved by different methods. Direct ligand derivatization significantly lowered the catalytic activity of Co(III) complex, while grafting the Co(III) complex onto silica surface through Si-O-Co linkage resulted in hybrid catalysts with excellent activity in CO2 reduction in the presence of p-terphenyl as a molecular photosensitizer. An interesting loading effect was observed, in which the optimal activity was achieved at a medium Co(III) surface density. Heterogenization of the Ni(II) complex on silica surface has also been implemented, the poor photocatalytic activity of the hybrid catalyst can be attributed to the intrinsic nature of the homogeneous analogue. This study highlighted the importance of appropriate linking strategies in preparing functional heterogenized molecular catalysts. Coupling molecular complexes with light-harvesting surfaces could avoid the use of expensive molecular photosensitizers. In Chapter 3, effective coupling of the macrocyclic Co(III) complex with titanium dioxide (TiO¬2) nanoparticles was achieved by two deposition methods. The synthesized hybrid photocatalysts were thoroughly characterized with a variety of techniques. Upon UV light irradiation, photoexcited electrons in TiO2 nanoparticles were transferred to the surface Co(III) catalyst for CO2 reduction. Production of carbon monoxide (CO) from CO2 was confirmed by isotope labeling combined with infrared spectroscopy. Deposition of the Co(III) catalyst through Ti-O-Co linkages was essential for the photo-induced electron transfer and CO2-reduction activity using the hybrid photocatalysts. In Chapter 4, molecular Re(I) and Co(II) catalysts were coupled with silicon-based photoelectrodes, including a silicon nanowire (SiNW) photoelectrode, to achieve photoelectrochemical CO2 reduction. Photovoltages between 300-600 mV were obtained using the molecular catalysts on the silicon photoelectrodes. SiNWs exhibited enhanced properties, including significantly higher photovoltages than a planar silicon photoelectrode, the ability to protect one of the molecular catalysts from photo-induced decomposition, and excellent selectivity towards CO production in CO2 reduction. Recent theoretical and experimental work have demonstrated low-energy, binuclear pathways for CO2-to-CO conversion using several molecular catalysts. In such binuclear pathways, two metal centers work cooperatively to achieve two-electron CO2 reduction. Chapter 5 describes our effort to promote the binuclear pathway by grafting the molecular Co(III) catalyst onto silica surfaces. Different linking strategies were attempted to achieve this goal by planting the surface Co(III) sites in close proximity.

The Role of H2O in the Carbonation of Forsterite in Supercritical CO2

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

Kwak, Ja Hun; Hu, Jian Z.; Turcu, Romulus VF

2011-07-01

The water concentration dependence of forsterite carbonation in supercritical CO2 (scCO2) at 80°C and 76 bars was investigated by a combination of NMR, XRD, TEM and XPS. Reaction products were not detected using scCO2 alone without added H2O. When trace amounts of water were included, limited reaction was observed. Below saturation, reaction products were a mixture of partially hydrated/hydroxylated magnesium carbonates and hydroxylated silica species that were mainly in an amorphous state, forming a non-resolved layer on the forsterite surface. At water concentrations above saturation, where forsterite was in contact with both a CO2-saturated aqueous fluid and a water-saturated scCO2more » fluid, solid reaction products were magnesite (MgCO3) and an amorphous polymerized SiO2 dominated by Q4, and to a lesser extent by Q3 silica coordination. Formation of these phases implies H2O initially bound in precursor hydrated/hydroxylated reaction products was liberated, inducing further reaction. Hence, for a given fluid/mineral ratio there is a water threshold above which a significant portion of the water serves in a catalytic role where more extensive carbonation reaction occurs. Defining the role of water, even in low water content environments, is therefore critical to determining the long term impact of CO2 reactivity in the subsurface.« less

New stable isotope results for reservoir and above zone monitoring in CCS from the Ketzin pilot site, Germany

NASA Astrophysics Data System (ADS)

Nowak, Martin; van Geldern, Robert; Myrttinen, Anssi; Veith, Becker; Zimmer, Martin; Barth, Johannes

2013-04-01

With rising atmospheric greenhouse gas concentrations, CCS technologies are a feasible option to diminish consequences of uncontrolled anthropogenic CO2 emissions and related climate change. However, application of CCS technologies requires appropriate and routine monitoring tools in order to ensure a safe and effective CO2 injection. Stable isotope techniques have proven as a useful geochemical monitoring tool at several CCS pilot projects worldwide. They can provide important information about gas - water - rock interactions, mass balances and CO2 migration in the reservoir and may serve as a tool to detect CO2 leakage in the subsurface and surface. Since the beginning of injection in 2008 at the Ketzin pilot site in Germany, more than 450 samples of fluids and gases have been analysed for their carbon and oxygen isotopic composition. Analytical advancements were achieved by modifying a conventional isotope ratio mass-spectrometer with a He dilution system. This allowed analyses of a larger number of CO2 gas samples from the injection well and observation wells. With this, a high-resolution monitoring program was established over a time period of one year. Results revealed that two isotopical distinct kinds of CO2 are injected at the Ketzin pilot site. The most commonly injected CO2 is so-called 'technical' CO2 with an average carbon isotopic value of about -31 ‰. Sporadically, natural source CO2 with an average δ13C value of -3 ‰ was injected. The injection of natural source CO2 generated a distinct isotope signal at the injection well that can be used as an ideal tracer. CO2 isotope values analysed at the observation wells indicate a highly dispersive migration of the supercritical CO2 that results in mixing of the two kinds of CO2 within the reservoir. Above-reservoir monitoring includes the first overlying aquifer above the cap rock. An observation well within this zone comprises an U-tube sampling device that allows frequent sampling of unaltered brine. The fluids were analysed among others for their carbon isotopic compositions of dissolved inorganic carbon (DIC). δ13CDIC values allowed to assess impacts of the carbonate-based drilling fluid during well development and helped to monitor successive geochemical re-equilibration processes of the brine. Based on the determined δ13C baseline values of the aquifer fluid, first concepts indicate the scale of change of the δ13CDIC values that would be necessary to detect CO2 leakage from the underlying storage reservoir. Recent efforts aim at applications of new laser-based isotope sensors that allow online measurements in the field. These devices are applied for CO2 gas tracer experiments as well as for monitoring of isotope composition of soil gases in the vicinity of the pilot site. This new development will allow much better temporal and spatial resolution of measurements at a lower price. Therefore, stable isotope analyses can become a strong and promising tool for subsurface as well as surface monitoring at future CCS sites.

Raman enhancement by graphene-Ga2O3 2D bilayer film.

PubMed

Zhu, Yun; Yu, Qing-Kai; Ding, Gu-Qiao; Xu, Xu-Guang; Wu, Tian-Ru; Gong, Qian; Yuan, Ning-Yi; Ding, Jian-Ning; Wang, Shu-Min; Xie, Xiao-Ming; Jiang, Mian-Heng

2014-01-28

2D β-Ga2O3 flakes on a continuous 2D graphene film were prepared by a one-step chemical vapor deposition on liquid gallium surface. The composite was characterized by optical microscopy, scanning electron microscopy, Raman spectroscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy (XPS). The experimental results indicate that Ga2O3 flakes grew on the surface of graphene film during the cooling process. In particular, tenfold enhancement of graphene Raman scattering signal was detected on Ga2O3 flakes, and XPS indicates the C-O bonding between graphene and Ga2O3. The mechanism of Raman enhancement was discussed. The 2D Ga2O3-2D graphene structure may possess potential applications.

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

Molecular modeling studies of interfacial reactions in wet supercritical CO2.

NASA Astrophysics Data System (ADS)

Glezakou, V.; McGrail, B. P.; Windisch, C. F.; Schaef, H. T.; Martin, P.

2011-12-01

In the recent years, Carbon Capture and Sequestration (CCS) technologies have gained considerable momentum in a globally organized effort to mitigate greenhouse emissions and adverse climate change. Co-sequestration refers to the capture and geologic sequestration of carbon dioxide and minor contaminants (sulfur compounds, NOx, Hg, etc.) in subsurface formations. Cosequestration offers the potential to make carbon management more economically acceptable to industry relative to sequestration of pure CO2. This may be achieved through significant savings in plant (and retrofit) capital cost, operating cost, and energy savings as well by eliminating the need for one or more individual pollutant capture systems (such as SO2 scrubbers). The latter point is important because co-sequestration may result in a net positive impact to the environment through avoided loss of power generation capacity from parasitic loads and reduced fuel needs. This paper will discuss our research on modeling, imaging and characterization of cosequestration processes and reactivity at a fundamental level. Our work examines the interactions of CO2-rich fluids with metal and mineral surfaces, and how these are affected by the presence of other gas components (e.g. SO2, H2O or NOx) commonly present in the CO2 streams. We have found that reactivity is also affected by the composition of the surface or, less obviously, by the surface exposed, for example, (104) vs (100 )of carbonate minerals. We combine experimental techniques such as XRD and Raman spectroscopy, which can detect and follow reactive processes, with ab initio modeling methods based on density functional theory, to establish a reliable correspondence between theory and experiment with predictive capability. Analysis of our molecular dynamics simulations, reveals structural information and vibrational density of states that can directly compare with XRD measurements and vibrational spectroscopy. While reactivity in CO2-containing aqueous environments has been widely studied, the reverse, i.e. reactivity in water-bearing condensed media, is not true. Our simulations show that mechanistic details in these environments can be drastically different, and they are very important in elucidating molecular transformations relevant to CCS or carbon conversion.

A novel label-free photoelectrochemical sensor based on N,S-GQDs and CdS co-sensitized hierarchical Zn2SnO4 cube for detection of cardiac troponin I.

PubMed

Fan, Dawei; Bao, Chunzhu; Khan, Malik Saddam; Wang, Chuanlei; Zhang, Yong; Liu, Qinze; Zhang, Xian; Wei, Qin

2018-05-30

A novel label-free photoelectrochemical (PEC) sensor based on graphene quantum dots doped with nitrogen and sulfur (N,S-GQDs) and CdS co-sensitized hierarchical Zn 2 SnO 4 cube was fabricated to detect cardiac troponin I (cTnI). The unique hierarchical Zn 2 SnO 4 cube was synthesized successfully by the solvothermal method, which has a large specific surface to load functional materials. N,S-GQDs nanoparticles were assembled to the surface of cubic Zn 2 SnO 4 coated ITO electrode, which efficiently accelerated the electronic transition and improved photo-to-current conversion efficiency. Then, CdS nanoparticles further were modified by in-situ growth method to form Zn 2 SnO 4 /N,S-GQDs/CdS composite with prominent photocurrent, which was 30 times that of the Zn 2 SnO 4 cube alone. In this work, the specific immune recognition between cTnI antigens and cTnI antibodies (anti-cTnI) reduced the intensity of the photoelectric signal. And the intensity decreased linearly with the logarithm of cTnI concentration range from 0.001 ng/mL to 50 ng/mL with a detection limit of 0.3 pg/mL. With high sensitivity, excellent selectivity, good stability and reproducibility, the fabricated PEC sensor showed promising applications in the sensor, clinical diagnosis of myocardial infarction and PEC analysis. Copyright © 2018 Elsevier B.V. All rights reserved.

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2.

PubMed

Favaro, Marco; Xiao, Hai; Cheng, Tao; Goddard, William A; Yano, Junko; Crumlin, Ethan J

2017-06-27

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2

PubMed Central

Favaro, Marco; Yano, Junko; Crumlin, Ethan J.

2017-01-01

A national priority is to convert CO2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO2 in the presence of water as the first step toward CO2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts. PMID:28607092

Volumetric strain in relation to particle displacements for body and surface waves in a general viscoelastic half-space

USGS Publications Warehouse

Borcherdt, R.D.

1988-01-01

Dilatational earth strain, associated with the radiation fields for several hundred local, regional, and teleseismic earthquakes, has been recorded over an extended bandwidth and dynamic range at four borehole sites near the San Andreas fault, CA. The general theory of linear viscoelasticity is applied to account for anelasticity of the near-surface materials and to provide a mathematical basis for interpretation of seismic radiation fields as detected simultaneously by co-located volumetric strain meters and seismometers. The general theory is applied to describe volumetric strain and displacement for general (homogeneous or inhomogeneous) P and S waves in an anelastic whole space. Solutions to the free-surface reflection problems for incident general P and S-I waves are used to evaluate the effect of the free surface on observations from co-located sensors. Corresponding expressions are derived for a Rayleigh-type surface wave on a linear viscoelastic half-space. The theory predicts a number of anelastic wave field characteristics that can be inferred from observation of volumetric strains and displacement fields as detected by co-located sensors that cannot be inferred from either sensor alone. -from Author

Optimization of CO2 Surface Flux using GOSAT Total Column CO2: First Results for 2009-2010

NASA Astrophysics Data System (ADS)

Basu, S.; Houweling, S.

2011-12-01

Constraining surface flux estimates of CO2 using satellite measurements has been one of the long-standing goals of the atmospheric inverse modeling community. We present the first results of inverting GOSAT total column CO2 measurements for obtaining global monthly CO2 flux maps over one year (June 2009 to May 2010). We use the SRON RemoTeC retrieval of CO2 for our inversions. The SRON retrieval has been shown to have no bias when compared to TCCON total column measurements, and latitudinal gradients of the retrieved CO2 are consistent with gradients deduced from the surface flask network [Butz et al, 2011]. This makes this retrieval an ideal candidate for atmospheric inversions, which are highly sensitive to spurious gradients. Our inversion system is analogous to the CarbonTracker (CT) data assimilation system; it is initialized with the prior CO2 fluxes of CT, and uses the same atmospheric transport model, i.e., TM5. The two major differences are (a) we add GOSAT CO2 data to the inversion in addition to flask data, and (b) we use a 4DVAR optimization system instead of a Kalman filter. We compare inversions using (a) only GOSAT total column CO2 measurements, (b) only surface flask CO2 measurements, and (c) the joint data set of GOSAT and surface flask measurements. We validate GOSAT-only inversions against the NOAA surface flask network and joint inversions against CONTRAIL and other aircraft campaigns. We see that inverted fluxes from a GOSAT-only inversion are consistent with fluxes from a stations-only inversion, reaffirming the low biases in SRON retrievals. From the joint inversion, we estimate the amount of added constraints upon adding GOSAT total column measurements to existing surface layer measurements.

Down-modulation of the G-protein-coupled Estrogen Receptor, GPER, from the Cell Surface Occurs via a trans-Golgi-Proteasome Pathway*

PubMed Central

Cheng, Shi-Bin; Quinn, Jeffrey A.; Graeber, Carl T.; Filardo, Edward J.

2011-01-01

GPER is a Gs-coupled seven-transmembrane receptor that has been linked to specific estrogen binding and signaling activities that are manifested by plasma membrane-associated enzymes. However, in many cell types, GPER is predominately localized to the endoplasmic reticulum (ER), and only minor amounts of receptor are detectable at the cell surface, an observation that has caused controversy regarding its role as a plasma membrane estrogen receptor. Here, we show that GPER constitutively buds intracellularly into EEA-1+ endosomes from clathrin-coated pits. Nonvisual arrestins-2/-3 do not co-localize with GPER, and expression of arrestin-2 dominant-negative mutants lacking clathrin- or β-adaptin interaction sites fails to block GPER internalization suggesting that arrestins are not involved in GPER endocytosis. Like β1AR, which recycles to the plasma membrane, GPER co-traffics with transferrin+, Rab11+ recycling endosomes. However, endocytosed GPER does not recycle to the cell surface, but instead returns to the trans-Golgi network (TGN) and does not re-enter the ER. GPER is ubiquitinated at the cell surface, exhibits a short half-life (t½ <1 h), and is protected from degradation by the proteasome inhibitor, MG132. Disruption of the TGN by brefeldin A induces the accumulation of endocytosed GPER in Rab11+ perinuclear endosomes and prevents GPER degradation. Our results provide an explanation as to why GPER is not readily detected on the cell surface in some cell types and further suggest that TGN serves as the checkpoint for degradation of endocytosed GPER. PMID:21540189

Detection of Vegetable Oil Variance Using Surface Plasmon Resonance (SPR) Technique

NASA Astrophysics Data System (ADS)

Supardianningsih; Panggabean, R. D.; Romadhon, I. A.; Laksono, F. D.; Nofianti, U.; Abraha, K.

2018-05-01

The difference between coconut oil, corn oil, olive oil, and palm oil has been detected using surface plasmon resonance (SPR) technique. This is a new method in material characterization that can be used to identify vegetable oil variance. The SPR curve was measured by SPR system consisting of optical instruments, mechanical instruments, Main UNIT, and user interface (computer). He-Ne laser beam of wavelength 633 nm was used as light source, while gold (Au) thin film evaporated on half cylinder prism was used as the base so that surface plasmon polariton (SPP) waves propagate at the interface. Tween-80 and PEG-400 are used as surfactant and co-surfactant to make water-oil emulsion from each sample. The sample was prepared with the ratio of oil: surfactant: co-surfactant as 1:2:1 and then stirred on the water to make emulsions. The angle shift was measured by the change of SPR angle from prism/Au/air system to prism/Au/water-oil emulsion. The different SPR angle of each sample has been detected in the various number of spray, a method that was used for depositing the emulsion. From this work, we conclude that the saturated fatty acid component was the most significant component that changes the refractive index in the vegetable oil in water emulsion that can be used to characterize the vegetable oil variance.

Enhanced Sensitivity of Wireless Chemical Sensor Based on Love Wave Mode

NASA Astrophysics Data System (ADS)

Wang, Wen; Oh, Haekwan; Lee, Keekeun; Yang, Sangsik

2008-09-01

A 440 MHz wireless and passive Love-wave-based chemical sensor was developed for CO2 detection. The developed device was composed of a reflective delay line patterned on 41° YX LiNbO3 piezoelectric substrate, a poly(methyl methacrylate) (PMMA) waveguide layer, and Teflon AF 2400 sensitive film. A theoretical model is presented to describe wave propagation in Love wave devices with large piezoelectricity and to allow the design of an optimized structure. In wireless device testing using a network analyzer, infusion of CO2 into the testing chamber induced large phase shifts of the reflection peaks owing to the interaction between the sensing film and the test gas (CO2). Good linearity and repeatability were observed at CO2 concentrations of 0-350 ppm. The obtained sensitivity from the Love wave device was approximately 7.07° ppm-1. The gas response properties of the fabricated Love-wave sensor in terms of linearity and sensitivity were provided, and a comparison to surface acoustic wave devices was also discussed.

Muon Tomography for Geological Repositories.

NASA Astrophysics Data System (ADS)

Woodward, D.; Kudryavtsev, V.; Gluyas, J.; Clark, S. J.; Thompson, L. F.; Klinger, J.; Spooner, N. J.; Blackwell, T. B.; Pal, S.; Lincoln, D. L.; Paling, S. M.; Mitchell, C. N.; Benton, C.; Coleman, M. L.; Telfer, S.; Cole, A.; Nolan, S.; Chadwick, P.

2015-12-01

Cosmic-ray muons are subatomic particles produced in the upper atmosphere in collisions of primary cosmic rays with atoms in air. Due to their high penetrating power these muons can be used to image the content (primarily density) of matter they pass through. They have already been used to image the structure of pyramids, volcanoes and other objects. Their applications can be extended to investigating the structure of, and monitoring changes in geological formations and repositories, in particular deep subsurface sites with stored CO2. Current methods of monitoring subsurface CO2, such as repeat seismic surveys, are episodic and require highly skilled personnel to operate. Our simulations based on simplified models have previously shown that muon tomography could be used to continuously monitor CO2 injection and migration and complement existing technologies. Here we present a simulation of the monitoring of CO2 plume evolution in a geological reservoir using muon tomography. The stratigraphy in the vicinity of the reservoir is modelled using geological data, and a numerical fluid flow model is used to describe the time evolution of the CO2 plume. A planar detection region with a surface area of 1000 m2 is considered, at a vertical depth of 776 m below the seabed. We find that one year of constant CO2 injection leads to changes in the column density of about 1%, and that the CO2 plume is already resolvable with an exposure time of less than 50 days. The attached figure show a map of CO2 plume in angular coordinates as reconstructed from observed muons. In parallel with simulation efforts, a small prototype muon detector has been designed, built and tested in a deep subsurface laboratory. Initial calibrations of the detector have shown that it can reach the required angular resolution for muon detection. Stable operation in a small borehole within a few months has been demonstrated.

Low temperature detection of phase transitions and relaxation processes in strontium titanate by means of cathodoluminescence

NASA Astrophysics Data System (ADS)

Yang, B.; Townsend, P. D.; Fromknecht, R.

2004-11-01

Cathodoluminescence is an effective tool for investigating phase changes and relaxation processes in insulators and data are presented for strontium titanate. The results demonstrate considerable sensitivity to the origin of the samples as the detailed spectra and intensity changes with temperature are strongly dependent on the growth conditions, trace impurities and radiation induced defects. It is of particular note that in the defective surface layer the normal second-order phase transition cited near 105 K transforms into a sharply defined first-order transition because of the relaxation of the near surface layer in doped crystals. Detection of the other main relaxation stages is also straightforward via intensity and spectral changes. Secondary effects of phase changes incorporated within the surface layers are clearly evident, particularly for the 197 K sublimation of CO2 nanoparticle inclusions.

The Composition of Titan's Lower Atmosphere and Simple Surface Volatiles as Measured by the Cassini-Huygens Probe Gas Chromatograph Mass Spectrometer Experiment

NASA Technical Reports Server (NTRS)

Niemann, H. B.; Atreya, S. K.; Demick, J. E.; Gautier, D.; Haberman, J. A.; Harpold, D. N.; Kasprzak, W. T.; Lunine, J. I.; Owen, T. C.; Raulin, F.

2010-01-01

The Cassini-Huygens Probe Gas Chromatograph Mass Spectrometer (GCMS) determined the composition of the Titan atmosphere from 140km altitude to the surface. After landing, it returned composition data of gases evaporated from the surface. Height profiles of molecular nitrogen (N2), methane (CH4) and molecular hydrogen (H2) were determined. Traces were detected on the surface of evaporating methane, ethane (C2H6), acetylene (C2H2), cyanogen (C2N2) and carbon dioxide (CO2). The methane data showed evidence that methane precipitation occurred recently. The methane mole fraction was (1.48+/-0.09) x 10(exp -2) in the lower stratosphere (139.8 km to 75.5 km) and (5.65+/-0.18) x 10(exp -2) near the surface (6.7 km to the surface). The molecular hydrogen mole fraction was (1.01+/-0.16) x 10(exp -3) in the atmosphere and (9.90+/-0.17) x 10(exp -4) on the surface. Isotope ratios were 167.7+/-0.6 for N-14/N-15 in molecular nitrogen, 91.1+/-1.4 for C-12/C-13 in methane and (1.35+/-0.30) x 10(exp -4) for D/H in molecular hydrogen. The mole fractions of Ar-36 and radiogenic Ar-40 are (2.1+/-0.8) x 10(exp -7) and (3.39 +/-0.12) x 10(exp -5) respectively. Ne-22 has been tentatively identified at a mole fraction of (2.8+/-2.1) x 10(exp -7) Krypton and xenon were below the detection threshold of 1 x 10(exp -8) mole fraction. Science data were not retrieved from the gas chromatograph subsystem as the abundance of the organic trace gases in the atmosphere and on the ground did not reach the detection threshold. Results previously published from the GCMS experiment are superseded by this publication.

Variability and trends in surface seawater pCO2 and CO2 flux in the Pacific Ocean

NASA Astrophysics Data System (ADS)

Sutton, A. J.; Wanninkhof, R.; Sabine, C. L.; Feely, R. A.; Cronin, M. F.; Weller, R. A.

2017-06-01

Variability and change in the ocean sink of anthropogenic carbon dioxide (CO2) have implications for future climate and ocean acidification. Measurements of surface seawater CO2 partial pressure (pCO2) and wind speed from moored platforms are used to calculate high-resolution CO2 flux time series. Here we use the moored CO2 fluxes to examine variability and its drivers over a range of time scales at four locations in the Pacific Ocean. There are significant surface seawater pCO2, salinity, and wind speed trends in the North Pacific subtropical gyre, especially during winter and spring, which reduce CO2 uptake over the 10 year record of this study. Starting in late 2013, elevated seawater pCO2 values driven by warm anomalies cause this region to be a net annual CO2 source for the first time in the observational record, demonstrating how climate forcing can influence the timing of an ocean region shift from CO2 sink to source.

Time-lapse processing of 2D seismic profiles with testing of static correction methods at the CO2 injection site Ketzin (Germany)

NASA Astrophysics Data System (ADS)

Bergmann, Peter; Yang, Can; Lüth, Stefan; Juhlin, Christopher; Cosma, Calin

2011-09-01

The Ketzin project provides an experimental pilot test site for the geological storage of CO2. Seismic monitoring of the Ketzin site comprises 2D and 3D time-lapse experiments with baseline experiments in 2005. The first repeat 2D survey was acquired in 2009 after 22 kt of CO2 had been injected into the Stuttgart Formation at approximately 630 m depth. Main objectives of the 2D seismic surveys were the imaging of geological structures, detection of injected CO2, and comparison with the 3D surveys. Time-lapse processing highlighted the importance of detailed static corrections to account for travel time delays, which are attributed to different near-surface velocities during the survey periods. Compensation for these delays has been performed using both pre-stack static corrections and post-stack static corrections. The pre-stack method decomposes the travel time delays of baseline and repeat datasets in a surface consistent manner, while the latter cross-aligns baseline and repeat stacked sections along a reference horizon. Application of the static corrections improves the S/N ratio of the time-lapse sections significantly. Based on our results, it is recommended to apply a combination of both corrections when time-lapse processing faces considerable near-surface velocity changes. Processing of the datasets demonstrates that the decomposed solution of the pre-stack static corrections can be used for interpretation of changes in near-surface velocities. In particular, the long-wavelength part of the solution indicates an increase in soil moisture or a shallower groundwater table in the repeat survey. Comparison with the processing results of 2D and 3D surveys shows that both image the subsurface, but with local variations which are mainly associated to differences in the acquisition geometry and source types used. Interpretation of baseline and repeat stacks shows that no CO2 related time-lapse signature is observable where the 2D lines allow monitoring of the reservoir. This finding is consistent with the time-lapse results of the 3D surveys, which show an increase in reflection amplitude centered around the injection well. To further investigate any potential CO2 signature, an amplitude versus offset (AVO) analysis was performed. The time-lapse analysis of the AVO does not indicate the presence of CO2, as expected, but shows signs of a pressure response in the repeat data.

Electrocatalytic behaviour of surface confined pentanethio cobalt (II) binuclear phthalocyanines towards the oxidation of 4-chlorophenol

NASA Astrophysics Data System (ADS)

Makinde, Zainab O.; Louzada, Marcel; Mashazi, Philani; Nyokong, Tebello; Khene, Samson

2017-12-01

Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.

Synthesis of HCN and HNC in Ion-Irradiated N2-Rich Ices

NASA Technical Reports Server (NTRS)

Moore, M. H.; Hudson, R. L.; Ferrante, R. F.

2002-01-01

Near-IR observations reveal that N2-rich ice containing small amounts of CH4, and CO, is abundant on the surfaces of Triton, a moon of Neptune, and Pluto. N2-rich ices may also exist, in interstellar environments. To investigate the radiation chemistry of such ices we performed a systematic IR study of ion-irradiated Nz-rich mixtures containing CH4 and CO. Irradiation of N2 + CH4 mixtures at 12 K, showed that HCN, HNC, diazomethane, and NH3 were produced. We also found that UV photolysis of these ices produced detectable HCN and HNC. Intrinsic band strengths, A(HCN) and A(HNC), were measured and used to calculate yields of HCN and HNC. Similar results were obtained on irradiation of N2 + CH4 + CO ices at 12 K, with the main difference being the formation of HNCO. In all cases we observed changes on warming. For example, when the temperature of irradiated Nz + CH4 + CO was raised from 12 to 30 K, HCN, HNC, and HNCO reacted with NH3, and OCN-, CN-, N3-, and NH4+ were produced. These ions, appearing at 30 K, are expected to form and survive on the surfaces of Triton, Pluto, and interstellar grains. Our results have astrobiological implications since some of these radiation products are involved in the syntheses of biomolecules such as amino acids and peptides.

Preparation and characterization of magnetic allylamine modified graphene oxide-poly(vinyl acetate-co-divinylbenzene) nanocomposite for vortex assisted magnetic solid phase extraction of some metal ions.

PubMed

Khan, Mansoor; Yilmaz, Erkan; Sevinc, Basak; Sahmetlioglu, Ertugrul; Shah, Jasmin; Jan, Muhammad Rasul; Soylak, Mustafa

2016-01-01

Magnetic allylamine modified graphene oxide-poly(vinyl acetate-co-divinylbenzene) (MGO-DVB-VA) was synthesized and used for magnetic solid phase extraction of Pb(II), Cd(II), Cu(II), Ni(II) and Co(II) prior to their determination by flame atomic absorption spectroscopy. The adsorbent surface functional group was characterized by using FT-IR and Raman spectroscopy. XRD pattern was used to determine the layers of GO. Surface morphology and elemental composition of the adsorbent were evaluated by using SEM and EDX analysis. Various parameters, effecting adsorption efficiency like initial solution pH, adsorbent dose, type and volume of eluent, volume of sample and diverse ions effects were optimized. The preconcentration factor (PF) is 40 for all the metals and the limits of detection for Pb, Cd, Cu, Ni and Co are in the range of 0.37-2.39 µg L(-1) and relative standard deviation below 3.1%. The method was validated by using the method for certified reference materials (Tobacco Leaves (INCT-OBTL-5), Tomato Leaves (1573a), Certified Water (SPS-ww2) and Certified Water (TMDA 64-2)). The method was successfully applied for natural water and food samples. Copyright © 2015 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.

Carbon dioxide laser polishing of fused silica surfaces for increased laser-damage resistance at 1064 nm.

PubMed

Temple, P A; Lowdermilk, W H; Milam, D

1982-09-15

Mechanically polished fused silica surfaces were heated with continuous-wave CO(2) laser radiation. Laser-damage thresholds of the surfaces were measured with 1064-nm 9-nsec pulses focused to small spots and with large-spot, 1064-nm, 1-nsec irradiation. A sharp transition from laser-damage-prone to highly laser-damage-resistant took place over a small range in CO(2) laser power. The transition to high damage resistance occurred at a silica surface temperature where material softening began to take place as evidenced by the onset of residual strain in the CO(2) laser-processed part. The small-spot damage measurements show that some CO(2) laser-treated surfaces have a local damage threshold as high as the bulk damage threshold of SiO(2). On some CO(2) laser-treated surfaces, large-spot damage thresholds were increased by a factor of 3-4 over thresholds of the original mechanically polished surface. These treated parts show no obvious change in surface appearance as seen in bright-field, Nomarski, or total internal reflection microscopy. They also show little change in transmissive figure. Further, antireflection films deposited on CO(2) laser-treated surfaces have thresholds greater than the thresholds of antireflection films on mechanically polished surfaces.

The Martian paleoclimate and enhanced atmospheric carbon dioxide

NASA Technical Reports Server (NTRS)

Cess, R. D.; Owen, T.; Ramanathan, V.

1980-01-01

Current evidence indicates that the Martian surface is abundant with water presently in the form of ice, while the atmosphere was at one time more massive with a past surface pressure of as much as 1 atm of CO2. In an attempt to understand the Martian paleoclimate, a past CO2-H2O greenhouse was modeled and global temperatures which are consistent with an earlier presence of liquid surface water are found in agreement with the extensive evidence for past fluvial erosion. An important aspect of the CO2-H2O greenhouse model is the detailed inclusion of CO2 hot bands. For a surface pressure of 1 atm of CO2, the present greenhouse model predicts a global mean surface temperature of 294 K, but if the hot bands are excluded, a surface temperature of only 250 K is achieved.

UV-enhanced CO sensing using Ga 2O 3-based nanorod arrays at elevated temperature

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

Lin, Hui-Jan; Gao, Haiyong; Gao, Pu-Xian

Monitoring and control of gaseous combustion process are critically important in advanced energy systems such as power plants, gas turbines, and automotive engines. However, very limited gas sensing solutions are available in the market for such application due to the inherent high temperature of combustion gaseous atmosphere. In this study, we fabricated and demonstrated high-performance metal oxide based nanorod array sensors assisted with ultra-violet (UV) illumination for in situ and real-time high-temperature gas detection. Without UV-illumination, it was found surface decoration of either 5 nm LSFO or 1 nm Pt nanoparticles can enhance the sensitivity over CO at 500 °Cmore » by an order of magnitude. Under the 254 nm UV illumination, CO gas-sensing performance of Ga 2O 3-based nanorod array sensors was further enhanced with the sensitivity boosted by 125 %, and the response time reduced by 30 % for La 0.8Sr 0.2FeO 3(LSFO)-decorated sample. The UV-enhanced detecting of CO might be due to the increased population of photo-induced electron-hole pairs. While for LSFO-decorated nanorod array sensor under UV illumination, the enhancement is through a combination of sensitizing effect and photocurrent effect.« less

UV-enhanced CO sensing using Ga 2O 3-based nanorod arrays at elevated temperature

DOE PAGES

Lin, Hui-Jan; Gao, Haiyong; Gao, Pu-Xian

2017-01-23

Monitoring and control of gaseous combustion process are critically important in advanced energy systems such as power plants, gas turbines, and automotive engines. However, very limited gas sensing solutions are available in the market for such application due to the inherent high temperature of combustion gaseous atmosphere. In this study, we fabricated and demonstrated high-performance metal oxide based nanorod array sensors assisted with ultra-violet (UV) illumination for in situ and real-time high-temperature gas detection. Without UV-illumination, it was found surface decoration of either 5 nm LSFO or 1 nm Pt nanoparticles can enhance the sensitivity over CO at 500 °Cmore » by an order of magnitude. Under the 254 nm UV illumination, CO gas-sensing performance of Ga 2O 3-based nanorod array sensors was further enhanced with the sensitivity boosted by 125 %, and the response time reduced by 30 % for La 0.8Sr 0.2FeO 3(LSFO)-decorated sample. The UV-enhanced detecting of CO might be due to the increased population of photo-induced electron-hole pairs. While for LSFO-decorated nanorod array sensor under UV illumination, the enhancement is through a combination of sensitizing effect and photocurrent effect.« less

UV-enhanced CO sensing using Ga2O3-based nanorod arrays at elevated temperature

NASA Astrophysics Data System (ADS)

Lin, Hui-Jan; Gao, Haiyong; Gao, Pu-Xian

2017-01-01

Monitoring and control of the gaseous combustion process are critically important in advanced energy systems such as power plants, gas turbines, and automotive engines. However, very limited gas sensing solutions are available in the market for such applications due to the inherent high temperature of the combustion gaseous atmosphere. In this study, we fabricated and demonstrated high-performance metal oxide based nanorod array sensors assisted with ultra-violet (UV) illumination for in situ and real-time high-temperature gas detection. Without UV-illumination, it was found that surface decoration of either 5 nm LSFO or 1 nm Pt nanoparticles can enhance the sensitivity over CO at 500 °C by an order of magnitude. Under the 254 nm UV illumination, the CO gas-sensing performance of Ga2O3-based nanorod array sensors was further enhanced with the sensitivity boosted by 125% and the response time reduced by 30% for the La0.8Sr0.2FeO3(LSFO)-decorated sample. The UV-enhanced detection of CO might be due to the increased population of photo-induced electron-hole pairs, whereas for LSFO-decorated nanorod array sensor under UV illumination, the enhancement is through a combination of the sensitizing effect and photocurrent effect.

Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity.

PubMed

Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta; Osawa, Masatoshi; Surendranath, Yogesh

2016-08-09

CO2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H2 We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H2 and CO production on polycrystalline Au electrodes. Under the conditions of CO2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis.

Exciton-Plasmon hybrids for surface catalysis detected by SERS.

PubMed

Cao, En; Sun, Mengtao; Song, Yu-Zhi; Liang, Wenjie

2018-06-25

Surface plasmons (SPs), the free electrons are collectively excited on the metal surface, which have been successfully used in the analysis chemical and signal detection. Generally, SPs possess two types of decay channels. One of that is radiation decay by reemitting photons. The other way is producing hot electrons with high kinetic energy that named non-radiation, which can be applied in surface catalysis. When the excitation light with special wavelength is irradiated on the surface of pasmonic nanostructure, the strong coupling interaction between electrons and light will occur on that, followed by a series of unique properties. More than a decade, two-dimensional (2D) materials have become a hot topic of research, since the graphene was found in 2004. Recently, the combination of graphene with metal NPs has been shown lots of supernormal advantages in that, such as high stability and catalytic activity, which also has been successfully applied in plasmon-exciton co-driven chemical reactions. © 2018 IOP Publishing Ltd.

Boletus edulis loaded with γ-Fe2O3 nanoparticles as a magnetic sorbent for preconcentration of Co(II) and Sn(II) prior to their determination by ICP-OES.

PubMed

Ozdemir, Sadin; Serkan Yalcin, M; Kilinc, Ersin; Soylak, Mustafa

2017-12-20

The authors show that the fungus Boletus edulis loaded with γ-Fe 2 O 3 nanoparticles is a viable sorbent for magnetic solid phase extraction of trace levels of Co(II) and Sn(II). The surface structure of immobilized magnetized B. edulis was characterized by FT-IR, SEM and EDX. Experimental parameters were optimized. Following elution with 1 M HCl, the ions were quantified by ICP-OES. The limits of detection are 21 pg·mL -1 for Co(II), and 19 pg·mL -1 for Sn(II). The preconcentration factors are 100 for both ions. The sorption capacities of the sorbent are 35.8 mg·g -1 for Co(II) and 29.6 mg·g -1 for Sn(II). The method was applied to the analysis of certificated reference materials and gave ≥95% recoveries with low RSDs. It was also successfully applied to the quantification of Co(II) and Sn(II) in spiked environmental and food samples. Graphical abstract The fungus Boletus edulis loaded with γ-Fe 2 O 3 nanoparticles is a viable biosorbent for magnetic solid phase extraction (MSPE) of trace levels of Co(II) and Sn(II). The surface structure of immobilized magnetized B. edulis was characterized by FT-IR, SEM and EDX. Experimental parameters were optimized.

Perchlorate Salts in the Martian Surface Environment - A Reexamination of the 1976 Viking Biology Results

NASA Astrophysics Data System (ADS)

Dillon, James; Quinn, R. C.

2010-01-01

The Viking Mars landers of 1976 conducted three biology experiments designed to detect the presence of microbial life in the Martian surface. The gas exchange experiment carried out by the Viking landers periodically sampled the gaseous headspace of Mars soil samples saturated with an organic/inorganic aqueous mixture, M4 nutrient. A gas chromatograph measured the change in concentrations of N2, O2, CO2, Kr, H2, and CH4 over various time intervals. The presence of metabolically active microbial life would be confirmed by the consumption or release of one of these gases. A significant release of O2 was detected after the addition of nutrient, however since the Gas Chromatograph - Mass Spectrometer experiment did not detect organics in the soil, this rapid release of O2 could not be attributed to microbial life, but rather a chemical reaction. The recent discovery of the oxidizer perchlorate in the Martian soil by the Phoenix Mars lander was investigated as the principal cause of this O2 release detected by the Viking gas exchange experiment. A variety of oxychloride salts ranging from hypochlorite to perchlorate were examined under conditions similar to the Viking experiment in order to determine if a rapid release of O2 would be detected upon addition of M4 nutrient. No oxychloride species examined decomposed with the kinetics required to support an oxychloride as the cause of the O2 response detected by the Viking experiment.

Deriving a sea surface climatology of CO2 fugacity in support of air-sea gas flux studies

NASA Astrophysics Data System (ADS)

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

2014-07-01

Climatologies, or long-term averages, of essential climate variables are useful for evaluating models and providing a baseline for studying anomalies. The Surface Ocean Carbon Dioxide (CO2) Atlas (SOCAT) has made millions of global underway sea surface measurements of CO2 publicly available, all in a uniform format and presented as fugacity, fCO2. fCO2 is highly sensitive to temperature and the measurements are only valid for the instantaneous sea surface temperature (SST) that is measured concurrent with the in-water CO2 measurement. To create a climatology of fCO2 data suitable for calculating air-sea CO2 fluxes it is therefore desirable to calculate fCO2 valid for climate quality SST. This paper presents a method for creating such a climatology. We recomputed SOCAT's fCO2 values for their respective measurement month and year using climate quality SST data from satellite Earth observation and then extrapolated the resulting fCO2 values to reference year 2010. The data were then spatially interpolated onto a 1° × 1° grid of the global oceans to produce 12 monthly fCO2 distributions for 2010. The partial pressure of CO2 (pCO2) is also provided for those who prefer to use pCO2. The CO2 concentration difference between ocean and atmosphere is the thermodynamic driving force of the air-sea CO2 flux, and hence the presented fCO2 distributions can be used in air-sea gas flux calculations together with climatologies of other climate variables.

Methylmercury oxidative degradation potentials in contaminated and pristine sediments of the Carson River, Nevada

USGS Publications Warehouse

Oremland, R.S.; Miller, L.G.; Dowdle, P.; Connell, T.; Barkay, T.

1995-01-01

Sediments from mercury-contaminated and uncontaminated reaches of the Carson River, Nevada, were assayed for sulfate reduction, methanogenesis, denitrification, and monomethylmercury (MeHg) degradation. Demethylation of [14C]MeHg was detected at all sites as indicated by the formation of 14CO2 and 14CH4. Oxidative demethylation was indicated by the formation of 14CO2 and was present at significant levels in all samples. Oxidized/reduced demethylation product ratios (i.e., 14CO2/14CH4 ratios) generally ranged from 4.0 in surface layers to as low as 0.5 at depth. Production of 14CO2 was most pronounced at sediment surfaces which were zones of active denitrification and sulfate reduction but was also significant within zones of methanogenesis. In a core taken from an uncontaminated site having a high proportion of oxidized, coarse-grain sediments, sulfate reduction and methanogenic activity levels were very low and 14CO2 accounted for 98% of the product formed from [14C]MeHg. There was no apparent relationship between the degree of mercury contamination of the sediments and the occurrence of oxidative demethylation. However, sediments from Fort Churchill, the most contaminated site, were most active in terms of demethylation potentials. Inhibition of sulfate reduction with molybdate resulted in significantly depressed oxidized/reduced demethylation product ratios, but overall demethylation rates of inhibited and uninhibited samples were comparable. Addition of sulfate to sediment slurries stimulated production of 14CO2 from [14C]MeHg, while 2-bromoethanesulfonic acid blocked production of 14CH4. These results reveal the importance of sulfate-reducing and methanogenic bacteria in oxidative demethylation of MeHg in anoxic environments.

Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.

PubMed

Sad, María E; Neurock, Matthew; Iglesia, Enrique

2011-12-21

This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions. © 2011 American Chemical Society

Ni-Co bimetal nanowires filled multiwalled carbon nanotubes for the highly sensitive and selective non-enzymatic glucose sensor applications

PubMed Central

Ramachandran, K.; Raj kumar, T.; Babu, K. Justice; Gnana kumar, G.

2016-01-01

The facile, time and cost efficient and environmental benign approach has been developed for the preparation of Nickel (Ni)-Cobalt (Co) alloy nanowires filled multiwalled carbon nanotubes (MWCNTs) with the aid of mesoporous silica nanoparticles (MSN)/Ni-Co catalyst. The controlled incorporation of Ni-Co nanostructures in the three dimensional (3D) pore structures of MSN yielded the catalytically active system for the MWCNT growth. The inner surface of MWCNTs was quasi-continuously filled with face-centered cubic (fcc) structured Ni-Co nanowires. The as-prepared nanostructures were exploited as non-enzymatic electrochemical sensor probes for the reliable detection of glucose. The electrochemical measurements illustrated that the fabricated sensor exhibited an excellent electrochemical performance toward glucose oxidation with a high sensitivity of 0.695 mA mM−1 cm−2, low detection limit of 1.2 μM, a wide linear range from 5 μM–10 mM and good selectivity. The unprecedented electrochemical performances obtained for the prepared nanocomposite are purely attributed to the synergistic effects of Ni-Co nanowires and MWCNTs. The constructed facile, selective and sensitive glucose sensor has also endowed its reliability in analyzing the human serum samples, which wide opened the new findings for exploring the novel nanostructures based glucose sensor devices with affordable cost and good stability. PMID:27833123

Ni-Co bimetal nanowires filled multiwalled carbon nanotubes for the highly sensitive and selective non-enzymatic glucose sensor applications

NASA Astrophysics Data System (ADS)

Ramachandran, K.; Raj Kumar, T.; Babu, K. Justice; Gnana Kumar, G.

2016-11-01

The facile, time and cost efficient and environmental benign approach has been developed for the preparation of Nickel (Ni)-Cobalt (Co) alloy nanowires filled multiwalled carbon nanotubes (MWCNTs) with the aid of mesoporous silica nanoparticles (MSN)/Ni-Co catalyst. The controlled incorporation of Ni-Co nanostructures in the three dimensional (3D) pore structures of MSN yielded the catalytically active system for the MWCNT growth. The inner surface of MWCNTs was quasi-continuously filled with face-centered cubic (fcc) structured Ni-Co nanowires. The as-prepared nanostructures were exploited as non-enzymatic electrochemical sensor probes for the reliable detection of glucose. The electrochemical measurements illustrated that the fabricated sensor exhibited an excellent electrochemical performance toward glucose oxidation with a high sensitivity of 0.695 mA mM-1 cm-2, low detection limit of 1.2 μM, a wide linear range from 5 μM-10 mM and good selectivity. The unprecedented electrochemical performances obtained for the prepared nanocomposite are purely attributed to the synergistic effects of Ni-Co nanowires and MWCNTs. The constructed facile, selective and sensitive glucose sensor has also endowed its reliability in analyzing the human serum samples, which wide opened the new findings for exploring the novel nanostructures based glucose sensor devices with affordable cost and good stability.

The (2×2) reconstructions on the surface of cobalt silicides: Atomic configuration at the annealed Co/Si(111) interface

NASA Astrophysics Data System (ADS)

Kotlyar, V. G.; Alekseev, A. A.; Olyanich, D. A.; Utas, T. V.; Zotov, A. V.; Saranin, A. A.

2017-08-01

We have used scanning tunneling microscopy (STM) and ab initio total-energy calculations to characterize surface and interfacial structure of Co-Si(111) system. It has been found experimentally that two different types of the (2×2) surface structures occur. The coexistence of two phases is demonstrated by the example of STM image of the surface formed at the early stages of cobalt silicide formation under moderate annealing temperatures (500 °C). The measured height difference between the adjacent (2×2) reconstructed patches equal to about 1.0 Å (as determined from the filled-state STM images). In addition, the shift of the atomic rows by half of the row spacing is observed. Two adatom models of the (2×2) surface structures are developed. According to our data, these structures are assigned to CaF2-type CoSi2 and CsCl-type CoSi with a (2×2) array of Si adatoms on their surfaces. If the latter is the case, it has а coherent double interface CoSi/CoSi2/Si(111) with a two-layer CoSi2. Both of these interfaces are characterized by the eightfold cobalt coordination and incorporate a grown-in stacking fault.

Feasibility of the Scalable, Automated, Semipermanent Seismic Array (SASSA) to Monitor Possible Carbon Dioxide Migration

NASA Astrophysics Data System (ADS)

Livers, A. J.; Burnison, S. A.; Salako, O.; Barajas-Olalde, C.; Hamling, J. A.; Gorecki, C. D.

2016-12-01

The feasibility of monitoring potential carbon dioxide (CO2) migration in a reservoir using a sparse seismic array is being evaluated by the Energy & Environmental Research Center (EERC) at the Denbury Onshore LLC-operated Bell Creek oil field in Montana, which is undergoing commercial CO2 enhanced oil recovery (EOR). This new method may provide an economical means of continuously monitoring the CO2 plume edge and the CO2 reservoir boundaries and/or to interpret vertical or lateral out-of-reservoir CO2 migration. A 96-station scalable, automated, semipermanent seismic array (SASSA) was deployed in October 2015 to detect and track CO2 plume migration not by imaging, but by monitoring discrete source-receiver midpoints. Midpoints were strategically located within and around four injector-producer patterns covering approximately one square mile. Three-dimensional (3-D) geophysical ray tracing was used to determine surface receiver locations. Receivers used were FairfieldNodal Zland three-component, autonomous, battery-powered nodes. A GISCO ESS850 accelerated weight drop source located in a secure structure was remotely fired on a weekly basis for one calendar year, including a two-month period prior to initiation of CO2 injection to establish a baseline. Fifty shots were fired one day each week to facilitate increased signal-to-noise through novel receiver domain processing and vertical stacking. Receiver domain processing allowed for individualization of processing parameters to maximize signal enhancement and noise attenuation. Reflection events in the processed SASSA data correlate well to 3-D surface survey data collected in the field. Preliminary time-lapse data results for several individual SASSA receivers show a phase shift in the reflection events below the reservoir after injection, suggesting possible migration of the CO2 in the reservoir to the corresponding midpoint locations. This work is supported by the U.S. Department of Energy National Energy Technology Laboratory under Award No. FE0012665.

Fault zones ruptured during the early 2014 Cephalonia Island (Ionian Sea, Western Greece) earthquakes (January 26 and February 3, Mw 6.0) based on the associated co-seismic surface ruptures

NASA Astrophysics Data System (ADS)

Lekkas, Efthymios L.; Mavroulis, Spyridon D.

2016-01-01

The early 2014 Cephalonia Island (Ionian Sea, Western Greece) earthquake sequence comprised two main shocks with almost the same magnitude (moment magnitude (Mw) 6.0) occurring successively within a short time (January 26 and February 3) and space (Paliki peninsula in Western Cephalonia) interval. Εach earthquake was induced by the rupture of a different pre-existing onshore active fault zone and produced different co-seismic surface rupture zones. Co-seismic surface rupture structures were predominantly strike-slip-related structures including V-shaped conjugate surface ruptures, dextral and sinistral strike-slip surface ruptures, restraining and releasing bends, Riedel structures ( R, R', P, T), small-scale bookshelf faulting, and flower structures. An extensional component was present across surface rupture zones resulting in ground openings (sinkholes), small-scale grabens, and co-seismic dip-slip (normal) displacements. A compressional component was also present across surface rupture zones resulting in co-seismic dip-slip (reverse) displacements. From the comparison of our field geological observations with already published surface deformation measurements by DInSAR Interferometry, it is concluded that there is a strong correlation among the surface rupture zones, the ruptured active fault zones, and the detected displacement discontinuities in Paliki peninsula.

Airborne Measurements of CO2 Column Concentration and Range Using a Pulsed Direct-Detection IPDA Lidar

NASA Technical Reports Server (NTRS)

Abshire, James B.; Ramanathan, Anand; Riris, Haris; Mao, Jianping; Allan, Graham R.; Hasselbrack, William E.; Weaver, Clark J.; Browell, Edward V.

2013-01-01

We have previously demonstrated a pulsed direct detection IPDA lidar to measure range and the column concentration of atmospheric CO2. The lidar measures the atmospheric backscatter profiles and samples the shape of the 1,572.33 nm CO2 absorption line. We participated in the ASCENDS science flights on the NASA DC-8 aircraft during August 2011 and report here lidar measurements made on four flights over a variety of surface and cloud conditions near the US. These included over a stratus cloud deck over the Pacific Ocean, to a dry lake bed surrounded by mountains in Nevada, to a desert area with a coal-fired power plant, and from the Rocky Mountains to Iowa, with segments with both cumulus and cirrus clouds. Most flights were to altitudes >12 km and had 5-6 altitude steps. Analyses show the retrievals of lidar range, CO2 column absorption, and CO2 mixing ratio worked well when measuring over topography with rapidly changing height and reflectivity, through thin clouds, between cumulus clouds, and to stratus cloud tops. The retrievals shows the decrease in column CO2 due to growing vegetation when flying over Iowa cropland as well as a sudden increase in CO2 concentration near a coal-fired power plant. For regions where the CO2 concentration was relatively constant, the measured CO2 absorption lineshape (averaged for 50 s) matched the predicted shapes to better than 1% RMS error. For 10 s averaging, the scatter in the retrievals was typically 2-3 ppm and was limited by the received signal photon count. Retrievals were made using atmospheric parameters from both an atmospheric model and from in situ temperature and pressure from the aircraft. The retrievals had no free parameters and did not use empirical adjustments, and >70% of the measurements passed screening and were used in analysis. The differences between the lidar-measured retrievals and in situ measured average CO2 column concentrations were <1.4 ppm for flight measurement altitudes >6 km.

Observed ices in the Solar System

USGS Publications Warehouse

Clark, Roger N.; Grundy, Will; Carlson, Robert R.; Noll, Keith; Gudipati, Murthy; Castillo-Rogez, Julie C.

2013-01-01

Ices have been detected and mapped on the Earth and all planets and/or their satellites further from the sun. Water ice is the most common frozen volatile observed and is also unambiguously detected or inferred in every planet and/or their moon(s) except Venus. Carbon dioxide is also extensively found in all systems beyond the Earth except Pluto although it sometimes appears to be trapped rather than as an ice on some objects. The largest deposits of carbon dioxide ice is on Mars. Sulfur dioxide ice is found in the Jupiter system. Nitrogen and methane ices are common beyond the Uranian system. Saturn’s moon Titan probably has the most complex active chemistry involving ices, with benzene (C6H6) and many tentative or inferred compounds including ices of Cyanoacetylene (HC3N), Toluene (C7H8), Cyanogen (C2N2), Acetonitrile (CH3CN), H2O, CO2, and NH3. Confirming compounds on Titan is hampered by its thick smoggy atmosphere. Ammonia was predicted on many icy moons but is notably absent among the definitively detected ices with the possible exception of Enceladus. Comets, storehouses of many compounds that could exist as ices in their nuclei, have only had small amounts of water ice definitively detected on their surfaces. Only one asteroid has had a direct detection of surface water ice, although its presence can be inferred in others. This chapter reviews some of the properties of ices that lead to their detection, and surveys the ices that have been observed on solid surfaces throughout the Solar System.

Silver Nanoparticles with Surface-Bonded Oxygen for Highly Selective CO 2 Reduction

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

Jiang, Kun; Kharel, Priti; Peng, Yande

Here, the surface electronic structures of catalysts need to be carefully engineered in CO 2 reduction reaction (CO 2RR), where the hydrogen evolution side reaction usually takes over under a significant overpotential, and thus dramatically lows the reaction selectivity. Surface oxides can play a critical role in tuning the surface oxidation state of metal catalysts for a proper binding with CO 2RR reaction intermediates, which may significantly improve the catalyst activity and selectivity. Here, we demonstrate the importance of surface-bonded oxygen on silver nanoparticles in altering the reaction pathways and improving the CO 2RR performances. A comparative investigation on air-annealedmore » Ag (Air-Ag) catalyst with or without the post-treatment of H 2 thermal annealing (H 2-Ag) was performed. In Air-Ag, the subsurface chemically bonded O species (O-Ag δ+) was identified by angle resolved X-ray photoelectron spectroscopy and X-ray absorption spectroscopy techniques, and contributed to the improved CO selectivity rather than H 2 in CO 2RR electrolysis. As a result, while the maximal CO Faradaic efficiency of H 2-Ag is at ~ 30 %, the Air-Ag catalyst presented a high CO selectivity of more than 90 % under a current density of ~ 21 mA/cm 2.« less

The role of CO 2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

DOE PAGES

Zhang, Li; Wu, Zili; Nelson, Nicholas; ...

2015-09-22

Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODHmore » reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.« less

Silver Nanoparticles with Surface-Bonded Oxygen for Highly Selective CO 2 Reduction

DOE PAGES

Jiang, Kun; Kharel, Priti; Peng, Yande; ...

2017-09-12

Here, the surface electronic structures of catalysts need to be carefully engineered in CO 2 reduction reaction (CO 2RR), where the hydrogen evolution side reaction usually takes over under a significant overpotential, and thus dramatically lows the reaction selectivity. Surface oxides can play a critical role in tuning the surface oxidation state of metal catalysts for a proper binding with CO 2RR reaction intermediates, which may significantly improve the catalyst activity and selectivity. Here, we demonstrate the importance of surface-bonded oxygen on silver nanoparticles in altering the reaction pathways and improving the CO 2RR performances. A comparative investigation on air-annealedmore » Ag (Air-Ag) catalyst with or without the post-treatment of H 2 thermal annealing (H 2-Ag) was performed. In Air-Ag, the subsurface chemically bonded O species (O-Ag δ+) was identified by angle resolved X-ray photoelectron spectroscopy and X-ray absorption spectroscopy techniques, and contributed to the improved CO selectivity rather than H 2 in CO 2RR electrolysis. As a result, while the maximal CO Faradaic efficiency of H 2-Ag is at ~ 30 %, the Air-Ag catalyst presented a high CO selectivity of more than 90 % under a current density of ~ 21 mA/cm 2.« less

Long- and short-term temporal variations of the diffuse CO2 emission from Timanfaya volcano, Lanzarote, Canary Islands

NASA Astrophysics Data System (ADS)

Hernández, P. A.; Padilla, G.; Calvo, D.; Padrón, E.; Melian, G.; Dionis, S.; Nolasco, D.; Barrancos, J.; Rodríguez, F.; Pérez, N.

2012-04-01

Lanzarote Island is an emergent part of the East Canary Ridge and it is situated approximately 100 km from the NW coast of Morocco, covering an area of about 795km2. The largest historical eruption of the Canary Islands, Timanfaya, took place during 1730-36 in this island when long-term eruptions from a NE-SW-trending fissure formed the Montañas del Fuego. The last eruption at Lanzarote Island occurred during 1824, Tinguaton volcano, and produced a much smaller lava flow that reached the SW coast. At present, one of the most prominent phenomena at Timanfaya volcanic field is the high maintained superficial temperatures occurring in the area since the 1730 volcanic eruption. The maximum temperatures recorded in this zone are 605°C, taken in a slightly inclined well 13 m deep. Since fumarolic activity is absent at the surface environment of Lanzarote, to study the diffuse CO2 emission becomes an ideal geochemical tool for monitoring its volcanic activity. Soil CO2 efflux surveys were conducted throughout Timanfaya volcanic field and surrounding areas during the summer periods of 2006, 2007, 2008, 2009, fall period of 2010 and winter, spring and summer periods of 2011 to investigate long and short-term temporal variations of the diffuse CO2 emission from Timanfaya volcano. Soil CO2 efflux surveys were undertaken at Timanfaya volcanic field always under stable weather conditions to minimize effects of meteorological conditions on the CO2 at the soil atmosphere. Approximately 370-430 sampling sites were selected at the surface environment of Timanfaya to obtain an even distribution of the sampling points over the study area. The accumulation chamber method (Parkinson et al., 1981) was used to perform soil CO2 efflux measurements in-situ by means of a portable non dispersive infrared (NDIR) CO2 analyzer, which was interfaced to a hand size computer that runs data acquisition software. At each sampling site, soil temperature at 15 and 40cm depth was also measured by means of a thermocouple together with soil gas samples collected during the campaign of 2010 to evaluate the chemical and isotopic composition of soil gases. Diffuse CO2 emission values have ranged between non detectable values to 34 g m-2 d-1, and most of the study area have shown relatively low values, around the detection limit of the instrument (~0,5 g m-2 d-1). Higher soil CO2 diffuse emission values were observed where thermal anomalies occur, indicating a convective mechanism transport of gas from depth at these areas. Total CO2 outputs of the study area have been estimated in the range 41-518 t d-1 during the study period. Long-term temporal variation on total CO2 diffuse emission shows a peak recorded on winter 2011, suggesting a seasonal control on the CO2 emission. As part of the volcanic surveillance program and to understand the dynamics of CO2 diffuse emission at Timanfaya volcanic zone, an automatic geochemical station was installed in July 2010 to monitor the CO2 emission and investigate the short-term temporal variation. Time series of soil CO2 efflux shows also a close relationship with seasonal changes mainly due to rainfall.

CO2 Annual and Semiannual Cycles from Satellite Retrievals and Models

NASA Astrophysics Data System (ADS)

Jiang, X.; Crisp, D.; Olsen, E. T.; Kulawik, S. S.; Miller, C. E.; Pagano, T. S.; Yung, Y. L.

2014-12-01

We have compared satellite CO2 retrievals from the Greenhouse gases Observing SATellite (GOSAT), Atmospheric Infrared Sounder (AIRS), and Tropospheric Emission Spectrometer (TES) with in-situ measurements from the Earth System Research Laboratory (NOAA-ESRL) Surface CO2 and Total Carbon Column Observing Network (TCCON), and utilized zonal means to characterize variability and distribution of CO2. In general, zonally averaged CO2 from the three satellite data sets are consistent with the surface and TCCON XCO2 data. Retrievals of CO2 from the three satellites show more (less) CO2 in the northern hemisphere than that in the southern hemisphere in the northern hemispheric winter (summer) season. The difference between the three satellite CO2 retrievals might be related to the different averaging kernels in the satellites CO2 retrievals. A multiple regression method was used to calculate the CO2 annual cycle and semiannual cycle amplitudes from different satellite CO2 retrievals. The CO2 annual cycle and semiannual cycle amplitudes are largest at the surface, as seen in the NOAA-ESRL CO2 data sets. The CO2 annual cycle and semiannual cycle amplitudes in the GOSAT XCO2, AIRS mid-tropospheric CO2, and TES mid-tropospheric CO2 are smaller compared with those from the surface CO2. Similar regression analysis was applied to the Model for OZone And Related chemical Tracers-2 (MOZART-2) and CarbonTracker model CO2. The convolved model CO2 annual cycle and semiannual cycle amplitudes are similar to those from the satellite CO2 retrievals, although the model tends to under-estimate the CO2 seasonal cycle amplitudes in the northern hemisphere mid-latitudes from the comparison with GOSAT and TES CO2 and underestimate the CO2 semi-annual cycle amplitudes in the high latitudes from the comparison with AIRS CO2. The difference between model and satellite CO2 can be used to identify possible deficiency in the model and improve the model in the future.

Magnetotelluric Detection Thresholds as a Function of Leakage Plume Depth, TDS and Volume

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

Yang, X.; Buscheck, T. A.; Mansoor, K.

We conducted a synthetic magnetotelluric (MT) data analysis to establish a set of specific thresholds of plume depth, TDS concentration and volume for detection of brine and CO 2 leakage from legacy wells into shallow aquifers in support of Strategic Monitoring Subtask 4.1 of the US DOE National Risk Assessment Partnership (NRAP Phase II), which is to develop geophysical forward modeling tools. 900 synthetic MT data sets span 9 plume depths, 10 TDS concentrations and 10 plume volumes. The monitoring protocol consisted of 10 MT stations in a 2×5 grid laid out along the flow direction. We model the MTmore » response in the audio frequency range of 1 Hz to 10 kHz with a 50 Ωm baseline resistivity and the maximum depth up to 2000 m. Scatter plots show the MT detection thresholds for a trio of plume depth, TDS concentration and volume. Plumes with a large volume and high TDS located at a shallow depth produce a strong MT signal. We demonstrate that the MT method with surface based sensors can detect a brine and CO 2 plume so long as the plume depth, TDS concentration and volume are above the thresholds. However, it is unlikely to detect a plume at a depth larger than 1000 m with the change of TDS concentration smaller than 10%. Simulated aquifer impact data based on the Kimberlina site provides a more realistic view of the leakage plume distribution than rectangular synthetic plumes in this sensitivity study, and it will be used to estimate MT responses over simulated brine and CO 2 plumes and to evaluate the leakage detectability. Integration of the simulated aquifer impact data and the MT method into the NRAP DREAM tool may provide an optimized MT survey configuration for MT data collection. This study presents a viable approach for sensitivity study of geophysical monitoring methods for leakage detection. The results come in handy for rapid assessment of leakage detectability.« less

Atlantic cod actively avoid CO2 and predator odour, even after long-term CO2 exposure.

PubMed

Jutfelt, Fredrik; Hedgärde, Maria

2013-12-27

The rising atmospheric CO2 level is continuously driving the dissolution of more CO2 into the oceans, and some emission scenarios project that the surface waters may reach 1000 μatm by the end of the century. It is not known if fish can detect moderately elevated CO2 levels, and if they avoid areas with high CO2. If so, avoidance behaviour to water with high CO2 could affect movement patterns and migrations of fish in the future. It is also being increasingly recognized that fish behaviour can be altered by exposure to CO2. Therefore this study investigated how long-term exposure to elevated pCO2 affects predator avoidance and CO2 avoidance in juvenile Atlantic cod (Gadus morhua). The fish were exposed to control water or CO2-enriched water (1000 μatm) for six weeks before being subjected to tests of behaviour. Despite long term exposure to elevated pCO2 the cod still strongly avoided the smell of a predator. These data are surprising because several coral reef fish have demonstrated reversal of olfactory responses after CO2 exposure, turning avoidance of predator cues into preference for predator cues. Fish from both treatment groups also demonstrated strong avoidance of CO2 when presented with the choice of control or CO2-acidified water, indicating that habituation to the CO2 sensory stimuli is negligible. As Atlantic cod maintained normal behavioural responses to olfactory cues, they may be tolerant to CO2-induced behavioural changes. The results also suggest that despite the long-term exposure to CO2-acidified water, the fish still preferred the control water over CO2-acidified water. Therefore, in the future, fish may alter their movements and migrations in search of waters with a lower CO2 content.

Atlantic cod actively avoid CO2 and predator odour, even after long-term CO2 exposure

PubMed Central

2013-01-01

Introduction The rising atmospheric CO2 level is continuously driving the dissolution of more CO2 into the oceans, and some emission scenarios project that the surface waters may reach 1000 μatm by the end of the century. It is not known if fish can detect moderately elevated CO2 levels, and if they avoid areas with high CO2. If so, avoidance behaviour to water with high CO2 could affect movement patterns and migrations of fish in the future. It is also being increasingly recognized that fish behaviour can be altered by exposure to CO2. Therefore this study investigated how long-term exposure to elevated pCO2 affects predator avoidance and CO2 avoidance in juvenile Atlantic cod (Gadus morhua). The fish were exposed to control water or CO2-enriched water (1000 μatm) for six weeks before being subjected to tests of behaviour. Results Despite long term exposure to elevated pCO2 the cod still strongly avoided the smell of a predator. These data are surprising because several coral reef fish have demonstrated reversal of olfactory responses after CO2 exposure, turning avoidance of predator cues into preference for predator cues. Fish from both treatment groups also demonstrated strong avoidance of CO2 when presented with the choice of control or CO2-acidified water, indicating that habituation to the CO2 sensory stimuli is negligible. Conclusions As Atlantic cod maintained normal behavioural responses to olfactory cues, they may be tolerant to CO2-induced behavioural changes. The results also suggest that despite the long-term exposure to CO2-acidified water, the fish still preferred the control water over CO2-acidified water. Therefore, in the future, fish may alter their movements and migrations in search of waters with a lower CO2 content. PMID:24373523

Synthesis of a new magnetic-MIP for the selective detection of 1-chloro-2,4-dinitrobenzene, a highly allergenic compound.

PubMed

Uzuriaga-Sánchez, Rosario Josefina; Wong, Ademar; Khan, Sabir; Pividori, Maria I; Picasso, Gino; Sotomayor, Maria D P T

2017-05-01

Molecularly imprinted polymers (MIPs) in combination with magnetic nanoparticles, in a core@shell format, were studied for selective detection of 1-chloro-2,4-dinitrobenzene (CDNB), a powerful allergenic substance. Magnetic nanoparticles were prepared by the co-precipitation method and mixed with oleic acid (OA). This material was then encapsulated in three types of hydrophobic polymeric matrix, poly-(MA-co-EDGMA), poly-(AA-co-EDGMA), and poly-(1-VN-co-EDGMA), by the mini-emulsion method. These matrices were used due to their ability to interact specifically with the functional groups of the analyte. Finally, the MIP-CDNB was obtained on the magnetic-hydrophobic surfaces using precipitation polymerization in the presence of the analyte. XRD diffraction patterns suggested the presence of magnetite in the composite and SEM analysis revealed a nanoparticle size between 10 and 18nm. Under the optimized adsorption conditions, the magnetic-MIP material showed a higher adsorption capacity (5.1mgg -1 ) than its non-magnetic counterpart (4.2mgg -1 ). In tests of the selectivity of the magnetic-MIP towards CDNB, α-values of 2.5 and 10.4, respectively, were obtained for dichlorophenol and o-nitrophenol, two structurally similar compounds, and no adsorption was observed for any other non-analogous analyte. The magnetic-MIP and magnetic-NIP were applied using water enriched with 0.5mgL -1 of CDNB, achieving recovery values of 83.8(±0.8)% and 66(±1)%, respectively, revealing the suitability of the material for detection of CDNB. Copyright © 2016 Elsevier B.V. All rights reserved.

High-frequency pressure variations in the vicinity of a surface CO2 flux chamber

Treesearch

Eugene S. Takle; James R. Brandle; R. A. Schmidt; Rick Garcia; Irina V. Litvina; William J. Massman; Xinhua Zhou; Geoffrey Doyle; Charles W. Rice

2003-01-01

We report measurements of 2Hz pressure fluctuations at and below the soil surface in the vicinity of a surface-based CO2 flux chamber. These measurements were part of a field experiment to examine the possible role of pressure pumping due to atmospheric pressure fluctuations on measurements of surface fluxes of CO2. Under the moderate wind speeds, warm temperatures,...

A joint data assimilation system (Tan-Tracker) to simultaneously estimate surface CO2 fluxes and 3-D atmospheric CO2 concentrations from observations

NASA Astrophysics Data System (ADS)

Tian, X.; Xie, Z.; Liu, Y.; Cai, Z.; Fu, Y.; Zhang, H.; Feng, L.

2014-12-01

We have developed a novel framework ("Tan-Tracker") for assimilating observations of atmospheric CO2 concentrations, based on the POD-based (proper orthogonal decomposition) ensemble four-dimensional variational data assimilation method (PODEn4DVar). The high flexibility and the high computational efficiency of the PODEn4DVar approach allow us to include both the atmospheric CO2 concentrations and the surface CO2 fluxes as part of the large state vector to be simultaneously estimated from assimilation of atmospheric CO2 observations. Compared to most modern top-down flux inversion approaches, where only surface fluxes are considered as control variables, one major advantage of our joint data assimilation system is that, in principle, no assumption on perfect transport models is needed. In addition, the possibility for Tan-Tracker to use a complete dynamic model to consistently describe the time evolution of CO2 surface fluxes (CFs) and the atmospheric CO2 concentrations represents a better use of observation information for recycling the analyses at each assimilation step in order to improve the forecasts for the following assimilations. An experimental Tan-Tracker system has been built based on a complete augmented dynamical model, where (1) the surface atmosphere CO2 exchanges are prescribed by using a persistent forecasting model for the scaling factors of the first-guess net CO2 surface fluxes and (2) the atmospheric CO2 transport is simulated by using the GEOS-Chem three-dimensional global chemistry transport model. Observing system simulation experiments (OSSEs) for assimilating synthetic in situ observations of surface CO2 concentrations are carefully designed to evaluate the effectiveness of the Tan-Tracker system. In particular, detailed comparisons are made with its simplified version (referred to as TT-S) with only CFs taken as the prognostic variables. It is found that our Tan-Tracker system is capable of outperforming TT-S with higher assimilation precision for both CO2 concentrations and CO2 fluxes, mainly due to the simultaneous estimation of CO2 concentrations and CFs in our Tan-Tracker data assimilation system. A experiment for assimilating the real dry-air column CO2 retrievals (XCO2) from the Japanese Greenhouse Gases Observation Satellite (GOSAT) further demonstrates its potential wide applications.

DFT study of CO2 conversion on InZr3(110) surface.

PubMed

Zhang, Minhua; Dou, Maobin; Yu, Yingzhe

2017-11-01

Methanol and methane synthesis from CO 2 hydrogenation on a InZr 3 (110) surface has been studied using density functional theory calculations. The CO 2 can be chemically adsorbed via a polydentated configuration and the H 2 molecule can dissociate to H atoms spontaneously. The methanol is primarily formed via the HCOO route instead of the RWGS route, due to its higher activation barrier of 1.35 eV for HCO hydrogenation. In the HCOO route, the adsorbed CO 2 consecutively hydrogenates to form HCOO, H 2 COO and the H 3 CO species. The H 3 COH is produced via the reaction of H 3 CO with a surface OH group. Furthermore, the C-O bonds of CO, CHO, CH 2 O and CH 3 O species prefer to dissociate to C, CH, CH 2 CH 3 and surface O species. Methane is formed via the hydrogenation of CH x (x = 0-3) monomers with the highest activation barrier of 1.19 eV for CH 3 hydrogenation, which is higher than that of the hydrogenation of H 2 COO in methanol synthesis via the HCOO route. The surface O species formed during CO 2 hydrogenation reacts with the adsorbed H 2 molecule to produce an OH group which reacts with a surface H atom to form H 2 O with an activation barrier of 1.13 eV, which then desorbs to the gas phase. Our calculated results indicate that the InZr 3 alloy is a potential candidate catalyst for CO 2 utilization and conversion.

Unraveling the dynamics of magmatic CO2 degassing at Mammoth Mountain, California

NASA Astrophysics Data System (ADS)

Peiffer, Loïc; Wanner, Christoph; Lewicki, Jennifer L.

2018-02-01

The accumulation of magmatic CO2 beneath low-permeability barriers may lead to the formation of CO2-rich gas reservoirs within volcanic systems. Such accumulation is often evidenced by high surface CO2 emissions that fluctuate over time. The temporal variability in surface degassing is believed in part to reflect a complex interplay between deep magmatic degassing and the permeability of degassing pathways. A better understanding of the dynamics of CO2 degassing is required to improve monitoring and hazards mitigation in these systems. Owing to the availability of long-term records of CO2 emissions rates and seismicity, Mammoth Mountain in California constitutes an ideal site towards such predictive understanding. Mammoth Mountain is characterized by intense soil CO2 degassing (up to ∼1000 t d-1) and tree kill areas that resulted from leakage of CO2 from a CO2-rich gas reservoir located in the upper ∼4 km. The release of CO2-rich fluids from deeper basaltic intrusions towards the reservoir induces seismicity and potentially reactivates faults connecting the reservoir to the surface. While this conceptual model is well-accepted, there is still a debate whether temporally variable surface CO2 fluxes directly reflect degassing of intrusions or variations in fault permeability. Here, we report the first large-scale numerical model of fluid and heat transport for Mammoth Mountain. We discuss processes (i) leading to the initial formation of the CO2-rich gas reservoir prior to the occurrence of high surface CO2 degassing rates and (ii) controlling current CO2 degassing at the surface. Although the modeling settings are site-specific, the key mechanisms discussed in this study are likely at play at other volcanic systems hosting CO2-rich gas reservoirs. In particular, our model results illustrate the role of convection in stripping a CO2-rich gas phase from a rising hydrothermal fluid and leading to an accumulation of a large mass of CO2 (∼107-108 t) in a shallow gas reservoir. Moreover, we show that both, short-lived (months to years) and long-lived (hundreds of years) events of magmatic fluid injection can lead to critical pressures within the reservoir and potentially trigger fault reactivation. Our sensitivity analysis suggests that observed temporal fluctuations in surface degassing are only indirectly controlled by variations in magmatic degassing and are mainly the result of temporally variable fault permeability. Finally, we suggest that long-term CO2 emission monitoring, seismic tomography and coupled thermal-hydraulic-mechanical modeling are important for CO2-related hazard mitigation.

Detection of magnetic microbeads and ferrofluid with giant magnetoresistance sensors

NASA Astrophysics Data System (ADS)

Feng, J.; Wang, Y. Q.; Li, F. Q.; Shi, H. P.; Chen, X.

2011-01-01

Giant magnetoresistance sensors based on multilayers [Cu/NiFeCo]×10/ Ta were fabricated by microfabrication technology. A GMR-bridge was used to detect the magnetic MyOne beads and Ferro fluid. The dependence of the GMR-bridge signals on the surface coverage of MyOne beads was studied. The results show that the GMR sensor is capable of detecting the magnetic beads. The detectable limit of MyOne beads is about 100, and the corresponding signal output is 8 μV. The GMR bridge signal is proportional to the surface coverage of the MyOne beads. The sensitivity of the GMR bridge is inversely proportional to the feature size of the GMR sensor. The GMR bridge integrated with microfludic channel was also used for dynamic detection of ferrofluid (suspension of Fe3O4 particles). The results show that the GMR bridge is capable of detecting the flow of ferrofluid, and the sensor signals are proportional to the concentration of the ferrofluid. The detection limit of concentration of the ferrofluid is 0.56 mg/ml, and the corresponding signal is 6.2 μV.

Detecting and Constraining N2 Abundances in Planetary Atmospheres Using Collisional Pairs

NASA Astrophysics Data System (ADS)

Schwieterman, Edward W.; Robinson, Tyler D.; Meadows, Victoria S.; Misra, Amit; Domagal-Goldman, Shawn

2015-09-01

Characterizing the bulk atmosphere of a terrestrial planet is important for determining surface pressure and potential habitability. Molecular nitrogen (N2) constitutes the largest fraction of Earth's atmosphere and is likely to be a major constituent of many terrestrial exoplanet atmospheres. Due to its lack of significant absorption features, N2 is extremely difficult to remotely detect. However, N2 produces an N2-N2 collisional pair, (N2)2, which is spectrally active. Here we report the detection of (N2)2 in Earth's disk-integrated spectrum. By comparing spectra from NASA's EPOXI mission to synthetic spectra from the NASA Astrobiology Institute's Virtual Planetary Laboratory three-dimensional spectral Earth model, we find that (N2)2 absorption produces a ˜35% decrease in flux at 4.15 μm. Quantifying N2 could provide a means of determining bulk atmospheric composition for terrestrial exoplanets and could rule out abiotic O2 generation, which is possible in rarefied atmospheres. To explore the potential effects of (N2)2 in exoplanet spectra, we used radiative transfer models to generate synthetic emission and transit transmission spectra of self-consistent N2-CO2-H2O atmospheres, and analytic N2-H2 and N2-H2-CO2 atmospheres. We show that (N2)2 absorption in the wings of the 4.3 μm CO2 band is strongly dependent on N2 partial pressures above 0.5 bar and can significantly widen this band in thick N2 atmospheres. The (N2)2 transit transmission signal is up to 10 ppm for an Earth-size planet with an N2-dominated atmosphere orbiting within the habitable zone of an M5V star and could be substantially larger for planets with significant H2 mixing ratios.

Modeling CO2-Water-Mineral Wettability and Mineralization for Carbon Geosequestration.

PubMed

Liang, Yunfeng; Tsuji, Shinya; Jia, Jihui; Tsuji, Takeshi; Matsuoka, Toshifumi

2017-07-18

Carbon dioxide (CO 2 ) capture and storage (CCS) is an important climate change mitigation option along with improved energy efficiency, renewable energy, and nuclear energy. CO 2 geosequestration, that is, to store CO 2 under the subsurface of Earth, is feasible because the world's sedimentary basins have high capacity and are often located in the same region of the world as emission sources. How CO 2 interacts with the connate water and minerals is the focus of this Account. There are four trapping mechanisms that keep CO 2 in the pores of subsurface rocks: (1) structural trapping, (2) residual trapping, (3) dissolution trapping, and (4) mineral trapping. The first two are dominated by capillary action, where wettability controls CO 2 and water two-phase flow in porous media. We review state-of-the-art studies on CO 2 /water/mineral wettability, which was found to depend on pressure and temperature conditions, salt concentration in aqueous solutions, mineral surface chemistry, and geometry. We then review some recent advances in mineral trapping. First, we show that it is possible to reproduce the CO 2 /water/mineral wettability at a wide range of pressures using molecular dynamics (MD) simulations. As the pressure increases, CO 2 gas transforms into a supercritical fluid or liquid at ∼7.4 MPa depending on the environmental temperature. This transition leads to a substantial decrease of the interfacial tension between CO 2 and reservoir brine (or pure water). However, the wettability of CO 2 /water/rock systems depends on the type of rock surface. Recently, we investigated the contact angle of CO 2 /water/silica systems with two different silica surfaces using MD simulations. We found that contact angle increased with pressure for the hydrophobic (siloxane) surface while it was almost constant for the hydrophilic (silanol) surface, in excellent agreement with experimental observations. Furthermore, we found that the CO 2 thin films at the CO 2 -hydrophilic silica and CO 2 -H 2 O interfaces displayed a linear correlation, which can in turn explain the constant contact angle on the hydrophilic silica surface. In view of the literature and our study results, a few recommendations seem necessary to construct a molecular system suitable to study wettability with MD simulations. Future work should be conducted to determine the influence of brine salinity on the wettability of minerals with high cation exchange capacity. Mineral trapping is believed to be an extremely slow process, likely taking thousands of years. However, a recent pilot study demonstrated that CO 2 mineralization occurs within 2 years in highly reactive basalt reservoirs. A first-principles MD study has also shown that carbonation reactions occur rapidly at the surface oxygen sites of a reactive mineral. We observed carbonate ions on both a newly cleaved quartz surface (without hydrolysis), and a basalt andesine surface after hydrolysis in a CO 2 -rich environment. Future work should consider the influence of water, gas impurities, and mineral cation type on carbonation.

Initial Reduction of CO2 on Pd-, Ru-, and Cu-Doped CeO2(111) Surfaces: Effects of Surface Modification on Catalytic Activity and Selectivity.

PubMed

Guo, Chen; Wei, Shuxian; Zhou, Sainan; Zhang, Tian; Wang, Zhaojie; Ng, Siu-Pang; Lu, Xiaoqing; Wu, Chi-Man Lawrence; Guo, Wenyue

2017-08-09

Surface modification by metal doping is an effective treatment technique for improving surface properties for CO 2 reduction. Herein, the effects of doped Pd, Ru, and Cu on the adsorption, activation, and reduction selectivity of CO 2 on CeO 2 (111) were investigated by periodic density functional theory. The doped metals distorted the configuration of a perfect CeO 2 (111) by weakening the adjacent Ce-O bond strength, and Pd doping was beneficial for generating a highly active O vacancy. The analyses of adsorption energy, charge density difference, and density of states confirmed that the doped metals were conducive for enhancing CO 2 adsorption, especially for Cu/CeO 2 (111). The initial reductive dissociation CO 2 → CO* + O* on metal-doped CeO 2 (111) followed the sequence of Cu- > perfect > Pd- > Ru-doped CeO 2 (111); the reductive hydrogenation CO 2 + H → COOH* followed the sequence of Cu- > perfect > Ru- > Pd-doped CeO 2 (111), in which the most competitive route on Cu/CeO 2 (111) was exothermic by 0.52 eV with an energy barrier of 0.16 eV; the reductive hydrogenation CO 2 + H → HCOO* followed the sequence of Ru- > perfect > Pd-doped CeO 2 (111). Energy barrier decomposition analyses were performed to identify the governing factors of bond activation and scission along the initial CO 2 reduction routes. Results of this study provided deep insights into the effect of surface modification on the initial reduction mechanisms of CO 2 on metal-doped CeO 2 (111) surfaces.

Development and Measurements of a Mid-Infrared Multi-Gas Sensor System for CO, CO2 and CH4 Detection

PubMed Central

Dong, Ming; Zheng, Chuantao; Miao, Shuzhuo; Zhang, Yu; Du, Qiaoling; Wang, Yiding

2017-01-01

A multi-gas sensor system was developed that uses a single broadband light source and multiple carbon monoxide (CO), carbon dioxide (CO2) and methane (CH4) pyroelectric detectors by use of the time division multiplexing (TDM) technique. A stepper motor-based rotating system and a single-reflection spherical optical mirror were designed and adopted to realize and enhance multi-gas detection. Detailed measurements under static detection mode (without rotation) and dynamic mode (with rotation) were performed to study the performance of the sensor system for the three gas species. Effects of the motor rotating period on sensor performances were also investigated and a rotation speed of 0.4π rad/s was required to obtain a stable sensing performance, corresponding to a detection period of ~10 s to realize one round of detection. Based on an Allan deviation analysis, the 1σ detection limits under static operation are 2.96, 4.54 and 2.84 parts per million in volume (ppmv) for CO, CO2 and CH4, respectively and the 1σ detection limits under dynamic operations are 8.83, 8.69 and 10.29 ppmv for the three gas species, respectively. The reported sensor has potential applications in various fields requiring CO, CO2 and CH4 detection such as in coal mines. PMID:28953260

Laser Sounder for Global Measurement of CO2 Concentrations in the Troposphere from Space

NASA Technical Reports Server (NTRS)

Abshire, James B.; Riris, Haris; Kawa, S. Randy; Sun, Xiaoli; Chen, Jeffrey; Stephen, Mark A.; Collatz, G. James; Mao, Jianping; Allan, Graham

2007-01-01

Measurements of tropospheric CO2 abundance with global-coverage, a few hundred km spatial and monthly temporal resolution are needed to quantify processes that regulate CO2 storage by the land and oceans. The Orbiting Carbon Observatory (OCO) is the first space mission focused on atmospheric CO2 for measuring total column CO, and O2 by detecting the spectral absorption in reflected sunlight. The OCO mission is an essential step, and will yield important new information about atmospheric CO2 distributions. However there are unavoidable limitations imposed by its measurement approach. These include best accuracy only during daytime at moderate to high sun angles, interference by cloud and aerosol scattering, and limited signal from CO2 variability in the lower tropospheric CO2 column. We have been developing a new laser-based technique for the remote measurement of the tropospheric CO2 concentrations from orbit. Our initial goal is to demonstrate a lidar technique and instrument technology that will permit measurements of the CO2 column abundance in the lower troposphere from aircraft. Our final goal is to develop a space instrument and mission approach for active measurements of the CO2 mixing ratio at the 1-2 ppmv level. Our technique is much less sensitive to cloud and atmospheric scattering conditions and would allow continuous measurements of CO2 mixing ratio in the lower troposphere from orbit over land and ocean surfaces during day and night. Our approach is to use the 1570nm CO2 band and a 3-channel laser absorption spectrometer (i.e. lidar used an altimeter mode), which continuously measures at nadir from a near polar circular orbit. The approach directs the narrow co-aligned laser beams from the instrument's lasers toward nadir, and measures the energy of the laser echoes reflected from land and water surfaces. It uses several tunable fiber laser transmitters which allowing measurement of the extinction from a single selected CO2 absorption line in the 1570 nm band. This band is free from interference from other gases and has temperature insensitive absorption lines. During the measurement the lasers are tuned on- and off- a selected CO2 line near 1572 nm and a selected O2 line near 768 nm in the Oxygen A band at kHz rates. The lasers use tunable diode seed lasers followed by fiber amplifiers, and have spectral widths much narrower than the gas absorption lines. The receiver uses a 1-m diameter telescope and photon counting detectors and measures the background light and energies of the laser echoes from the surface. The extinction and column densities for the CO2 and O2 gases are estimated from the ratio of the on and offline surface echo via the differential optical absorption technique. Our technique rapidly alternates between several on-line wavelengths set to the sides of the selected gas absorption lines. It exploits the atmospheric pressure broadening of the lines to weight the measurement sensitivity to the atmospheric column below 5 km. This maximizes sensitivity to CO2 in the boundary layer, where variations caused by surface sources and sinks are largest. Simultaneous measurements of O2 column will use an identical approach with an O2 line. Thee laser frequencies are tunable and have narrow (MHz) line widths. In combination with sensitive photon counting detectors these enables much higher spectral resolution and precision than is possible with passive spectrometer. 1aser backscatter profiles are also measured, which permits identifying measurements made to cloud tops and through aerosol layers. The measurement approach using lasers in common-nadir-zenith path allows retrieving CO2 column mixing ratios in the lower troposphere irrespective of sun angle. Pulsed laser signals, time gated receiver and a narrow receiver field-of-view are used to isolate the surface laser echo signals and to exclude photons scattered from clouds and aerosols. Nonetheless, the optical absorption change due to a change of a few ppO2 is small, <1 % which makes achieving the needed measurement sensitivities and stabilities quite challenging. Measurement SNRs and stabilities of >600:1 are needed to estimate CO2 mixing ratio at the 1-2 ppm level. We have calculated characteristics of the technique and have demonstrated aspects of the laser, detector and receiver approaches in th e laboratory We have also measured O2 in an absorption cell, and made C02 measurements over a 400 m long (one way) horizontal path using a sensor breadboard. We will describe these and more details of our approach in the paper.

The OceanFlux Greenhouse Gases methodology for deriving a sea surface climatology of CO2 fugacity in support of air-sea gas flux studies

NASA Astrophysics Data System (ADS)

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

2015-07-01

Climatologies, or long-term averages, of essential climate variables are useful for evaluating models and providing a baseline for studying anomalies. The Surface Ocean CO2 Atlas (SOCAT) has made millions of global underway sea surface measurements of CO2 publicly available, all in a uniform format and presented as fugacity, fCO2. As fCO2 is highly sensitive to temperature, the measurements are only valid for the instantaneous sea surface temperature (SST) that is measured concurrently with the in-water CO2 measurement. To create a climatology of fCO2 data suitable for calculating air-sea CO2 fluxes, it is therefore desirable to calculate fCO2 valid for a more consistent and averaged SST. This paper presents the OceanFlux Greenhouse Gases methodology for creating such a climatology. We recomputed SOCAT's fCO2 values for their respective measurement month and year using monthly composite SST data on a 1° × 1° grid from satellite Earth observation and then extrapolated the resulting fCO2 values to reference year 2010. The data were then spatially interpolated onto a 1° × 1° grid of the global oceans to produce 12 monthly fCO2 distributions for 2010, including the prediction errors of fCO2 produced by the spatial interpolation technique. The partial pressure of CO2 (pCO2) is also provided for those who prefer to use pCO2. The CO2 concentration difference between ocean and atmosphere is the thermodynamic driving force of the air-sea CO2 flux, and hence the presented fCO2 distributions can be used in air-sea gas flux calculations together with climatologies of other climate variables.

An optically detectable CO2 sensor utilizing polyethylenimine and starch functionalized InGaN/GaN multiple quantum wells

NASA Astrophysics Data System (ADS)

Chen, Y. C.; Shih, H. Y.; Chen, J. Y.; Tan, W. J.; Chen, Y. F.

2013-07-01

An optically detectable gas sensor based on the high surface sensitivity of functionalized polyethylenimine/starch In0.15Ga0.85N/GaN strained semiconductor multiple quantum wells (MQWs) has been developed. Due to the excellent piezoelectricity of the MQWs, the change of surface charges caused by chemical interaction can introduce a strain and induce an internal field. In turn, it tilts the energy levels of the MQWs and modifies the optical properties. Through the measurement of the changes in photoluminescence as well as Raman scattering spectra under different concentrations of carbon dioxide gas, we demonstrate the feasibility and high sensitivity of the sensors derived from our methodology.

Monthly CO2 at A4HDYD station in a productive shallow marginal sea (Yellow Sea) with a seasonal thermocline: Controlling processes

NASA Astrophysics Data System (ADS)

Xu, Xuemei; Zang, Kunpeng; Zhao, Huade; Zheng, Nan; Huo, Cheng; Wang, Juying

2016-07-01

Based upon 21 field surveys conducted from March 2011 to November 2013, monthly variation of carbon dioxide partial pressure (pCO2) and other carbon system parameters were investigated for the first time (to our knowledge) at A4HDYD station (38°40‧N, 122°10‧E) located in the North Yellow Sea, a region with a seasonal thermocline. Surface pCO2 was undersaturated from March to May and nearly in equilibrium with the atmosphere from June to August. During September and November, pCO2 declined to a lower level than that from June to August, but reached the highest level in December. In contrast, pCO2 declined to atmospheric CO2 levels in February. Overall, the study area was a net CO2 sink at a rate of 0.85 ± 0.59 mol C m- 2 yr- 1. The underlying processes governing the variation of pCO2 were also examined. In general, temperature had an important influence on the monthly variation of pCO2, but its effect was counterbalanced by biological production in spring and vertical mixing in early winter. Our study indicated that dynamic mechanism studies based on high temporal resolution observations are urgently needed to understand the complexity of the carbon cycle and detect biogeochemical changes or ecosystem responses to climate change on continental margins.

Geological Carbon Sequestration: A New Approach for Near-Surface Assurance Monitoring

PubMed Central

Wielopolski, Lucian

2011-01-01

There are two distinct objectives in monitoring geological carbon sequestration (GCS): Deep monitoring of the reservoir’s integrity and plume movement and near-surface monitoring (NSM) to ensure public health and the safety of the environment. However, the minimum detection limits of the current instrumentation for NSM is too high for detecting weak signals that are embedded in the background levels of the natural variations, and the data obtained represents point measurements in space and time. A new approach for NSM, based on gamma-ray spectroscopy induced by inelastic neutron scatterings (INS), offers novel and unique characteristics providing the following: (1) High sensitivity with a reducible error of measurement and detection limits, and, (2) temporal- and spatial-integration of carbon in soil that results from underground CO2 seepage. Preliminary field results validated this approach showing carbon suppression of 14% in the first year and 7% in the second year. In addition the temporal behavior of the error propagation is presented and it is shown that for a signal at the level of the minimum detection level the error asymptotically approaches 47%. PMID:21556180

Acetaldehyde Adsorption and Reaction onCeO2(100) Thin Films

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

Mullins, David R; Albrecht, Peter M

2013-01-01

This study reports and compares the adsorption and dissociation of acetaldehyde on oxidized and reduced CeOX(100) thin films. Acetaldehyde reacts and decomposes on fully oxidized CeO2(100) whereas it desorbs molecularly at low temperature on CeO2(111). The primary products are CO, CO2 and water along with trace amounts of crotonaldehyde and acetylene. The acetaldehyde adsorbs as the 2-acetaldehyde species, dioxyethylene. Decomposition proceeds by dehydrogenation through acetate and enolate intermediates. The reaction pathway is similar on the reduced CeO2-X(100) surface however the inability to react with surface O on the reduced surface results in H2 rather than H2O desorption and C ismore » left on the surface rather than producing CO and CO2. C-O bond cleavage in the enolate intermediate followed by reaction with surface H results in ethylene desorption.« less

Metal-Organic Frameworks-Derived Hierarchical Co3O4 Structures as Efficient Sensing Materials for Acetone Detection.

PubMed

Zhang, Rui; Zhou, Tingting; Wang, Lili; Zhang, Tong

2018-03-21

Highly sensitive and stable gas sensors have attracted much attention because they are the key to innovations in the fields of environment, health, energy savings and security, etc. Sensing materials, which influence the practical sensing performance, are the crucial parts for gas sensors. Metal-organic frameworks (MOFs) are considered as alluring sensing materials for gas sensors because of the possession of high specific surface area, unique morphology, abundant metal sites, and functional linkers. Herein, four kinds of porous hierarchical Co 3 O 4 structures have been selectively controlled by optimizing the thermal decomposition (temperature, rate, and atmosphere) using ZIF-67 as precursor that was obtained from coprecipitation method with the co-assistance of cobalt salt and 2-methylimidazole in the solution of methanol. These hierarchical Co 3 O 4 structures, with controllable cross-linked channels, meso-/micropores, and adjustable surface area, are efficient catalytic materials for gas sensing. Benefits from structural advantages, core-shell, and porous core-shell Co 3 O 4 exhibit enhanced sensing performance compared to those of porous popcorn and nanoparticle Co 3 O 4 to acetone gas. These novel MOF-templated Co 3 O 4 hierarchical structures are so fantastic that they can be expected to be efficient sensing materials for development of low-temperature operating gas sensors.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Subsurface oxide plays a critical role in CO 2 activation by Cu(111) surfaces to form chemisorbed CO 2, the first step in reduction of CO 2

DOE PAGES

Favaro, Marco; Xiao, Hai; Cheng, Tao; ...

2017-06-12

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide ismore » essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.« less

Detecting Patterns of Changing Carbon Uptake in Alaska Using Sustained In Situ and Remote Sensing CO2 Observations

NASA Astrophysics Data System (ADS)

Parazoo, N.; Miller, C. E.; Commane, R.; Wofsy, S. C.; Koven, C.; Lawrence, D. M.; Lindaas, J.; Chang, R. Y. W.; Sweeney, C.

2015-12-01

The future trajectory of Arctic ecosystems as a carbon sink or source is of global importance due to vast quantities of carbon in permafrost soils. Over the last few years, a sustained set of airborne (NOAA-PFA, NOAA-ACG, and CARVE) and satellite (OCO-2 and GOSAT) atmospheric CO2 mole fraction measurements have provided unprecedented space and time scale sampling density across Alaska, making it possible to study the Arctic carbon cycle in more detail than ever before. Here, we use a synthesis of airborne and satellite CO2 over the 2009-2013 period with simulated concentrations from CLM4.5 and GEOS-Chem to examine the extent to which regional-scale carbon cycle changes in Alaska can be distinguished from interannual variability and long-range transport. We show that observational strategies focused on sustained profile measurements spanning continental interiors provide key insights into magnitude, duration, and variability of Summer sink activity, but that cold season sources are currently poorly resolved due to lack of sustained spatial sampling. Consequently, although future CO2 budgets dominated by enhanced cold season emission sources under climate warming and permafrost thaw scenarios are likely to produce substantial changes to near-surface CO2 gradients and seasonal cycle amplitude, they are unlikely to be detected by current observational strategies. We conclude that airborne and ground-based networks that provide more spatial coverage in year round profiles will help compensate for systematic sampling gaps in NIR passive satellite systems and provide essential constraints for Arctic carbon cycle changes.

A MOLECULAR STAR FORMATION LAW IN THE ATOMIC-GAS-DOMINATED REGIME IN NEARBY GALAXIES

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

Schruba, Andreas; Walter, Fabian; Dumas, Gaelle

2011-08-15

We use the IRAM HERACLES survey to study CO emission from 33 nearby spiral galaxies down to very low intensities. Using 21 cm line atomic hydrogen (H I) data, mostly from THINGS, we predict the local mean CO velocity based on the mean H I velocity. By re-normalizing the CO velocity axis so that zero corresponds to the local mean H I velocity we are able to stack spectra coherently over large regions. This enables us to measure CO intensities with high significance as low as I{sub CO} {approx} 0.3 K km s{sup -1} ({Sigma}{sub H{sub 2}}{approx}1 M{sub sun} pc{supmore » -2}), an improvement of about one order of magnitude over previous studies. We detect CO out to galactocentric radii r{sub gal} {approx} r{sub 25} and find the CO radial profile to follow a remarkably uniform exponential decline with a scale length of {approx}0.2 r{sub 25}. Here we focus on stacking as a function of radius, comparing our sensitive CO profiles to matched profiles of H I, H{alpha}, far-UV (FUV), and Infrared (IR) emission at 24 {mu}m and 70 {mu}m. We observe a tight, roughly linear relationship between CO and IR intensity that does not show any notable break between regions that are dominated by molecular gas ({Sigma}{sub H{sub 2}}>{Sigma}{sub H{sub i}}) and those dominated by atomic gas ({Sigma}{sub H{sub 2}}<{Sigma}{sub H{sub i}}). We use combinations of FUV+24 {mu}m and H{alpha}+24 {mu}m to estimate the recent star formation rate (SFR) surface density, {Sigma}{sub SFR}, and find approximately linear relations between {Sigma}{sub SFR} and {Sigma}{sub H{sub 2}}. We interpret this as evidence of stars forming in molecular gas with little dependence on the local total gas surface density. While galaxies display small internal variations in the SFR-to-H{sub 2} ratio, we do observe systematic galaxy-to-galaxy variations. These galaxy-to-galaxy variations dominate the scatter in relationships between CO and SFR tracers measured at large scales. The variations have the sense that less massive galaxies exhibit larger ratios of SFR-to-CO than massive galaxies. Unlike the SFR-to-CO ratio, the balance between atomic and molecular gas depends strongly on the total gas surface density and galactocentric radius. It must also depend on additional parameters. Our results reinforce and extend to lower surface densities, a picture in which star formation in galaxies can be separated into two processes: the assembly of star-forming molecular clouds and the formation of stars from H{sub 2}. The interplay between these processes yields a total gas-SFR relation with a changing slope, which has previously been observed and identified as a star formation threshold.« less

[Partial pressure of CO2 and CO2 degassing fluxes of Huayuankou and Xiaolangdi Station affected by Xiaolangdi Reservoir].

PubMed

Zhang, Yong-ling; Yang, Xiao-lin; Zhang, Dong

2015-01-01

According to periodic sampling analysis per month in Xiaolangdi station and Huayuankou station from November 2011 to October 2012, combined with continuous sampling analysis of Xiaolangdi Reservoir during runoff and sediment control period in 2012, partial pressure of CO2 (pCO2) in surface water were calculated based on Henry's Law, pCO2 features and air-water CO2 degassing fluxes of Huayuankou station and Xiaolangdi station affected by Xiaolangdi Reservoir were studied. The results were listed as follows, when Xiaolangdi Reservoir operated normally, pCO2 in surface water of Xiaolangdi station and Huayuankou station varied from 82 to 195 Pa and from 99 to 228 Pa, moreover, pCO2 in surface water from July to September were distinctly higher than those in other months; meanwhile, pCO, in surface water from Huayuankou station were higher than that from Xiaolangdi station. During runoff and sediment control period of Xiaolangdi Reservoir, two hydrological stations commonly indicated that pCO2 in surface water during water draining were obviously lower than those during sediment releasing. Whether in the period of normal operation or runoff and sediment control, pCO2 in surface water had positive relations to DIC content in two hydrological stations. Since the EpCO,/AOU value was higher than the theoretical value of 0. 62, the biological aerobic respiration effect had distinct contribution to pCO2. Throughout the whole year, air-water CO2 degassing fluxes from Xiaolangdi station and Huayuankou station were 0.486 p.mol (m2 s) -l and 0.588 pmol (m2 x s)(-1) respectively; When Xiaolangdi Reservoir operated normally, air-water CO, degassing fluxes in Huayuankou station were higher than that in Xiaolangdi station; during runoff and sediment control from Xiaolangdi Reservoir, two hydrological stations had one observation result in common, namely, air-water CO2 degassing fluxes in the period of water draining were obviously lower than that in the period of sediment releasing.

Inverse modeling of CO2 sources and sinks using satellite observations of CO2 from TES and surface flask measurements

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

Nassar, Ray; Jones, DBA; Kulawik, SS

2011-01-01

We infer CO2 surface fluxes using satellite observations of mid-tropospheric CO2 from the Tropospheric Emission Spectrometer (TES) and measurements of CO2 from surface flasks in a time-independent inversion analysis based on the GEOS-Chem model. Using TES CO2 observations over oceans, spanning 40 S 40 N, we find that the horizontal and vertical coverage of the TES and flask data are complementary. This complementarity is demonstrated by combining the datasets in a joint inversion, which provides better constraints than from either dataset alone, when a posteriori CO2 distributions are evaluated against independent ship and aircraft CO2 data. In particular, the jointmore » inversion offers improved constraints in the tropics where surface measurements are sparse, such as the tropical forests of South America. Aggregating the annual surface-to-atmosphere fluxes from the joint inversion for the year 2006 yields 1.13 0.21 PgC for the global ocean, 2.77 0.20 PgC for the global land biosphere and 3.90 0.29 PgC for the total global natural flux (defined as the sum of all biospheric, oceanic, and biomass burning contributions but excluding CO2 emissions from fossil fuel combustion). These global ocean and global land fluxes are shown to be near the median of the broad range of values from other inversion results for 2006. To achieve these results, a bias in TES CO2 in the Southern Hemisphere was assessed and corrected using aircraft flask data, and we demonstrate that our results have low sensitivity to variations in the bias correction approach. Overall, this analysis suggests that future carbon data assimilation systems can benefit by integrating in situ and satellite observations of CO2 and that the vertical information provided by satellite observations of mid-tropospheric CO2 combined with measurements of surface CO2, provides an important additional constraint for flux inversions.« less

Theoretical study of the promotional effect of ZrO2 on In2O3 catalyzed methanol synthesis from CO2 hydrogenation

NASA Astrophysics Data System (ADS)

Zhang, Minhua; Dou, Maobin; Yu, Yingzhe

2018-03-01

Methanol synthesis from CO2 hydrogenation on the ZrO2 doped In2O3(110) surface (Zr-In2O3(110)) with oxygen vacancy has been studied using the density functional theory calculations. The calculated results show that the doped ZrO2 species prohibits the excessive formation of oxygen vacancies and dissociation of H2 on In2O3 surface slightly, but enhances the adsorption of CO2 on both perfect and defective Zr-In2O3(110) surface. Methanol is formed via the HCOO route. The hydrogenation of CO2 to HCOO is both energetically and kinetically facile. The HCOO hydrogenates to polydentate H2CO (p-H2CO) species with an activation barrier of 0.75 eV. H3CO is produced from the hydrogenation of monodentate H2CO (mono-H2CO), transformation from p-H2CO with 0.82 eV reaction energy, with no barrier whether there is hydroxyl group between the mono-H2CO and the neighboring hydride or not. Methanol is the product of H3CO protonation with 0.75 eV barrier. The dissociation and protonation of CO2 are both energetically and kinetically prohibited on Zr-In2O3(110) surface. The doped ZrO2 species can further enhance the adsorption of all the intermediates involved in CO2 hydrogenation to methanol, activate the adsorbed CO2 and H2CO, and stabilize the HCOO, H2CO and H3CO, especially prohibit the dissociation of H2CO or the reaction of H2CO with neighboring hydride to form HCOO and gas phase H2. All these effects make the ZrO2 supported In2O3 catalyst exhibit higher activity and selectivity on methanol synthesis from CO2 hydrogenation.

Composites of ionic liquid and amine-modified SAPO 34 improve CO2 separation of CO2-selective polymer membranes

NASA Astrophysics Data System (ADS)

Hu, Leiqing; Cheng, Jun; Li, Yannan; Liu, Jianzhong; Zhang, Li; Zhou, Junhu; Cen, Kefa

2017-07-01

Mixed matrix membranes with ionic liquids and molecular sieve particles had high CO2 permeabilities, but CO2 separation from small gas molecules such as H2 was dissatisfied because of bad interfacial interaction between ionic liquid and molecular sieve particles. To solve that, amine groups were introduced to modify surface of molecular sieve particles before loading with ionic liquid. SAPO 34 was adopted as the original filler, and four mixed matrix membranes with different fillers were prepared on the outer surface of ceramic hollow fibers. Both surface voids and hard agglomerations disappeared, and the surface became smooth after SAPO 34 was modified by amine groups and ionic liquid [P66614][2-Op]. Mixed matrix membranes with composites of amine-modified SAPO 34 and ionic liquid exhibited excellent CO2 permeability (408.9 Barrers) and CO2/H2 selectivity (22.1).

Physical Activation of Oil Palm Empty Fruit Bunch via CO2 Activation Gas for CO2 Adsorption

NASA Astrophysics Data System (ADS)

Joseph, C. G.; Quek, K. S.; Daud, W. M. A. W.; Moh, P. Y.

2017-06-01

In this study, different parameters for the preparation of activated carbon were investigated for their yield and CO2 capture capabilities. The activated carbon was prepared from Oil Palm Empty Fruit Bunch (OPEFB) via a 2-step physical activation process. The OPEFB was pyrolyzed under inert conditions at 500 °C and activated via CO2. A 2-factorial design was employed and the effects of activation temperature, activation dwell time and gas flow rate on yield and CO2 capture capabilities were compared and studied. The yield obtained ranged from between 20 - 26, whereby the temperature was determined to be the most significant factor in influencing CO2 uptake. The CO2 capture capacity was determined using Temperature Programmed Desorption (TPD) technique. The CO2 uptake of EFB activated carbon achieved was between 1.85 - 2.09 mmol/g. TPD analysis has shown that the surface of AC were of basic nature. AC was found to be able to withhold the CO2 up to 663°C before maximum desorption occurs. The surface area and pore size of OPEFB obtained from BET analysis is 2.17 m2 g-1 and 0.01 cm3 g-1. After activation, both surface area and pore size increased with a maximum observed surface area and pore size of 548.07 m2 g-1 and 0.26 cm3 g-1. Surface morphology, functional groups, pore size and surface area were analyzed using SEM, FT-IR, TPD and BET.

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

DOE PAGES

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

2015-07-30

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

CO Adsorption on Reconstructed Ir(100) Surfaces from UHV to mbar Pressure: A LEED, TPD, and PM-IRAS Study

PubMed Central

2016-01-01

Clean and stable surface modifications of an iridium (100) single crystal, i.e., the (1 × 1) phase, the (5 × 1) reconstruction, and the oxygen-terminated (2 × 1)-O surface, were prepared and characterized by low energy electron diffraction (LEED), temperature-programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS) and polarization modulation IRAS (PM-IRAS). The adsorption of CO in UHV and at elevated (mbar) pressure/temperature was followed both ex situ and in situ on all three surface modifications, with a focus on mbar pressures of CO. The Ir(1 × 1) surface exhibited c(4 × 2)/c(2 × 2) and c(6 × 2) CO structures under low pressure conditions, and remained stable up to 100 mbar and 700 K. For the (2 × 1)-O reconstruction CO adsorption induced a structural change from (2 × 1)-O to (1 × 1), as confirmed by LEED, TPD, and IR. For Ir (2 × 1)-O TPD indicated that CO reacted with surface oxygen forming CO2. The (5 × 1) reconstruction featured a reversible and dynamic behavior upon CO adsorption, with a local lifting of the reconstruction to (1 × 1). After CO desorption, the (5 × 1) structure was restored. All three reconstructions exhibited CO adsorption with on-top geometry, as evidenced by IR. With increasing CO exposure the resonances shifted to higher wavenumber, due to adsorbate–adsorbate and adsorbate–substrate interactions. The largest wavenumber shift (from 2057 to 2100 cm–1) was observed for Ir(5 × 1) upon CO dosing from 1 L to 100 mbar. PMID:27257467

Effects of Hydration and Oxygen Vacancy on CO2 Adsorption and Activation on β-Ga2O3(100)

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

Pan, Yunxiang; Liu, Chang-jun; Mei, Donghai

The effects of hydration and oxygen vacancy on CO2 adsorption on the β-Ga2O3(100) surface have been studied using density functional theory slab calculations. Adsorbed CO2 is activated on the dry perfect β-Ga2O3(100) surface, resulting in a carbonate species. This adsorption is slightly endothermic, with an adsorption energy of 0.07 eV. Water is preferably adsorbed molecularly on the dry perfect β-Ga2O3(100) surface with an adsorption energy of -0.56 eV, producing a hydrated perfect β-Ga2O3(100) surface. Adsorption of CO2 on the hydrated surface as a carbonate species is also endothermic, with an adsorption energy of 0.14 eV, indicating a slight repulsive interactionmore » when H2O and CO2 are coadsorbed. The carbonate species on the hydrated perfect surface can be protonated by the co-adsorbed H2O to a bicarbonate species, making the overall process exothermic with an adsorption energy of -0.13 eV. The effect of defects on CO2 adsorption and activation has been examined by creating an oxygen vacancy on the dry β-Ga2O3(100) surface. The formation of an oxygen vacancy is endothermic, by 0.34 eV, with respect to a free O2 molecule in the gas phase. Presence of the oxygen vacancy promoted the adsorption and activation of CO2. In the most stable CO2 adsorption configuration on the dry defective β-Ga2O3(100) surface with an oxygen vacancy, one of the oxygen atoms of the adsorbed CO2 occupies the oxygen vacancy site and the CO2 adsorption energy is -0.31 eV. Water favors dissociative adsorption at the oxygen vacancy site on the defective surface. This process is instantaneous with an adsorption energy of -0.62 eV. These results indicate that, when water and CO2 are both present in the adsorption system simultaneously, the water molecule will compete with CO2 for the oxygen vacancy sites and impact CO2 adsorption and conversion negatively. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. A portion of the computing time was granted by the scientific user projects using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). The EMSL is a DOE national scientific user facility located at PNNL, and supported by the DOE’s Office of Science, Biological and Environmental Research.« less

Nanoscale PdO Catalyst Functionalized Co3O4 Hollow Nanocages Using MOF Templates for Selective Detection of Acetone Molecules in Exhaled Breath.

PubMed

Koo, Won-Tae; Yu, Sunmoon; Choi, Seon-Jin; Jang, Ji-Soo; Cheong, Jun Young; Kim, Il-Doo

2017-03-08

The increase of surface area and the functionalization of catalyst are crucial to development of high-performance semiconductor metal oxide (SMO) based chemiresistive gas sensors. Herein, nanoscale catalyst loaded Co 3 O 4 hollow nanocages (HNCs) by using metal-organic framework (MOF) templates have been developed as a new sensing platform. Nanoscale Pd nanoparticles (NPs) were easily loaded on the cavity of Co based zeolite imidazole framework (ZIF-67). The porous structure of ZIF-67 can restrict the size of Pd NPs (2-3 nm) and separate Pd NPs from each other. Subsequently, the calcination of Pd loaded ZIF-67 produced the catalytic PdO NPs functionalized Co 3 O 4 HNCs (PdO-Co 3 O 4 HNCs). The ultrasmall PdO NPs (3-4 nm) are well-distributed in the wall of Co 3 O 4 HNCs, the unique structure of which can provide high surface area and high catalytic activity. As a result, the PdO-Co 3 O 4 HNCs exhibited improved acetone sensing response (R gas /R air = 2.51-5 ppm) compared to PdO-Co 3 O 4 powders (R gas /R air = 1.98), Co 3 O 4 HNCs (R gas /R air = 1.96), and Co 3 O 4 powders (R gas /R air = 1.45). In addition, the PdO-Co 3 O 4 HNCs showed high acetone selectivity against other interfering gases. Moreover, the sensor array clearly distinguished simulated exhaled breath of diabetics from healthy people's breath. These results confirmed the novel synthesis of MOF templated nanoscale catalyst loaded SMO HNCs for high performance gas sensors.

CO 2 Adsorption on Anatase TiO 2 (101) Surfaces in the Presence of Subnanometer Ag/Pt Clusters: Implications for CO 2 Photoreduction

DOE PAGES

Yang, Chi-Ta; Wood, Brandon C.; Bhethanabotla, Venkat R.; ...

2014-10-20

We show how CO 2 adsorption on perfect and reduced anatase TiO 2 (101) surfaces can be substantially modified by the presence of surface Ag and Pt octamer clusters, using density functional theory calculations. Furthermore, we found that adsorption was affected even at sites where the adsorbate was not in direct contact with the octamer, which we attributed to charge donation to CO 2 from the Ag/Pt-modified surface, as well as an electrostatic competition between attractive (Ti–O) and repulsive (Ti–C) interactions. Additionally, TiO 2-supported Pt octamers offer key advantages that could be leveraged for CO 2 photoreduction, including providing additionalmore » stable adsorption sites for bent CO 2 species and facilitating charge transfer to aid in CO 2– anion formation. Electronic structure analysis suggests these factors arise primarily from the hybridization of the bonding molecular orbitals of CO 2 with d orbitals of the Pt atoms. Our results show that, for adsorption on TiO 2-supported Pt octamers, the O–C–O bending and C–O asymmetric stretching frequencies can be used as reliable indicators of the presence of the CO 2– anion intermediate as well as to distinguish unique adsorption geometries or sites. Finally, we suggest a possible pathway for subsequent CO 2 dissociation to CO at the surface of a reduced anatase TiO 2 (101)-supported Pt octamer, which has a computed energy barrier of 1.01 eV.« less

Leaf size and surface characteristics of Betula papyrifera exposed to elevated CO2 and O3

Treesearch

Johanna Riikonen; Kevin E. Percy; Minna Kivimaenpaa; Mark E. Kubiske; Neil D. Nelson; Elina Vapaavuori; David F. Karnosky

2010-01-01

Betula papyrifera trees were exposed to elevated concentrations of CO2 (1.4 x ambient), O3 (1.2 x ambient) or CO2 + O3 at the Aspen Free-air CO2 Enrichment Experiment. The treatment effects on leaf surface characteristics were studied...

Localization of a continuous CO2 leak from an isotropic flat-surface structure using acoustic emission detection and near-field beamforming techniques

NASA Astrophysics Data System (ADS)

Yan, Yong; Cui, Xiwang; Guo, Miao; Han, Xiaojuan

2016-11-01

Seal capacity is of great importance for the safety operation of pressurized vessels. It is crucial to locate the leak hole timely and accurately for reasons of safety and maintenance. This paper presents the principle and application of a linear acoustic emission sensor array and a near-field beamforming technique to identify the location of a continuous CO2 leak from an isotropic flat-surface structure on a pressurized vessel in the carbon capture and storage system. Acoustic signals generated by the leak hole are collected using a linear high-frequency sensor array. Time-frequency analysis and a narrow-band filtering technique are deployed to extract effective information about the leak. The impacts of various factors on the performance of the localization technique are simulated, compared and discussed, including the number of sensors, distance between the leak hole and sensor array and spacing between adjacent sensors. Experiments were carried out on a laboratory-scale test rig to assess the effectiveness and operability of the proposed method. The results obtained suggest that the proposed method is capable of providing accurate and reliable localization of a continuous CO2 leak.

Detection and impacts of leakage from sub-seafloor deep geological carbon dioxide storage

NASA Astrophysics Data System (ADS)

Blackford, Jerry; Stahl, Henrik; Bull, Jonathan M.; Bergès, Benoît J. P.; Cevatoglu, Melis; Lichtschlag, Anna; Connelly, Douglas; James, Rachael H.; Kita, Jun; Long, Dave; Naylor, Mark; Shitashima, Kiminori; Smith, Dave; Taylor, Peter; Wright, Ian; Akhurst, Maxine; Chen, Baixin; Gernon, Tom M.; Hauton, Chris; Hayashi, Masatoshi; Kaieda, Hideshi; Leighton, Timothy G.; Sato, Toru; Sayer, Martin D. J.; Suzumura, Masahiro; Tait, Karen; Vardy, Mark E.; White, Paul R.; Widdicombe, Steve

2014-11-01

Fossil fuel power generation and other industrial emissions of carbon dioxide are a threat to global climate, yet many economies will remain reliant on these technologies for several decades. Carbon dioxide capture and storage (CCS) in deep geological formations provides an effective option to remove these emissions from the climate system. In many regions storage reservoirs are located offshore, over a kilometre or more below societally important shelf seas. Therefore, concerns about the possibility of leakage and potential environmental impacts, along with economics, have contributed to delaying development of operational CCS. Here we investigate the detectability and environmental impact of leakage from a controlled sub-seabed release of CO2. We show that the biological impact and footprint of this small leak analogue (<1 tonne CO2 d-1) is confined to a few tens of metres. Migration of CO2 through the shallow seabed is influenced by near-surface sediment structure, and by dissolution and re-precipitation of calcium carbonate naturally present in sediments. Results reported here advance the understanding of environmental sensitivity to leakage and identify appropriate monitoring strategies for full-scale carbon storage operations.

Rapid detection and characterization of surface CO2 leakage through the real-time measurement of δ13C signatures in CO2 flux from the ground

NASA Astrophysics Data System (ADS)

Krevor, S.; Perrin, J.; Esposito, A.; Rella, C.; Benson, S. M.

2009-12-01

A portable stable carbon isotope ratio analyzer for carbon dioxide, based on wavelength scanned cavity ringdown spectroscopy, has been used to detect and characterize an intentional leakage of CO2 from an underground pipeline at the ZERT experimental facility in Bozeman, Montana. Rapid (~1 hour) walking surveys of the entire 100m x 100m site were collected using this mobile, real-time instrument. The resulting concentration and 13C isotopic abundance maps were processed using simple yet powerful analysis techniques, permitting not only the identification of specific leakage locations, but providing the ability to distinguish petrogenic sources of CO2 from biogenic sources. At the site an approximately 100-meter horizontal well has been drilled below an alfalfa field at a depth between 1-3 meters below the surface. The well has perforations along the central 70 meters of the well. The overlying strata are highly permeable sand, silt, and topsoil. The flora consists generally of long grasses and was cut to a height of less than 6 inches before the start of the experiment. For 30 days starting July 15, 2009, CO2 was injected at a rate of 0.2 tonnes per day. The injection rate is designed to simulate leakage from a mature storage reservoir at an annual rate of between .001 and .01%. The isotopic composition of the gas from the tank is at δ13C signature of approximately -52‰, far more negative than either atmospheric (approx. -8‰) or CO2 from soil respiration (approx. -26‰) at the site. The CO2 isotopic and concentration measurements were taken with a Picarro WS-CRDS analyzer with 1/8” tubing connected to a sampling inlet. Simultaneous with CO2 concentrations (including 13C), position data was logged using a GPS receiver. Datapoints are taken around every second. The analyzer was powered using batteries and housed in a conventional garden cart. The surveys consisted of traverses of the site along the length of the pipeline and extending out 100 meters on either side of the pipeline with the end of the gas inlet tube approximate 9 cm above the ground at a walking speed of 1-2m/sec. This simulates the type of survey that could be easily performed if the actual or potential site of a leak was known to within an area on the order of 100 square kilometers or less, the scale of expected industrial CO2 sequestration operations. The surveys were performed both during the day and during the evening when CO2 flux due to respiration from the soil is markedly different. Keeling plots were used to characterize the spatially varying 13C composition of ground source CO2 across the site. A map constructed from this data shows that CO2 flux from sources of leakage was characterized by a δ 13C of -40‰ or less whereas locations away from the leakage spots had much higher δ 13C signatures, -25‰ or higher. The distinct isotopic signature allows for a clear discernment between leakage of petrogenic CO2 and that of natural CO2 fluxes from soil respiration. This is particularly valuable in the circumstance where the leak is slow enough that it could not be identified from CO2 concentration or flux changes above the natural background signal alone.

Radon, helium and CO2 measurements in soils overlying a former exploited oilfield, Pechelbronn district, Bas-Rhin, France.

PubMed

Michel-le pierres, Karine; Gal, Frédérick; Brach, Michel; Guignat, Stéphanie

2010-10-01

The Pechelbronn oilfield (Rhine Graben, France), where mining activity ended in the 1960s, has been used for waste disposal for twenty years. Since the wastes are varied, work is underway to identify the discharged materials and their derivatives, as well as to locate and quantify potential discharge sites. Two major goals were assigned to the present work. The first was to identify or refine the location of hidden structures that could facilitate gas emanation up to the surface, by studying soil gas concentrations (mainly (222)Rn, CO(2), CH(4) and helium) and carbon isotope ratios in the CO(2) phase. The second was devoted to examining, from a health and safety viewpoint, if the use of the oilfield as a waste disposal site might have led to enhanced or modified gas emanation throughout the area. It appeared that CO(2) and (222)Rn evolution in the whole area were similar, except near some of the faults and fractures that are known through surface mapping and underground observations. These (222)Rn and CO(2) anomalies made it possible to highlight more emissive zones that are either related to main faults or to secondary fractures acting as migration pathways. In that sense, the CO(2) phase can be used to evaluate (222)Rn activities distant from tectonic structures but can lead to erroneous evaluations near to gas migration pathways. Dumping of wastes, as well as oil residues, did not appear to have a strong influence on soil gaseous species and emanation. Similarly, enhanced gas migration due to underground galleries and exploitation wells has not been established. Carbon isotope ratios suggested a balance of biological phenomena, despite the high CO(2) contents reached. Other monitored gaseous species (N(2), Ar, H(2) and alkanes), when detected, always showed amounts close to those found subsurface and/or in atmospheric gases. Copyright 2010 Elsevier Ltd. All rights reserved.

Time-Resolved Detection of Fingermarks on Non-Porous and Semi-Porous Substrates Using Sr2MgSi2O7:Eu2+, Dy3+ Phosphors.

PubMed

Xiong, Xiaobo; Yuan, Ximing; Song, Jiangqi; Yin, Guoxiang

2016-06-01

Eu(2+), Dy(3+) co-doped strontium-magnesium silicate phosphors, Sr2MgSi2O7:Eu(2+), Dy(3+) (SMSEDs), have shown great potential in optoelectronic device due to their unique luminescent property. However, their potential applications in forensic science, latent fingermark detection in particular, are still being investigated. In this contribution, SMSEDs were successfully employed to latent fingermarks on a variety of non-porous and semi-porous surfaces, including aluminum foil, porcelain, glass, painted wood, colored paper, and leather. All the results illustrated that this luminescent powder, as a long-lasting phosphorescence material (LLP), was an ideal time-resolved detection reagent of fingermark for elimination of background interferences from various difficult substrates, and offered a good contrast to allow their identification without the need to enhance the results compared to nanosized organic fluorescent powder. © The Author(s) 2016.

Raman enhancement by graphene-Ga2O3 2D bilayer film

PubMed Central

2014-01-01

2D β-Ga2O3 flakes on a continuous 2D graphene film were prepared by a one-step chemical vapor deposition on liquid gallium surface. The composite was characterized by optical microscopy, scanning electron microscopy, Raman spectroscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy (XPS). The experimental results indicate that Ga2O3 flakes grew on the surface of graphene film during the cooling process. In particular, tenfold enhancement of graphene Raman scattering signal was detected on Ga2O3 flakes, and XPS indicates the C-O bonding between graphene and Ga2O3. The mechanism of Raman enhancement was discussed. The 2D Ga2O3-2D graphene structure may possess potential applications. PMID:24472433

Characterization and Modeling Of Microbial Carbon Metabolism In Thawing Permafrost

NASA Astrophysics Data System (ADS)

Graham, D. E.; Phelps, T. J.; Xu, X.; Carroll, S.; Jagadamma, S.; Shakya, M.; Thornton, P. E.; Elias, D. A.

2012-12-01

Increased annual temperatures in the Arctic are warming the surface and subsurface, resulting in thawing permafrost. Thawing exposes large pools of buried organic carbon to microbial degradation, increasing greenhouse gas generation and emission. Most global-scale land-surface models lack depth-dependent representations of carbon conversion and GHG transport; therefore they do not adequately describe permafrost thawing or microbial mineralization processes. The current work was performed to determine how permafrost thawing at moderately elevated temperatures and anoxic conditions would affect CO2 and CH4 generation, while parameterizing depth-dependent GHG production processes with respect to temperature and pH in biogeochemical models. These enhancements will improve the accuracy of GHG emission predictions and identify key biochemical and geochemical processes for further refinement. Three core samples were obtained from discontinuous permafrost terrain in Fairbanks, AK with a mean annual temperature of -3.3 °C. Each core was sectioned into surface/near surface (0-0.8 m), active layer (0.8-1.6 m), and permafrost (1.6-2.2 m) horizons, which were homogenized for physico-chemical characterization and microcosm construction. Surface samples had low pH values (6.0), low water content (18% by weight), low organic carbon (0.8%), and high C:N ratio (43). Active layer samples had higher pH values (6.4), higher water content (34%), more organic carbon (1.4%) and a lower C:N ratio (24). Permafrost samples had the highest pH (6.5), highest water content (46%), high organic carbon (2.5%) and the lowest C:N ratio (19). Most organic carbon was quantified as labile or intermediate pool versus stable pool in each sample, and all samples had low amounts of carbonate. Surface layer microcosms, containing 20 g sediment in septum-sealed vials, were incubated under oxic conditions, while similar active and permafrost layer samples were anoxic. These microcosms were incubated at -2, +3, or +5 °C for 6 months. The pH decreased in all samples (5.5 to 5.9). The proportions of carbon in labile and intermediate turnover pools from permafrost samples decreased during incubation, while microbial biomass carbon increased in all cases. Microcosm samples and original core material were analyzed by 16S rDNA pyrosequencing and showed increased populations of bacteria that ferment simple and complex carbohydrates, as well as acidophilic bacteria. Microbial diversity declined in permafrost samples. Concentrations of CO2 and CH4 were measured monthly by gas chromatography. CO2 production was highest in the surface/near surface incubations (4-14%) while CH4 was undetectable. Active layer sediments produced considerably less CO2 (0.2-0.7%) but CH4 was detected up to 0.25%. Concentrations of CO2 found in the deep permafrost incubations were comparable to those in the active layer, while CH4 was considerably higher ranging from 0.2-0.6%. Overall, the CO2 generation rate (0.02-0.12 μmol/g/month) was roughly 50 times that of methanogenesis (0.002-0.007 μmol/g/month). GHG levels peaked after 4 months, and the decreasing pH suggested that organic acid accumulation could control GHG biogenesis. Surprisingly, increasing temperature and water content did not necessarily increase GHG emission rates or proportions of CO2 and CH4.

Synthesis of oxocarbon-encapsulated gold nanoparticles with blue-shifted localized surface plasmon resonance by pulsed laser ablation in water with CO2 absorbers

NASA Astrophysics Data System (ADS)

Del Rosso, T.; Rey, N. A.; Rosado, T.; Landi, S.; Larrude, D. G.; Romani, E. C.; Freire Junior, F. L.; Quinteiro, S. M.; Cremona, M.; Aucelio, R. Q.; Margheri, G.; Pandoli, O.

2016-06-01

Colloidal suspensions of oxocarbon-encapsulated gold nanoparticles have been synthesized in a one-step procedure by pulsed-laser ablation (PLA) at 532 nm of a solid gold target placed in aqueous solution containing CO2 absorbers, but without any stabilizing agent. Multi-wavelength surface enhanced Raman spectroscopy allows the identification of adsorbed amorphous carbon and graphite, Au-carbonyl, Au coordinated CO2-derived bicarbonates/carbonates and hydroxyl groups around the AuNPs core. Scanning electron microscopy, energy dispersive x-ray analysis and high resolution transmission electron microscopy highlight the organic shell structure around the crystalline metal core. The stability of the colloidal solution of nanocomposites (NCs) seems to be driven by solvation forces and is achieved only in neutral or basic pH using monovalent hydroxide counter-ions (NaOH, KOH). The NCs are characterized by a blue shift of the localized surface plasmon resonance (LSPR) band typical of metal-ligand stabilization by terminal π-back bonding, attributed to a core charging effect caused by Au-carbonyls. Total organic carbon measurements detect the final content of organic carbon in the colloidal solution of NCs that is about six times higher than the value of the water solution used to perform PLA. The colloidal dispersions of NCs are stable for months and are applied as analytical probes in amino glycoside antibiotic LSPR based sensing.

Synthesis of oxocarbon-encapsulated gold nanoparticles with blue-shifted localized surface plasmon resonance by pulsed laser ablation in water with CO2 absorbers.

PubMed

Del Rosso, T; Rey, N A; Rosado, T; Landi, S; Larrude, D G; Romani, E C; Junior, F L Freire; Quinteiro, S M; Cremona, M; Aucelio, R Q; Margheri, G; Pandoli, O

2016-06-24

Colloidal suspensions of oxocarbon-encapsulated gold nanoparticles have been synthesized in a one-step procedure by pulsed-laser ablation (PLA) at 532 nm of a solid gold target placed in aqueous solution containing CO2 absorbers, but without any stabilizing agent. Multi-wavelength surface enhanced Raman spectroscopy allows the identification of adsorbed amorphous carbon and graphite, Au-carbonyl, Au coordinated CO2-derived bicarbonates/carbonates and hydroxyl groups around the AuNPs core. Scanning electron microscopy, energy dispersive x-ray analysis and high resolution transmission electron microscopy highlight the organic shell structure around the crystalline metal core. The stability of the colloidal solution of nanocomposites (NCs) seems to be driven by solvation forces and is achieved only in neutral or basic pH using monovalent hydroxide counter-ions (NaOH, KOH). The NCs are characterized by a blue shift of the localized surface plasmon resonance (LSPR) band typical of metal-ligand stabilization by terminal π-back bonding, attributed to a core charging effect caused by Au-carbonyls. Total organic carbon measurements detect the final content of organic carbon in the colloidal solution of NCs that is about six times higher than the value of the water solution used to perform PLA. The colloidal dispersions of NCs are stable for months and are applied as analytical probes in amino glycoside antibiotic LSPR based sensing.

Synthesis of hydrophilic and conductive molecularly imprinted polyaniline particles for the sensitive and selective protein detection.

PubMed

Luo, Jing; Huang, Jing; Wu, Yunan; Sun, Jun; Wei, Wei; Liu, Xiaoya

2017-08-15

In this work, a novel kind of water-dispersible molecular imprinted conductive polyaniline particles was prepared through a facile and efficient macromolecular co-assembly of polyaniline with amphiphilic copolymer, and applied as the molecular recognition element to construct protein electrochemical sensor. In our strategy, an amphiphilic copolymer P(AMPS-co-St) was first synthesized using 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and styrene (St) as monomer, which could co-assemble with PANI in aqueous solution to generate PANI particles driven by the electrostatic interaction. During this process, ovalbumin (OVA) as template protein was added and trapped into the PANI NPs particles owing to their interactions, resulting in the formation of molecular imprinted polyaniline (MIP-PANI) particles. When utilizing the MIP-PANI particles as recognition element, the resultant imprinted PANI sensor not only exhibited good selectivity toward template protein (the imprinting factor α is 5.31), but also a wide linear range over OVA concentration from 10 -11 to 10 -6 mgmL -1 with a significantly lower detection limit of 10 -12 mgmL -1 , which outperformed most of reported OVA detecting methods. In addition, an ultrafast response time of less than 3min has also been demonstrated. The superior performance is ascribed to the water compatibility, large specific surface area of PANI particles and the electrical conductivity of PANI which provides a direct path for the conduction of electrons from the imprinting sites to the electrode surface. The outstanding sensing performance combined with its facile, quick, green preparation procedure as well as low production cost makes the MIP-PANI particles attractive in specific protein recognition and sensing. Copyright © 2017 Elsevier B.V. All rights reserved.

CO2 lasers and applications II; Proceedings of the Third European Congress on Optics, The Hague, Netherlands, Mar. 12-14, 1990

NASA Technical Reports Server (NTRS)

Opower, Hans (Editor)

1990-01-01

Recent advances in CO2 laser technology and its applications are examined. Topics discussed include the excitation of CO2 lasers by microwave discharge, a compact RF-excited 12-kW CO2 laser, a robotic laser for three-dimensional cutting and welding, three-dimensional CO2-laser material processing with gantry machine systems, and a comparison of hollow metallic waveguides and optical fibers for transmitting CO2-laser radiation. Consideration is given to an aerodynamic window with a pump cavity and a supersonic jet, cutting and welding Al using a high-repetition-rate pulsed CO2 laser, speckle reduction in CO2 heterodyne laser radar systems, high-power-laser float-zone crystal growth, melt dynamics in surface processing with laser radiation, laser hardfacing, surface melting of AlSi10Mg with CO2 laser radiation, material processing with Cu-vapor lasers, light-induced flow at a metal surface, and absorption measurements in high-power CW CO2-laser processing of materials.

Insights into the mechanism of the capture of CO2 by K2CO3 sorbent: a DFT study.

PubMed

Liu, Hongyan; Qin, Qiaoyun; Zhang, Riguang; Ling, Lixia; Wang, Baojun

2017-09-13

The adsorption and reactions of CO 2 and H 2 O on both monoclinic and hexagonal crystal K 2 CO 3 were investigated using the density functional theory (DFT) approach. The calculated adsorption energies showed that adsorption of H 2 O molecules was clearly substantially stronger on the K 2 CO 3 surface than the adsorption of CO 2 , except on the (001)-1 surface of hexagonal K 2 CO 3 , where CO 2 is competitively adsorbed with H 2 O. Carbonation reactions easily occur on pure K 2 CO 3 and involve two parallel paths: one is where adsorbed H 2 O reacts with molecular CO 2 in gas to form the bicarbonate, while the other is where H 2 O dissociates into OH and H before bicarbonate formation, and then OH reacts with gaseous CO 2 to form a bicarbonate. Our results indicate that adding a support or promoter or using a special technique to expose more (001)-1 surfaces in hexagonal K 2 CO 3 may improve the conversion of CO 2 to the bicarbonate, which provides a theoretical direction for the experimental preparation of the K 2 CO 3 sorbent to capture CO 2 .

CO2 adhesion on hydrated mineral surfaces.

PubMed

Wang, Shibo; Tao, Zhiyuan; Persily, Sara M; Clarens, Andres F

2013-10-15

Hydrated mineral surfaces in the environment are generally hydrophilic but in certain cases can strongly adhere CO2, which is largely nonpolar. This adhesion can significantly alter the wettability characteristics of the mineral surface and consequently influence capillary/residual trapping and other multiphase flow processes in porous media. Here, the conditions influencing adhesion between CO2 and homogeneous mineral surfaces were studied using static pendant contact angle measurements and captive advancing/receding tests. The prevalence of adhesion was sensitive to both surface roughness and aqueous chemistry. Adhesion was most widely observed on phlogopite mica, silica, and calcite surfaces with roughness on the order of ~10 nm. The incidence of adhesion increased with ionic strength and CO2 partial pressure. Adhesion was very rarely observed on surfaces equilibrated with brines containing strong acid or base. In advancing/receding contact angle measurements, adhesion could increase the contact angle by a factor of 3. These results support an emerging understanding of adhesion of, nonpolar nonaqueous phase fluids on mineral surfaces influenced by the properties of the electrical double layer in the aqueous phase film and surface functional groups between the mineral and CO2.

The Role of CO2 Clouds on the Stability of the Early Mars Atmosphere Against Collapse

NASA Astrophysics Data System (ADS)

Kahre, Melinda A.; Haberle, Robert; Steakley, Kathryn; Murphy, Jim; Kling, Alexandre

2017-10-01

The early Mars atmosphere was likely significantly more massive than it is today, given the growing body of evidence that liquid water flowed on the surface early in the planet’s history. Although the CO2 inventory was likely larger in the past, there is much we still do not understand about the state of that CO2. As surface pressure increases, the temperature at which CO2 condenses also increases, making it more likely that CO2 ice would form and persist on the surface when the atmospheric mass increases. An atmosphere that is stable against collapse must contain enough energy, distributed globally, to prohibit the formation of permanents CO2 ice reservoirs that lead to collapse. The presence of the “faint young sun” compounds this issue. Previous global climate model (GCM) investigations show that atmospheres within specific ranges of obliquities and atmospheric masses are stable against collapse. We use the NASA Ames Mars GCM to expand on these works by focusing specifically on the role of CO2 clouds in atmospheric stability. Two end member simulations are executed, one that includes CO2 cloud formation and one that does not. The simulation that explicitly includes CO2 clouds is stable, while the simulation without CO2 clouds collapses into permanent surface CO2 reservoirs. In both cases, significant atmospheric condensation is occurring in the atmosphere throughout the year. In the case without CO2 clouds, all atmospheric condensation (even if it occurs at altitude) leads directly to the accumulation of surface ice, whereas in the case with CO2 clouds, there is a finite settling timescale for the cloud particles. Depending on this timescale and the local conditions, the cloud particles could stay aloft or sublimate as they fall toward the surface. Thus, the striking difference between these two cases illustrates the important role of CO2 clouds. We plan to conduct and present further simulations to better understand how atmospheric stability depends on the details of CO2 cloud microphysical processes and assumptions.

Can increasing CO2 cool Antarctica?

NASA Astrophysics Data System (ADS)

Schmithuesen, Holger; Notholt, Justus; König-Langlo, Gert; Lemke, Peter

2014-05-01

CO2 is the strongest anthropogenic forcing agent for climate change since pre-industrial times. Like other greenhouse gases, CO2 absorbs terrestrial surface radiation and causes emission from the atmosphere to space. As the surface is generally warmer than the atmosphere, the total long-wave emission to space is commonly less than the surface emission. However, this does not hold true for the high elevated areas of central Antarctica. Our investigations show, that for the high elevated areas of Antarctica the greenhouse effect (GHE) of CO2 is commonly around zero or even negative. This is based on the quantification of GHE as the difference between long-wave surface emission and top of atmosphere emission. We demonstrate this behaviour with the help of three models: a simple two-layer model, line-by-line calculations, and an ECMWF experiment. Additionally, in this region an increase in CO2 concentration leads to an instantaneous increased long-wave energy loss to space, which is a cooling effect on the earth-atmosphere system. However, short-wave warming by the weak absorption of solar radiation by CO2 are not taken into account here. The reason for this counter-intuitive behaviour is the fact that in the interior of Antarctica the surface is often colder than the stratosphere above. Radiation from the surface in the atmospheric window emitted to space is then relatively lower compared to radiation in the main CO2 band around 15 microns, which originates mostly from the stratosphere. Increasing CO2 concentration leads to increasing emission from the atmosphere to space, while blocking additional portions of surface emission. If the surface is colder than the stratosphere, this leads to additional long-wave energy loss to space for increasing CO2. Our findings for central Antarctica are in strong contrast to the generally known effect that increasing CO2 has on the long-wave emission to space, and hence on the Antarctic climate.

In Situ FT-IR Spectroscopic Study of CO2 and CO Adsorption on Y2O3, ZrO2, and Yttria-Stabilized ZrO2

PubMed Central

2013-01-01

In situ FT-IR spectroscopy was exploited to study the adsorption of CO2 and CO on commercially available yttria-stabilized ZrO2 (8 mol % Y, YSZ-8), Y2O3, and ZrO2. All three oxides were pretreated at high temperatures (1173 K) in air, which leads to effective dehydroxylation of pure ZrO2. Both Y2O3 and YSZ-8 show a much higher reactivity toward CO and CO2 adsorption than ZrO2 because of more facile rehydroxylation of Y-containing phases. Several different carbonate species have been observed following CO2 adsorption on Y2O3 and YSZ-8, which are much more strongly bound on the former, due to formation of higher-coordinated polydentate carbonate species upon annealing. As the crucial factor governing the formation of carbonates, the presence of reactive (basic) surface hydroxyl groups on Y-centers was identified. Therefore, chemisorption of CO2 most likely includes insertion of the CO2 molecule into a reactive surface hydroxyl group and the subsequent formation of a bicarbonate species. Formate formation following CO adsorption has been observed on all three oxides but is less pronounced on ZrO2 due to effective dehydroxylation of the surface during high-temperature treatment. The latter generally causes suppression of the surface reactivity of ZrO2 samples regarding reactions involving CO or CO2 as reaction intermediates. PMID:24009780

Stress-induced chemical detection using flexible metal-organic frameworks.

PubMed

Allendorf, Mark D; Houk, Ronald J T; Andruszkiewicz, Leanne; Talin, A Alec; Pikarsky, Joel; Choudhury, Arnab; Gall, Kenneth A; Hesketh, Peter J

2008-11-05

In this work we demonstrate the concept of stress-induced chemical detection using metal-organic frameworks (MOFs) by integrating a thin film of the MOF HKUST-1 with a microcantilever surface. The results show that the energy of molecular adsorption, which causes slight distortions in the MOF crystal structure, can be converted to mechanical energy to create a highly responsive, reversible, and selective sensor. This sensor responds to water, methanol, and ethanol vapors, but yields no response to either N2 or O2. The magnitude of the signal, which is measured by a built-in piezoresistor, is correlated with the concentration and can be fitted to a Langmuir isotherm. Furthermore, we show that the hydration state of the MOF layer can be used to impart selectivity to CO2. Finally, we report the first use of surface-enhanced Raman spectroscopy to characterize the structure of a MOF film. We conclude that the synthetic versatility of these nanoporous materials holds great promise for creating recognition chemistries to enable selective detection of a wide range of analytes.

Atmospheric Collapse on Early Mars: The Role of CO2 Clouds

NASA Technical Reports Server (NTRS)

Kahre, M. A.; Haberle, R. M.; Steakley, K. E.; Murphy, J. R.; Kling, A.

2017-01-01

The abundance of evidence that liquid water flowed on the surface early in Mars' history strongly implies that the early Martian atmosphere was significantly more massive than it is today. While it seems clear that the total CO2 inventory was likely substantially larger in the past, the fundamental question about the physical state of that CO2 is not completely understood. Because the temperature at which CO2 condenses increases with surface pressure, surface CO2 ice is more likely to form and persist as the atmospheric mass increases. For the atmosphere to remain stable against collapse, there must be enough energy, distributed planet wide, to stave off the formation of permanent CO2 caps that leads to atmospheric collapse. The presence of a "faint young sun" that was likely about 25 percent less luminous 3.8 billion years ago than the sun today makes this even more difficult. Several physical processes play a role in the ultimate stability of a CO2 atmosphere. The system is regulated by the energy balance between solar insolation, the radiative effects of the atmosphere and its constituents, atmospheric heat transport, heat exchange between the surface and the atmosphere, and latent heating/cooling. Specific considerations in this balance for a given orbital obliquity/eccentricity and atmospheric mass are the albedo of the caps, the dust content of the atmosphere, and the presence of water and/or CO2 clouds. Forget et al. show that, for Mars' current obliquity (in a circular orbit), CO2 atmospheres ranging in surface pressure from 500 hectopascals to 3000 hectopascals would have been stable against collapsing into permanent surface ice reservoirs. Soto et al. examined a similar range in initial surface pressure to investigate atmospheric collapse and to compute collapse rates. CO2 clouds and their radiative effects were included in Forget et al. but they were not included in Soto et al. Here we focus on how CO2 clouds affect the stability of the atmosphere against collapse.

Selective removal of demineralized enamel using a CO2 laser coupled with near-IR reflectance imaging

NASA Astrophysics Data System (ADS)

Tom, Henry; Chan, Kenneth H.; Saltiel, Daniel; Fried, Daniel

2015-02-01

Detection and diagnosis of early dental caries lesions can be difficult due to variable tooth coloration, staining of the teeth and poor contrast between sound and demineralized enamel. These problems can be overcome by using near-infrared (NIR) imaging. Previous studies have demonstrated that lasers can be integrated with NIR imaging devices, allowing image-guided ablation. The aim of this study was to demonstrate that NIR light at 1500 - 1700 nm can be used to guide a 9.3-μm CO2 laser for the selective ablation of early demineralization on tooth occlusal surfaces. The occlusal surfaces of ten sound human molars were used in this in-vitro study. Shallow simulated caries lesions of varying depth and position were produced on tooth occlusal surfaces using a demineralization solution. Sequential NIR reflectance images at 1500 - 1700 nm were used to guide the laser for selective ablation of the lesion areas. Digital microscopy and polarization sensitive optical coherence tomography (PS-OCT) were used to assess the selectivity of removal. This study demonstrates that high contrast NIR reflectance images can be used for the image-guided laser ablation of early demineralization from tooth occlusal surfaces.

Active Oxygen Vacancy Site for Methanol Synthesis from CO2 Hydrogenation on In2O3(110): A DFT Study

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

Ye, Jingyun; Liu, Changjun; Mei, Donghai

2013-06-03

Methanol synthesis from CO2 hydrogenation on the defective In2O3(110) surface with surface oxygen vacancies has been investigated using periodic density functional theory calculations. The relative stabilities of six possible surface oxygen vacancies numbered from Ov1 to Ov6 on the perfect In2O3(110) surface were examined. The calculated oxygen vacancy formation energies show that the D1 surface with the Ov1 defective site is the most thermodynamically favorable while the D4 surface with the Ov4 defective site is the least stable. Two different methanol synthesis routes from CO2 hydrogenation over both D1 and D4 surfaces were studied and the D4 surface was foundmore » to be more favorable for CO2 activation and hydrogenation. On the D4 surface, one of the O atoms of the CO2 molecule fills in the Ov4 site upon adsorption. Hydrogenation of CO2 to HCOO on the D4 surface is both thermodynamically and kinetically favorable. Further hydrogenation of HCOO involves both forming the C-H bond and breaking the C-O bond, resulting in H2CO and hydroxyl. The HCOO hydrogenation is slightly endothermic with an activation barrier of 0.57 eV. A high barrier of 1.14 eV for the hydrogenation of H2CO to H3CO indicates that this step is the rate-limiting step in the methanol synthesis on the defective In2O3(110) surface. We gratefully acknowledge the supports from the National Natural Science Foundation of China (#20990223) and from US Department of Energy, Basic Energy Science program (DE-FG02-05ER46231). D. Mei was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The computations were performed in part using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory in Richland, Washington. PNNL is a multiprogram national laboratory operated for DOE by Battelle.« less

Biogenic unmodified gold nanoparticles for selective and quantitative detection of cerium using UV-vis spectroscopy and photon correlation spectroscopy (DLS).

PubMed

Priyadarshini, E; Pradhan, N; Panda, P K; Mishra, B K

2015-06-15

The ability of self-functionalized biogenic GNPs towards highly selective colorimetric detection of rare earth element cerium is being reported for the first time. GNPs underwent rapid aggregation on addition of cerium indicated by red shift of SPR peak followed by complete precipitation. Hereby, this concept of co-ordination of cerium ions onto the GNP surface has been utilized for detection of cerium. The remarkable capacity of GNPs to sensitively detect Ce without proves beneficial compared to previous reports of colorimetric sensing. MDL was 15 and 35 ppm by DLS and UV-vis spectroscopy respectively, suggesting DLS to be highly sensitive and a practical alternative in ultrasensitive detection studies. The sensing system showed a good linear fit favouring feasible detection of cerium in range of 2-50 ppm. Similar studies further showed the superior selectivity of biogenic GNPs compared to chemically synthesized counterparts. The sensing system favours on-site analysis as it overcomes need of complex instrumentation, lengthy protocols and surface modification of GNP. Copyright © 2015 Elsevier B.V. All rights reserved.

Fingerprinting postblast explosive residues by portable capillary electrophoresis with contactless conductivity detection.

PubMed

Kobrin, Eeva-Gerda; Lees, Heidi; Fomitšenko, Maria; Kubáň, Petr; Kaljurand, Mihkel

2014-04-01

A portable capillary electrophoretic system with contactless conductivity detection was used for fingerprint analysis of postblast explosive residues from commercial organic and improvised inorganic explosives on various surfaces (sand, concrete, metal witness plates). Simple extraction methods were developed for each of the surfaces for subsequent simultaneous capillary electrophoretic analysis of anions and cations. Dual-opposite end injection principle was used for fast (<4 min) separation of 10 common anions and cations from postblast residues using an optimized separation electrolyte composed of 20 mM MES, 20 mM l-histidine, 30 μM CTAB and 2 mM 18-crown-6. The concentrations of all ions obtained from the electropherograms were subjected to principal component analysis to classify the tested explosives on all tested surfaces, resulting in distinct cluster formations that could be used to verify (each) type of the explosive. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sulfur Dioxide and the Production of Sulfuric Acid on Present-Day and Early Mars: Implications for the Lack of Detected Carbonates on the Surface

NASA Technical Reports Server (NTRS)

Levine, Joel S.; Summers, Michael E.

2008-01-01

In the early history of Mars, volcanic activity associated with the formation of the Tharsis ridge produced a very large amount of atmospheric SO2--on the order of a bar of atmospheric SO2. In the present-day atmosphere of Mars, the lifetime of SO2 is relatively short with a lifetime of less than a day. The short lifetime of SO2 in the present Mars atmosphere makes the production of significant levels of H2SO4 very difficult since the SO2 may be destroyed by various chemical and photochemical processes before the SO2 can be converted to H2SO4. However, photochemical calculations performed and described here, indicate that enhanced atmospheric levels of CO2 in the early atmosphere of Mars resulted in a significantly enhanced atmospheric lifetime for SO2 up to several years. With a significantly enhanced atmospheric lifetime, SO2 could readily form large amounts of H2SO4, which precipitated out of the atmosphere in the form of droplets. The precipitated H2SO4 then reacted with potential surface carbonates, destroying the carbonates and resulting in the abundant and widespread distribution of sulfates on the surface of Mars as detected by recent Mars missions.

Real-time observation of coadsorption layers on Ru(001) using a temperature-programmed ESDIAD/TOF system

NASA Astrophysics Data System (ADS)

Sasaki, T.; Itai, Y.; Iwasawa, Y.

1997-11-01

For the purpose of utilizing ESDIAD as a real-time probe for surface processes, we have developed an instrument which can measure ESDIAD images and time of flight (TOF) spectra of desorbing ions in temperature-programmed surface processes. TOF measurements are carried out to identify the mass and to determine the kinetic energy distribution of the desorbed ions. This temperature-programmed (TP-) ESDIAD/TOF system was used to observe coadsorption layers of methylamine and CO on Ru(001) which have been previously studied by our group using LEED, TPD and HREELS, also drawing upon a comparison of findings with the coadsorption system of CO and ammonia. ESDIAD images acquired for temperature-programmed surface processes in real time were found to provide new insight into the dynamic behaviour of the coadsorption layers. As to the pure adsorption of ammonia and methylamine, the second and the first (chemisorbed) layers can be easily discriminated in their different ESD detection efficiency due to the difference in neutralization rate. The intensity change of H + ions with temperature shows the process of the decomposition of methylamine to be dependent on CO coverage. The intensity of O + originating from CO changes due to the change of CO adsorption site in the reaction process. The angular distribution of H + ions which correspond to CH2NH…Ru species appears at 250-300 K in the presence of high CO pre-coverage.

Detection of CO2 leaks from carbon capture and storage sites to the atmosphere with combined CO2 and O2 measurements

NASA Astrophysics Data System (ADS)

van Leeuwen, Charlotte; Meijer, Harro A. J.

2015-04-01

One of the main issues in carbon capture and storage (CCS) is the possibility of leakage of CO2 from the storage reservoir to the atmosphere, both from a public health and a climate change combat perspective. Detecting these leaks in the atmosphere is difficult due to the rapid mixing of the emitted CO2 with the surrounding air masses and the high natural variability of the atmospheric CO2 concentration. Instead of measuring only the CO2 concentration of the atmosphere, its isotopes or chemical tracers that are released together with the CO2, our method uses O2 measurements in addition to CO2 measurements to detect a leak from a CCS site. CO2 and O2 are coupled in most processes on earth. In photosynthesis, plants take up CO2 and release O2 at the same time. In respiration and fossil fuel burning, O2 is consumed while CO2 is released. In case of a leak from a CCS site, however, there is no relationship between CO2 and O2. A CO2 leak can therefore be distinguished from other sources of CO2 by looking at the atmospheric CO2-O2 ratio. A natural increase of the CO2 concentration is accompanied by a drop in the O2 concentration, while an increase in the CO2 concentration caused by a leak from a CCS site does not have any effect on the O2 concentration. To demonstrate this leak detection strategy we designed and built a transportable CO2 and O2 measurement system, that is capable of measuring the relatively minute (ppm's variations on a 21% concentration) changes in the O2 concentration. The system comprises of three cases that contain the instrumentation and gas handling equipment, the gas cylinders used as reference and calibration gases and a drying system, respectively. Air is pumped to the system from an air inlet that is placed in a small tower in the field. At the conference, we will demonstrate the success of leak detection with our system by showing measurements of several CO2 release experiments, where CO2 was released at a small distance from the air inlet of our instrument.

Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates.

PubMed

Wang, Zhijiang; Wu, Lina; Sun, Kun; Chen, Ting; Jiang, Zhaohua; Cheng, Tao; Goddard, William A

2018-05-23

We have explored functionalizing metal catalysts with surface ligands as an approach to facilitate electrochemical carbon dioxide reduction reaction (CO 2 RR). To provide a molecular level understanding of the mechanism by which this enhancement occurs, we combine in situ spectroscopy analysis with an interpretation based on quantum mechanics (QM) calculations. We find that a surface ligand can play a critical role in stabilizing the chemisorbed CO 2 , which facilitates CO 2 activation and leads to a 0.3 V decrease in the overpotential for carbon monoxide (CO) formation. Moreover, the presence of the surface ligand leads to nearly exclusive CO production. At -0.6 V (versus reversible hydrogen electrode, RHE), CO is the only significant product with a faradic efficiency of 93% and a current density of 1.9 mA cm -2 . This improvement corresponds to 53-fold enhancement in turnover frequency compared with the Ag nanoparticles (NPs) without surface ligands.

Exploring the effects of data quality, data worth, and redundancy of CO2 gas pressure and saturation data on reservoir characterization through PEST Inversion

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

Fang, Zhufeng; Hou, Zhangshuan; Lin, Guang

2014-04-01

This study examined the impacts of reservoir properties on CO2 migration after subsurface injection and evaluated the possibility of characterizing reservoir properties using CO2 monitoring data such as saturation distribution. The injection reservoir was assumed to be located 1400-1500 m below the ground surface such that CO2 remained in the supercritical state. The reservoir was assumed to contain layers with alternating conductive and resistive properties, which is analogous to actual geological formations such as the Mount Simon Sandstone unit. The CO2 injection simulation used a cylindrical grid setting in which the injection well was situated at the center of themore » domain, which extended up to 8000 m from the injection well. The CO2 migration was simulated using the PNNL-developed simulator STOMP-CO2e (the water-salt-CO2 module). We adopted a nonlinear parameter estimation and optimization modeling software package, PEST, for automated reservoir parameter estimation. We explored the effects of data quality, data worth, and data redundancy on the detectability of reservoir parameters using CO2 saturation monitoring data, by comparing PEST inversion results using data with different levels of noises, various numbers of monitoring wells and locations, and different data collection spacing and temporal sampling intervals. This study yielded insight into the use of CO2 saturation monitoring data for reservoir characterization and how to design the monitoring system to optimize data worth and reduce data redundancy.« less

Unraveling the dynamics of magmatic CO2 degassing at Mammoth Mountain, California

USGS Publications Warehouse

Pfeiffer, Loic; Wanner, Christoph; Lewicki, Jennifer L.

2018-01-01

The accumulation of magmatic CO2 beneath low-permeability barriers may lead to the formation of CO2-rich gas reservoirs within volcanic systems. Such accumulation is often evidenced by high surface CO2 emissions that fluctuate over time. The temporal variability in surface degassing is believed in part to reflect a complex interplay between deep magmatic degassing and the permeability of degassing pathways. A better understanding of the dynamics of CO2 degassing is required to improve monitoring and hazards mitigation in these systems. Owing to the availability of long-term records of CO2 emissions rates and seismicity, Mammoth Mountain in California constitutes an ideal site towards such predictive understanding. Mammoth Mountain is characterized by intense soil CO2 degassing (up to ∼1000 t d−1) and tree kill areas that resulted from leakage of CO2 from a CO2-rich gas reservoir located in the upper ∼4 km. The release of CO2-rich fluids from deeper basaltic intrusions towards the reservoir induces seismicity and potentially reactivates faults connecting the reservoir to the surface. While this conceptual model is well-accepted, there is still a debate whether temporally variable surface CO2 fluxes directly reflect degassing of intrusions or variations in fault permeability. Here, we report the first large-scale numerical model of fluid and heat transport for Mammoth Mountain. We discuss processes (i) leading to the initial formation of the CO2-rich gas reservoir prior to the occurrence of high surface CO2 degassing rates and (ii) controlling current CO2 degassing at the surface. Although the modeling settings are site-specific, the key mechanisms discussed in this study are likely at play at other volcanic systems hosting CO2-rich gas reservoirs. In particular, our model results illustrate the role of convection in stripping a CO2-rich gas phase from a rising hydrothermal fluid and leading to an accumulation of a large mass of CO2 (∼107–108 t) in a shallow gas reservoir. Moreover, we show that both, short-lived (months to years) and long-lived (hundreds of years) events of magmatic fluid injection can lead to critical pressures within the reservoir and potentially trigger fault reactivation. Our sensitivity analysis suggests that observed temporal fluctuations in surface degassing are only indirectly controlled by variations in magmatic degassing and are mainly the result of temporally variable fault permeability. Finally, we suggest that long-term CO2 emission monitoring, seismic tomography and coupled thermal–hydraulic–mechanical modeling are important for CO2-related hazard mitigation.

Spin Uncoupling in Chemisorbed OCCO and CO 2: Two High-Energy Intermediates in Catalytic CO 2 Reduction

DOE PAGES

Hedstrom, Svante; dos Santos, Egon Campos; Liu, Chang; ...

2018-05-08

Here, the production of useful compounds via the electrochemical carbon dioxide reduction reaction (CO2RR) is a matter of intense research. Although the thermodynamics and kinetic barriers of CO2RR are reported in previous computational studies, the electronic structure details are often overlooked. We study two important CO2RR intermediates: ethylenedione (OCCO) and CO 2 covalently bound to cluster and slab models of the Cu(100) surface. Both molecules exhibit a near-unity negative charge as chemisorbed, but otherwise they behave quite differently, as explained by a spin-uncoupling perspective. OCCO adopts a high-spin, quartetlike geometry, allowing two covalent bonds to the surface with an averagemore » gross interaction energy of –1.82 eV/bond. The energy cost for electronically exciting OCCO– to the quartet state is 1.5 eV which is readily repaid via the formation of its two surface bonds. CO 2, conversely, retains a low-spin, doubletlike structure upon chemisorption, and its single unpaired electron forms a single covalent surface bond of –2.07 eV. The 5.0 eV excitation energy to the CO 2 – quartet state is prohibitively costly and cannot be compensated for by an additional surface bond.« less

Room temperature CO and H2 sensing with carbon nanoparticles.

PubMed

Kim, Daegyu; Pikhitsa, Peter V; Yang, Hongjoo; Choi, Mansoo

2011-12-02

We report on a shell-shaped carbon nanoparticle (SCNP)-based gas sensor that reversibly detects reducing gas molecules such as CO and H(2) at room temperature both in air and inert atmosphere. Crystalline SCNPs were synthesized by laser-assisted reactions in pure acetylene gas flow, chemically treated to obtain well-dispersed SCNPs and then patterned on a substrate by the ion-induced focusing method. Our chemically functionalized SCNP-based gas sensor works for low concentrations of CO and H(2) at room temperature even without Pd or Pt catalysts commonly used for splitting H(2) molecules into reactive H atoms, while metal oxide gas sensors and bare carbon-nanotube-based gas sensors for sensing CO and H(2) molecules can operate only at elevated temperatures. A pristine SCNP-based gas sensor was also examined to prove the role of functional groups formed on the surface of functionalized SCNPs. A pristine SCNP gas sensor showed no response to reducing gases at room temperature but a significant response at elevated temperature, indicating a different sensing mechanism from a chemically functionalized SCNP sensor.

on the growth and photochemical efficiency of Acropora cervicornis

NASA Astrophysics Data System (ADS)

Enochs, I. C.; Manzello, D. P.; Carlton, R.; Schopmeyer, S.; van Hooidonk, R.; Lirman, D.

2014-06-01

The effects of light and elevated pCO2 on the growth and photochemical efficiency of the critically endangered staghorn coral, Acropora cervicornis, were examined experimentally. Corals were subjected to high and low treatments of CO2 and light in a fully crossed design and monitored using 3D scanning and buoyant weight methodologies. Calcification rates, linear extension, as well as colony surface area and volume of A. cervicornis were highly dependent on light intensity. At pCO2 levels projected to occur by the end of the century from ocean acidification (OA), A. cervicornis exhibited depressed calcification, but no change in linear extension. Photochemical efficiency ( F v / F m ) was higher at low light, but unaffected by CO2. Amelioration of OA-depressed calcification under high-light treatments was not observed, and we suggest that the high-light intensity necessary to reach saturation of photosynthesis and calcification in A. cervicornis may limit the effectiveness of this potentially protective mechanism in this species. High CO2 causes depressed skeletal density, but not linear extension, illustrating that the measurement of extension by itself is inadequate to detect CO2 impacts. The skeletal integrity of A. cervicornis will be impaired by OA, which may further reduce the resilience of the already diminished populations of this endangered species.

Adsorption and Dissociation of CO2 on Ru(0001)

PubMed Central

2017-01-01

The adsorption and dissociation of carbon dioxide on a Ru(0001) single crystal surface was investigated by reflection–absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) spectroscopy for CO2 adsorbed at 85 K. RAIRS spectroscopy shows that the adsorption of CO2 on a Ru(0001) single crystal is partially dissociative, resulting in CO2 and CO. The CO vibrational mode was also observed to split into two distinct modes, indicating two general populations of CO present at the surface. Furthermore, a time-dependent blue-shift is observed, which is characteristic of increasing CO surface coverage. TPD showed that coverages of up to 0.3 ML were obtained, and no evidence for chemisorption of oxygen on ruthenium was found. PMID:28413569

PEGylated PLGA-based nanoparticles targeting M cells for oral vaccination.

PubMed

Garinot, Marie; Fiévez, Virginie; Pourcelle, Vincent; Stoffelbach, François; des Rieux, Anne; Plapied, Laurence; Theate, Ivan; Freichels, Hélène; Jérôme, Christine; Marchand-Brynaert, Jacqueline; Schneider, Yves-Jacques; Préat, Véronique

2007-07-31

To improve the efficiency of orally delivered vaccines, PEGylated PLGA-based nanoparticles displaying RGD molecules at their surface were designed to target human M cells. RGD grafting was performed by an original method called "photografting" which covalently linked RGD peptides mainly on the PEG moiety of the PCL-PEG, included in the formulation. First, three non-targeted formulations with size and zeta potential adapted to M cell uptake and stable in gastro-intestinal fluids, were developed. Their transport by an in vitro model of the human Follicle associated epithelium (co-cultures) was largely increased as compared to mono-cultures (Caco-2 cells). RGD-labelling of nanoparticles significantly increased their transport by co-cultures, due to interactions between the RGD ligand and the beta(1) intregrins detected at the apical surface of co-cultures. In vivo studies demonstrated that RGD-labelled nanoparticles particularly concentrated in M cells. Finally, ovalbumin-loaded nanoparticles were orally administrated to mice and induced an IgG response, attesting antigen ability to elicit an immune response after oral delivery.

Silicon photonic dual-gas sensor for H2 and CO2 detection.

PubMed

Mi, Guangcan; Horvath, Cameron; Van, Vien

2017-07-10

We report a silicon photonic dual-gas sensor based on a wavelength-multiplexed microring resonator array for simultaneous detection of H 2 and CO 2 gases. The sensor uses Pd as the sensing layer for H 2 gas and a novel functional material based on the Polyhexamethylene Biguanide (PHMB) polymer for CO 2 gas sensing. Gas sensing experiments showed that the PHMB-functionalized microring exhibited high sensitivity to CO 2 gas and excellent selectivity against H 2 . However, the Pd-functionalized microring was found to exhibit sensitivity to both H 2 and CO 2 gases, rendering it ineffective for detecting H 2 in a gas mixture containing CO 2 . We show that the dual-gas sensing scheme can allow for accurate measurement of H 2 concentration in the presence of CO 2 by accounting for the cross-sensitivity of Pd to the latter.

Smart bi-metallic perovskite nanofibers as selective and reusable sensors of nano-level concentrations of non-steroidal anti-inflammatory drugs.

PubMed

Mohamed, Mona A; Hasan, Menna M; Abdullah, Ibrahim H; Abdellah, Ahmed M; Yehia, Ali M; Ahmed, Nashaat; Abbas, Walaa; Allam, Nageh K

2018-08-01

A strategy for trace-level carbon-based electrochemical sensors is investigated via exploring the interesting properties of BaNb 2 O 6 nanofibers (NFs). Utilizing adsorptive stripping square wave voltammetry (ASSWV), an electrochemical sensing platform was developed based on BaNb 2 O 6 nanofibers-modified carbon paste electrode (CPE) for the sensitive detection of lornoxicam (LOR). Different techniques were used to characterize the fabricated BaNb 2 O 6 perovskite NFs. The obtained data show the feasibility to electro-oxidize LOR and paracetamol (PAR) on the surface of the fabricated sensor. The amount of nanofiber and testing conditions were optimized using response surface methodology and ASSWV technique. The optimized BaNb 2 O 6 /CPE sensor exhibits low detection limit of 6.39 × 10 -10 mol L -1 , even in the presence of the co-formulated drug paracetamol (PAR). The sensor was successfully applied for biological applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Surface Complexation Modeling of Calcite Zeta Potential Measurement in Mixed Brines for Carbonate Wettability Characterization

NASA Astrophysics Data System (ADS)

Song, J.; Zeng, Y.; Biswal, S. L.; Hirasaki, G. J.

2017-12-01

We presents zeta potential measurements and surface complexation modeling (SCM) of synthetic calcite in various conditions. The systematic zeta potential measurement and the proposed SCM provide insight into the role of four potential determining cations (Mg2+, SO42- , Ca2+ and CO32-) and CO2 partial pressure in calcite surface charge formation and facilitate the revealing of calcite wettability alteration induced by brines with designed ionic composition ("smart water"). Brines with varying potential determining ions (PDI) concentration in two different CO2 partial pressure (PCO2) are investigated in experiments. Then, a double layer SCM is developed to model the zeta potential measurements. Moreover, we propose a definition for contribution of charged surface species and quantitatively analyze the variation of charged species contribution when changing brine composition. After showing our model can accurately predict calcite zeta potential in brines containing mixed PDIs, we apply it to predict zeta potential in ultra-low and pressurized CO2 environments for potential applications in carbonate enhanced oil recovery including miscible CO2 flooding and CO2 sequestration in carbonate reservoirs. Model prediction reveals that pure calcite surface will be positively charged in all investigated brines in pressurized CO2 environment (>1atm). Moreover, the sensitivity of calcite zeta potential to CO2 partial pressure in the various brine is found to be in the sequence of Na2CO3 > Na2SO4 > NaCl > MgCl2 > CaCl2 (Ionic strength=0.1M).

Advances in High Energy Solid-State Pulsed 2-Micron Lidar Development for Ground and Airborne Wind, Water Vapor and CO2 Measurements

NASA Technical Reports Server (NTRS)

Singh, Upendra N.; Yu, Jirong; Petros, Mulugeta; Refaat, Tamer; Kavaya, Michael J.; Remus, Ruben

2015-01-01

NASA Langley Research Center has a long history of developing 2-micron lasers. From fundamental spectroscopy research, theoretical prediction of new materials, laser demonstration and engineering of lidar systems, it has been a very successful program spanning around two decades. Successful development of 2-micron lasers has led to development of a state-of-the-art compact lidar transceiver for a pulsed coherent Doppler lidar system for wind measurement with an unprecedented laser pulse energy of 250 millijoules in a rugged package. This high pulse energy is produced by a Ho:Tm:LuLiF laser with an optical amplifier. While the lidar is meant for use as an airborne instrument, ground-based tests were carried out to characterize performance of the lidar. Atmospheric measurements will be presented, showing the lidar's capability for wind measurement in the atmospheric boundary layer and free troposphere. Lidar wind measurements are compared to a balloon sonde, showing good agreement between the two sensors. Similar architecture has been used to develop a high energy, Ho:Tm:YLF double-pulsed 2-micron Integrated Differential Absorption Lidar (IPDA) instrument based on direct detection technique that provides atmospheric column CO2 measurements. This instrument has been successfully used to measure atmospheric CO2 column density initially from a ground mobile lidar trailer, and then it was integrated on B-200 plane and 20 hours of flight measurement were made from an altitude ranging 1500 meters to 8000 meters. These measurements were compared to in-situ measurements and National Oceanic and Atmospheric Administration (NOAA) airborne flask measurement to derive the dry mixing ratio of the column CO2 by reflecting the signal by various reflecting surfaces such as land, vegetation, ocean surface, snow and sand. The lidar measurements when compared showed a very agreement with in-situ and airborne flask measurement. NASA Langley Research Center is currently developing a triple-pulsed 2-micron Integrated Differential Absorption Lidar (IPDA) instrument for simultaneous measurement of water vapor and carbon-dioxide column density measurement from an air-borne platform. This presentation will give an overview of the 2 decades of 2-micron coherent and direction detection of laser/lidar development at NASA Langley Research Center and will present the ground and airborne wind and column CO2 measurement intercomparison with in-situ, balloon and flask measurements.

Occurrence of pesticides and contaminants of emerging concern in surface waters: Influence of surrounding land use and evaluation of sampling methods

USDA-ARS?s Scientific Manuscript database

Biologically active compounds originating from agricultural, residential, and industrial sources have been detected in surface waters, which have invoked concern of their potential ecological and human health effects. Automated and grab surface water samples, passive water samples - Polar Organic Co...

Colloidally stable surface-modified iron oxide nanoparticles: Preparation, characterization and anti-tumor activity

NASA Astrophysics Data System (ADS)

Macková, Hana; Horák, Daniel; Donchenko, Georgiy Viktorovich; Andriyaka, Vadim Ivanovich; Palyvoda, Olga Mikhailovna; Chernishov, Vladimir Ivanovich; Chekhun, Vasyl Fedorovich; Todor, Igor Nikolaevich; Kuzmenko, Oleksandr Ivanovich

2015-04-01

Maghemite (γ-Fe2O3) nanoparticles were obtained by co-precipitation of Fe(II) and Fe(III) chlorides and subsequent oxidation with sodium hypochlorite and coated with poly(N,N-dimethylacrylamide-co-acrylic acid) [P(DMAAm-AA)]. They were characterized by a range of methods including transmission electron microscopy (TEM), elemental analysis, dynamic light scattering (DLS) and zeta potential measurements. The effect of superparamagnetic P(DMAAm-AA)-γ-Fe2O3 nanoparticles on oxidation of blood lipids, glutathione and proteins in blood serum was detected using 2-thiobarbituric acid and the ThioGlo fluorophore. Finally, mice received magnetic nanoparticles administered per os and the antitumor activity of the particles was tested on Lewis lung carcinoma (LLC) in male mice line C57BL/6 as an experimental in vivo metastatic tumor model; the tumor size was measured and the number of metastases in lungs was determined. Surface-modified γ-Fe2O3 nanoparticles showed higher antitumor and antimetastatic activities than commercial CuFe2O4 particles and the conventional antitumor agent cisplatin.

Improvement of gas-adsorption performances of Ag-functionalized monolayer MoS2 surfaces: A first-principles study

NASA Astrophysics Data System (ADS)

Song, Jian; Lou, Huan

2018-05-01

Investigations of the adsorptions of representative gases (NO2, NH3, H2S, SO2, CO, and HCHO) on different Ag-functionalized monolayer MoS2 surfaces were performed by first principles methods. The adsorption configurations, adsorption energies, electronic structure properties, and charge transfer were calculated, and the results show that the adsorption activities to gases of monolayer MoS2 are dramatically enhanced by the Ag-modification. The Ag-modified perfect MoS2 (Ag-P) and MoS2 with S-vacancy (Ag-Vs) substrates exhibit a more superior adsorption activity to NO2 than other gases, which is consistent with the experimental reports. The charge transfer processes of different molecules adsorbed on different surfaces exhibit various characteristics, with potential benefits to gas selectivity. For instance, the NO2 and SO2 obtain more electrons from both Ag-P and Ag-Vs substrates but the NH3 and H2S donate more electrons to materials than others. In addition, the CO and HCHO possess totally opposite charge transfer directs on both substrates, respectively. The BS and PDOS calculations show that semiconductor types of gas/Ag-MoS2 systems are more determined by the metal-functionalization of material, and the directs and numbers of charge transfer process between gases and adsorbents can cause the increase or decline of material resistance theoretically, which is helpful to gas detection and distinction. The further analysis indicates suitable co-operation between the gain-lost electron ability of gas and metallicity of featuring metal might adjust the resistivity of complex and contribute to new thought for metal-functionalization. Our works provide new valuable ideas and theoretical foundation for the potential improvement of MoS2-based gas sensor performances, such as sensitivity and selectivity.

Enhanced human osteoblast cell adhesion and proliferation on 316 LS stainless steel by means of CO2 laser surface treatment.

PubMed

Hao, L; Lawrence, J; Phua, Y F; Chian, K S; Lim, G C; Zheng, H Y

2005-04-01

An effective and novel technique for improving the biocompatibility of a biograde 316 LS stainless steel through the application of CO(2) laser treatment to modify the surface properties of the material is described herein. Different surface properties, such as surface roughness, surface oxygen content, and surface energy for CO(2) laser-treated 316 LS stainless steel, untreated, and mechanically roughened samples were analyzed, and their effects on the wettability characteristics of the material were studied. It was found that modification of the wettability characteristics of the 316 LS stainless steel following CO(2) laser treatment was achieved. This improvement was identified as being mainly due to the change in the polar component of the surface energy. One-day cell adhesion tests showed that cells not only adhered and spread better, but also grew faster on the CO(2) laser-treated sample than on either the untreated or mechanically roughened sample. Further, compared with the untreated sample, MTT cell proliferation analysis revealed that the mechanically roughed surface resulted in a slight enhancement, and CO(2) laser treatment brought about a significant increase in cell proliferation. An increase in the wettability of the 316 LS stainless steel was observed to positively correlate with the cell proliferation. (c) 2004 Wiley Periodicals, Inc.

Colorimetric detection of trivalent chromium in aqueous solution using tartrate-capped silver nanoparticles as probe.

PubMed

Xu, Yunbo; Dong, Yangjun; Jiang, Xue; Zhu, Ningning

2013-10-01

This study describes a simple and highly selective method for the colorimetric detection of trivalent chromium (Cr3+) using tartrate-capped silver nanoparticles (AgNPs) as probe. The addition of tartrate to the initially prepared AgNPs gives tartrate-stabilized AgNPs ascribing to the electrostatic repulsion of the highly negatively charged tartrate ions covered on the surface of AgNPs. It is found that, in the presence of Cr3+ in aqueous solution, the aggregation of tartrate-stabilized AgNPs occurs. The color of AgNPs suspension changes from yellow to pink and the surface plasmon absorption band broadens and red shifts, which could be applied for the colorimetric detection of Cr3+ in aqueous solution. The utilization of tartrate-stabilized AgNPs as probe substantially increases the selectivity and sensitivity for colorimetric detection of Cr3+. Control experiments with the addition of over 14 other metal ions, such as Pb2+, Zn2+, Cr2O7(2-), Cd2+, Co2+, Cu2+, Al3+, Ni2+, Mn2+, Ba2+, Fe3+, Ca2+, Mg2+, Sr+ do not result in a distinct change in the color or in the spectrum of the suspension, indicating that these metal ions do not interfere with the colorimetric detection of Cr3+. Under the conditions employed here, A502/A393 (ratio of absorption value at 502 nm to 393 nm) is linear with the concentration of Cr3+ within a concentration range from 0.1 to 1.17 microM with a detection limit of 0.06 microM. This study may offer a simple, rapid and sensitive approach to colorimetric detection of Cr3+ in aqueous solution.

Processing of ammonia-containing ices by heavy ions and its relevance to outer Solar System surfaces

NASA Astrophysics Data System (ADS)

Pilling, Sergio; Seperuelo Duarte, Eduardo; da Silveira, Enio F.; Domaracka, Alicja; Balanzat, Emmanuel; Rothard, Hermann; Boduch, Philippe

Ammonia-containing ices have been detected or postulated as important components of the icy surfaces of planetary satellites (e.g. Enceladus, Miranda), in the outer Solar System objects (e.g. Charon, Quaoar) and in Oort cloud comets. We present experimental studies of the interaction of heavy, highly-charged, and energetic ions with ammonia-containing ices (pure NH3 ; NH3 :CO; NH3 :H2 O and NH3 :H2 O:CO) in an attempt to simulate the physical chemistry induced by heavy-ion cosmic rays and heavy-ion solar wind particles at outer Solar System surfaces. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accelerateur National d'Ions Lourds) in Caen, France. The gas samples were deposited onto a polished CsI substrate previously cooled to 13 K. In-situ analysis was performed by a Fourier transform infrared spectrometer (FTIR) at different ion fluences. The dissociation cross-section and sputtering yield of ammonia and other ice compounds have been determined. Half-life of frozen ammonia due to heavy ion bombardment at different Solar System surfaces has been estimated. Radiolysis products have been identified and their implications for the chemistry on outer Solar System surfaces are discussed.

New Signal Amplification Strategy Using Semicarbazide as Co-reaction Accelerator for Highly Sensitive Electrochemiluminescent Aptasensor Construction.

PubMed

Ma, Meng-Nan; Zhuo, Ying; Yuan, Ruo; Chai, Ya-Qin

2015-11-17

A highly sensitive electrochemiluminescent (ECL) aptasensor was constructed using semicarbazide (Sem) as co-reaction accelerator to promote the ECL reaction rate of CdTe quantum dots (CdTe QDs) and the co-reactant of peroxydisulfate (S2O8(2-)) for boosting signal amplification. The co-reaction accelerator is a species that when it is introduced into the ECL system containing luminophore and co-reactant, it can interact with co-reactant rather than luminophore to promote the ECL reaction rate of luminophore and co-reactant; thus the ECL signal is significantly amplified in comparison with that in which only luminophore and co-reactant are present. In this work, the ECL signal probes were first fabricated by alternately assembling the Sem and Au nanoparticles (AuNPs) onto the surfaces of hollow Au nanocages (AuNCs) via Au-N bond to obtain the multilayered nanomaterials of (AuNPs-Sem)n-AuNCs for immobilizing amino-terminated detection aptamer of thrombin (TBA2). Notably, the Sem with two -NH2 terminal groups could not only serve as cross-linking reagent to assemble AuNPs and AuNCs but also act as co-reaction accelerator to enhance the ECL reaction rate of CdTe QDs and S2O8(2-) for signal amplification. With the sandwich-type format, TBA2 signal probes could be trapped on the CdTe QD-based sensing interface in the presence of thrombin (TB) to achieve a considerably enhanced ECL signal in S2O8(2-) solution. As a result, the Sem in the TBA2 signal probes could accelerate the reduction of S2O8(2-) to produce the more oxidant mediators of SO4(•-), which further boosted the production of excited states of CdTe QDs to emit light. With the employment of the novel co-reaction accelerator Sem, the proposed ECL biosensor exhibited ultrahigh sensitivity to quantify the concentration of TB from 1 × 10(-7) to 1 nM with a detection limit of 0.03 fM, which demonstrated that the co-reaction accelerator could provide a simple, efficient, and low-cost approach for signal amplification and hold great potential for other ECL biosensors construction.

ISS and TPD study of the adsorption and interaction of CO and H2 on polycrystalline Pt

NASA Technical Reports Server (NTRS)

Melendez, Orlando; Hoflund, Gar B.; Schryer, David R.

1990-01-01

The adsorption and interaction of CO and H2 on polycrystalline Pt has been studied using ion scattering spectroscopy (ISS) and temperature programmed desorption (TPD). The ISS results indicate that the initial CO adsorption on Pt takes place very rapidly and saturates the Pt surface with coverage close to a monolayer. ISS also shows that the CO molecules adsorb at an angular orientation from the surface normal and perhaps parallel to the surface. A TPD spectrum obtained after coadsorbing C-12 O-16 and C-13 O-18 on Pt shows no isotopic mixing, which is indicative of molecular CO adsorption. TPD spectra obtained after coadsorbing H2 and CO on polycrystalline Pt provides evidence for the formation of a CO-H surface species.

How increasing CO2 leads to an increased negative greenhouse effect in Antarctica

NASA Astrophysics Data System (ADS)

Schmithüsen, Holger; Notholt, Justus; König-Langlo, Gert; Lemke, Peter; Jung, Thomas

2015-12-01

CO2 is the strongest anthropogenic forcing agent for climate change since preindustrial times. Like other greenhouse gases, CO2 absorbs terrestrial surface radiation and causes emission from the atmosphere to space. As the surface is generally warmer than the atmosphere, the total long-wave emission to space is commonly less than the surface emission. However, this does not hold true for the high elevated areas of central Antarctica. For this region, the emission to space is higher than the surface emission; and the greenhouse effect of CO2 is around zero or even negative, which has not been discussed so far. We investigated this in detail and show that for central Antarctica an increase in CO2 concentration leads to an increased long-wave energy loss to space, which cools the Earth-atmosphere system. These findings for central Antarctica are in contrast to the general warming effect of increasing CO2.

Induced Seismicity Monitoring System

NASA Astrophysics Data System (ADS)

Taylor, S. R.; Jarpe, S.; Harben, P.

2014-12-01

There are many seismological aspects associated with monitoring of permanent storage of carbon dioxide (CO2) in geologic formations. Many of these include monitoring underground gas migration through detailed tomographic studies of rock properties, integrity of the cap rock and micro seismicity with time. These types of studies require expensive deployments of surface and borehole sensors in the vicinity of the CO2 injection wells. Another problem that may exist in CO2 sequestration fields is the potential for damaging induced seismicity associated with fluid injection into the geologic reservoir. Seismic hazard monitoring in CO2 sequestration fields requires a seismic network over a spatially larger region possibly having stations in remote settings. Expensive observatory-grade seismic systems are not necessary for seismic hazard deployments or small-scale tomographic studies. Hazard monitoring requires accurate location of induced seismicity to magnitude levels only slightly less than that which can be felt at the surface (e.g. magnitude 1), and the frequencies of interest for tomographic analysis are ~1 Hz and greater. We have developed a seismo/acoustic smart sensor system that can achieve the goals necessary for induced seismicity monitoring in CO2 sequestration fields. The unit is inexpensive, lightweight, easy to deploy, can operate remotely under harsh conditions and features 9 channels of recording (currently 3C 4.5 Hz geophone, MEMS accelerometer and microphone). An on-board processor allows for satellite transmission of parameter data to a processing center. Continuous or event-detected data is kept on two removable flash SD cards of up to 64+ Gbytes each. If available, data can be transmitted via cell phone modem or picked up via site visits. Low-power consumption allows for autonomous operation using only a 10 watt solar panel and a gel-cell battery. The system has been successfully tested for long-term (> 6 months) remote operations over a wide range of environments including summer in Arizona to winter above 9000' in the mountains of southern Colorado. Statistically based on-board processing is used for detection, arrival time picking, back azimuth estimation and magnitude estimates from coda waves and acoustic signals.

Chemisorption studies of Pt/SnO2 catalysts

NASA Technical Reports Server (NTRS)

Brown, Kenneth G.; Ohorodnik, Susan K.; Vannorman, John D.; Schryer, Jacqueline; Upchurch, Billy T.; Schryer, David R.

1990-01-01

The low temperature CO oxidation catalysts that are being developed and tested at NASA-Langley are fairly unique in their ability to efficiently oxidize CO at low temperatures (approx. 303 K). The bulk of the reaction data that has been collected in the laboratory has been determined using plug flow reactors with a low mass of Pt/SnO2/SiO2 catalyst (approx. 0.1 g) and a modest flow rate (5 to 10 sc sm). The researchers have previously characterized the surface solely in terms of N2 BET surface areas. These surface areas have not been that indicative of reaction rate. Indeed, some of the formulations with high BET surface area have yielded lower reaction rates than those with lower BET surface areas. As a result researchers began a program of determining the chemisorption of the various species involved in the reaction; CO, O2 and CO2. Such a determination of will lead to a better understanding of the mechanism and overall kinetics of the reaction. The pulsed-reactor technique, initially described by Freel, is used to determine the amount of a particular molecule that is adsorbed on the catalyst. Since there is some reaction of CO with the surface to produce CO2, the pulsed reactor had to be coupled with a gas chromatograph in order to distinguish between the loss of CO that is due to adsorption by the surface and the loss that is due to reaction with the surface.

Field demonstration of CO2 leakage detection in potable aquifers with a pulselike CO2-release test.

PubMed

Yang, Changbing; Hovorka, Susan D; Delgado-Alonso, Jesus; Mickler, Patrick J; Treviño, Ramón H; Phillips, Straun

2014-12-02

This study presents two field pulselike CO2-release tests to demonstrate CO2 leakage detection in a shallow aquifer by monitoring groundwater pH, alkalinity, and dissolved inorganic carbon (DIC) using the periodic groundwater sampling method and a fiber-optic CO2 sensor for real-time in situ monitoring of dissolved CO2 in groundwater. Measurements of groundwater pH, alkalinity, DIC, and dissolved CO2 clearly deviated from their background values, showing responses to CO2 leakage. Dissolved CO2 observed in the tests was highly sensitive in comparison to groundwater pH, DIC, and alkalinity. Comparison of the pulselike CO2-release tests to other field tests suggests that pulselike CO2-release tests can provide reliable assessment of geochemical parameters indicative of CO2 leakage. Measurements by the fiber-optic CO2 sensor, showing obvious leakage signals, demonstrated the potential of real-time in situ monitoring of dissolved CO2 for leakage detection at a geologic carbon sequestration (GCS) site. Results of a two-dimensional reactive transport model reproduced the geochemical measurements and confirmed that the decrease in groundwater pH and the increases in DIC and dissolved CO2 observed in the pulselike CO2-release tests were caused by dissolution of CO2 whereas alkalinity was likely affected by carbonate dissolution.

In situ Investigation of Methane Dry Reforming on M-CeO 2(111) {M= Co, Ni, Cu} Surfaces: Metal-Support Interactions and the activation of C-H bonds at Low Temperature

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

Rodriguez, Jose A.; Liu, Zongyuan; Lustemberg, Pablo

Studies with a series of M-CeO 2(111) {M= Co, Ni, Cu} surfaces indicate that metal-oxide interactions can play a very important role for the activation of methane and its reforming with CO 2 at relatively low temperatures (600-700 K). Among the systems examined, Co-CeO 2(111) exhibits the best performance and Cu-CeO 2(111) has negligible activity. Experiments using ambient pressure XPS indicate that methane dissociates on Co-CeO2(111), at temperatures as low as 300 K, generating CH x and CO x species on the catalyst surface. The results of density-functional calculations show a reduction in the methane activation barrier from 1.07 eVmore » on Co(0001) to 0.87 eV on Co 2+/CeO 2(111), and to only 0.05 eV on Co 0/CeO 2-x(111). At 700 K, under methane dry reforming conditions, CO 2 dissociates on the oxide surface and a catalytic cycle is established without coke deposition. In conclusion, a significant part of the CH x formed on the Co 0/CeO 2-x (111) catalyst recombines to yield ethane or ethylene.« less

In situ Investigation of Methane Dry Reforming on M-CeO 2(111) {M= Co, Ni, Cu} Surfaces: Metal-Support Interactions and the activation of C-H bonds at Low Temperature

DOE PAGES

Rodriguez, Jose A.; Liu, Zongyuan; Lustemberg, Pablo; ...

2017-08-16

Studies with a series of M-CeO 2(111) {M= Co, Ni, Cu} surfaces indicate that metal-oxide interactions can play a very important role for the activation of methane and its reforming with CO 2 at relatively low temperatures (600-700 K). Among the systems examined, Co-CeO 2(111) exhibits the best performance and Cu-CeO 2(111) has negligible activity. Experiments using ambient pressure XPS indicate that methane dissociates on Co-CeO2(111), at temperatures as low as 300 K, generating CH x and CO x species on the catalyst surface. The results of density-functional calculations show a reduction in the methane activation barrier from 1.07 eVmore » on Co(0001) to 0.87 eV on Co 2+/CeO 2(111), and to only 0.05 eV on Co 0/CeO 2-x(111). At 700 K, under methane dry reforming conditions, CO 2 dissociates on the oxide surface and a catalytic cycle is established without coke deposition. In conclusion, a significant part of the CH x formed on the Co 0/CeO 2-x (111) catalyst recombines to yield ethane or ethylene.« less

A Lanthanide MOF Thin-Film Fixed with Co3 O4 Nano-Anchors as a Highly Efficient Luminescent Sensor for Nitrofuran Antibiotics.

PubMed

Zhang, Feng; Yao, Hua; Chu, Tianshu; Zhang, Gaowei; Wang, Yi; Yang, Yangyi

2017-08-01

Nitrofurans are a group of widely used veterinary antibiotics, which have been banned due to antibiotics pollution. Development of a rapid and effective method for the detection of nitrofuran antibiotics (NFAs) is an important challenge. Herein, we designed a chemical sensor based on a thin-film composed of the lanthanide metal-organic framework (Ln-MOF) {[Eu 2 (BCA) 3 (H 2 O)(DMF) 3 ]⋅0.5DMF⋅H 2 O} n (Eu-BCA, in which BCA is 2,2'-biquinoline-4,4'-dicarboxylate) coated on a cost-effective stainless steel wire mesh (SSWM) by Co 3 O 4 nano-anchor fixation method. The MOF coatings were well adhered to the SSWM, resulting in a three-dimensional porous, flexible, and processable sensor. The structure of the as-prepared MOF thin-film was confirmed by powder X-ray diffraction (PXRD), and the surface morphology was examined by scanning electron microscopy (SEM). Significantly, the Eu-BCA thin-film was highly selective and sensitive to NFAs, and yet remained unaffected by other common antibiotics that may be present. The limits of detection for nitrofurantoin (NFT) and nitrofurazone (NFZ) are 0.21 and 0.16 μm, respectively. NFAs were also successfully detected in water from the Pearl River in Guangzhou, and from bovine serum samples. Hence, the reported Ln-MOF thin-film is a promising sensor for the detection of NFAs, thereby helping to protect human beings from all manner of hazards that arise from the abuse of antibiotics in livestock breeding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Boosting hot electron flux and catalytic activity at metal-oxide interfaces of PtCo bimetallic nanoparticles.

PubMed

Lee, Hyosun; Lim, Juhyung; Lee, Changhwan; Back, Seoin; An, Kwangjin; Shin, Jae Won; Ryoo, Ryong; Jung, Yousung; Park, Jeong Young

2018-06-08

Despite numerous studies, the origin of the enhanced catalytic performance of bimetallic nanoparticles (NPs) remains elusive because of the ever-changing surface structures, compositions, and oxidation states of NPs under reaction conditions. An effective strategy for obtaining critical clues for the phenomenon is real-time quantitative detection of hot electrons induced by a chemical reaction on the catalysts. Here, we investigate hot electrons excited on PtCo bimetallic NPs during H 2 oxidation by measuring the chemicurrent on a catalytic nanodiode while changing the Pt composition of the NPs. We reveal that the presence of a CoO/Pt interface enables efficient transport of electrons and higher catalytic activity for PtCo NPs. These results are consistent with theoretical calculations suggesting that lower activation energy and higher exothermicity are required for the reaction at the CoO/Pt interface.

Real-time breath gas analysis of CO and CO2 using an EC-QCL

NASA Astrophysics Data System (ADS)

Ghorbani, Ramin; Schmidt, Florian M.

2017-05-01

Real-time breath gas analysis is a promising, non-invasive tool in medical diagnostics, and well-suited to investigate the physiology of carbon monoxide (CO), a potential biomarker for oxidative stress and respiratory diseases. A sensor for precise, breath-cycle resolved, simultaneous detection of exhaled CO (eCO) and carbon dioxide (eCO2) was developed based on a continuous wave, external-cavity quantum cascade laser (EC-QCL), a low-volume multi-pass cell and wavelength modulation spectroscopy. The system achieves a noise-equivalent (1σ) sensitivity of 8.5 × 10-8 cm-1 Hz-1/2 and (2σ) detection limits of 9 ± 2 ppbv and 650 ± 7 ppmv at 0.14 s spectrum acquisition time for CO and CO2, respectively. Integration over 15 s yields a precision of 0.6 ppbv for CO. The fact that the eCO2 expirograms measured by capnography and laser spectroscopy have essentially identical shape confirms true real-time detection. It is found that the individual eCO exhalation profiles from healthy non-smokers have a slightly different shape than the eCO2 profiles and exhibit a clear dependence on exhalation flow rate and breath-holding time. Detection of indoor air CO and broadband breath profiling across the 93 cm-1 mode-hop-free tuning range of the EC-QCL are also demonstrated.

The Effect of Excess Electron and hole on CO2 Adsorption and Activation on Rutile (110) surface

PubMed Central

Yin, Wen-Jin; Wen, Bo; Bandaru, Sateesh; Krack, Matthias; Lau, MW; Liu, Li-Min

2016-01-01

CO2 capture and conversion into useful chemical fuel attracts great attention from many different fields. In the reduction process, excess electron is of key importance as it participates in the reaction, thus it is essential to know whether the excess electrons or holes affect the CO2 conversion. Here, the first-principles calculations were carried out to explore the role of excess electron on adsorption and activation of CO2 on rutile (110) surface. The calculated results demonstrate that CO2 can be activated as CO2 anions or CO2 cation when the system contains excess electrons and holes. The electronic structure of the activated CO2 is greatly changed, and the lowest unoccupied molecular orbital of CO2 can be even lower than the conduction band minimum of TiO2, which greatly facilities the CO2 reduction. Meanwhile, the dissociation process of CO2 undergoes an activated CO2− anion in bend configuration rather than the linear, while the long crossing distance of proton transfer greatly hinders the photocatalytic reduction of CO2 on the rutile (110) surface. These results show the importance of the excess electrons on the CO2 reduction process. PMID:26984417

Airborne remote-sensing of atmospheric CH4 and CO2 with MAMap: first results of measurements over wetlands in Germany and a N-S transect from Canada to Chile

NASA Astrophysics Data System (ADS)

Tretner, A.; Gerilowski, K.; Bovensmann, H.; Buchwitz, M.; Bertagnolio, P. P.; Erzinger, J.; Burrows, J.

2008-12-01

The Methane Airborne Mapper (MAMap) was designed for CO2 and CH4 remote sensing of the atmospheric column between an aircraft and the Earth's surface. The instrument is specified to detect mixing ratio variations below the aircraft of <3% of the atmospheric background as well as a ground pixel size of 20m x 20m (700m flight height, 200 km/h flight speed). It allows the detection of CO2 and CH4 gradients on a local, regional and global scale, and provides a link between ground-based and satellite- based measurements. The goal of the MAMap measurements is to improve the knowledge of CH4 and CO2 sources and sinks. In 2007 and 2008, several flight campaigns over bogs and wetlands have been conducted in Germany and correlated to ground-based measurements. A first version of the data retrieval has been developed using a modified version of the WFM-DOAS algorithm. WFM-DOAS is also used for the retrieval of CH4 and CO2 column concentrations from nadir measurements by SCIAMACHY onboard ENVISAT. In November 2008, a transect from Oshawa, Canada to Punta Arenas, Chile will be flown onboard the AWI POLAR 5 aircraft. Along the flight path CH4 and CO2 measurements will be conducted by MAMap. Besides the N-S track (Canada-USA-Bahamas-Panama-Ecuador-Peru-Chile), an additional W-E track from Guayaquil (Ecuador) to Iquitos (Peru) and back is planned, covering large areas of Peruvian rainforest. One focus of this project is the evaluation of tropical rain forest and savannah as sources/sinks of CH4 and CO2. Discrepancies between the models and satellite data regarding atmospheric CH4 concentrations over the tropics have been reported in the past. A first assessment of MAMap measurements performed in 2008 over wetlands in Germany and the AWI-POLAR 5 campaign will be presented.

Detection of CO and HCN in Pluto's atmosphere with ALMA

NASA Astrophysics Data System (ADS)

Lellouch, E.; Gurwell, M.; Butler, B.; Fouchet, T.; Lavvas, P.; Strobel, D. F.; Sicardy, B.; Moullet, A.; Moreno, R.; Bockelée-Morvan, D.; Biver, N.; Young, L.; Lis, D.; Stansberry, J.; Stern, A.; Weaver, H.; Young, E.; Zhu, X.; Boissier, J.

2017-04-01

Observations of the Pluto-Charon system, acquired with the ALMA interferometer on June 12-13, 2015, have led to the detection of the CO(3-2) and HCN(4-3) rotational transitions from Pluto (including the hyperfine structure of HCN), providing a strong confirmation of the presence of CO, and the first observation of HCN in Pluto's atmosphere. The CO and HCN lines probe Pluto's atmosphere up to ∼450 km and ∼900 km altitude, respectively, with a large contribution due to limb emission. The CO detection yields (i) a much improved determination of the CO mole fraction, as 515 ± 40 ppm for a 12 μbar surface pressure (ii) strong constraints on Pluto's mean atmospheric dayside temperature profile over ∼50-400 km, with clear evidence for a well-marked temperature decrease (i.e., mesosphere) above the 30-50 km stratopause and a best-determined temperature of 70 ± 2 K at 300 km, somewhat lower than previously estimated from stellar occultations (81 ± 6 K), and in agreement with recent inferences from New Horizons / Alice solar occultation data. The HCN line shape implies a high abundance of this species in the upper atmosphere, with a mole fraction >1.5 × 10-5 above 450 km and a value of 4 × 10-5 near 800 km. Assuming HCN at saturation, this would require a warm (>92 K) upper atmosphere layer; while this is not ruled out by the CO emission, it is inconsistent with the Alice-measured CH4 and N2 line-of-sight column densities. Taken together, the large HCN abundance and the cold upper atmosphere imply supersaturation of HCN to a degree (7-8 orders of magnitude) hitherto unseen in planetary atmospheres, probably due to a lack of condensation nuclei above the haze region and the slow kinetics of condensation at the low pressure and temperature conditions of Pluto's upper atmosphere. HCN is also present in the bottom ∼100 km of the atmosphere, with a 10-8-10-7 mole fraction; this implies either HCN saturation or undersaturation there, depending on the precise stratopause temperature. The HCN column is (1.6 ± 0.4)× 1014 cm-2 , suggesting a surface-referred vertically-integrated net production rate of ∼2 × 107 cm-2 s-1. Although HCN rotational line cooling affects Pluto's atmosphere heat budget, the amounts determined in this study are insufficient to explain the well-marked mesosphere and upper atmosphere's ∼70 K temperature, which if controlled by HCN cooling would require HCN mole fractions of (3-7) ×10-4 over 400-800 km. We finally report an upper limit on the HC3N column density (<2 × 1013 cm-2) and on the HC15N / HC14N ratio (<1/125).

Quantifying the flux of CaCO3 and organic carbon from the surface ocean using in situ measurements of O2, N2, pCO2, and pH

NASA Astrophysics Data System (ADS)

Emerson, Steven; Sabine, Christopher; Cronin, Meghan F.; Feely, Richard; Cullison Gray, Sarah E.; Degrandpre, Mike

2011-09-01

Ocean acidification from anthropogenic CO2 has focused our attention on the importance of understanding the rates and mechanisms of CaCO3 formation so that changes can be monitored and feedbacks predicted. We present a method for determining the rate of CaCO3 production using in situ measureme nts of fCO2 and pH in surface waters of the eastern subarctic Pacific Ocean. These quantities were determined on a surface mooring every 3 h for a period of about 9 months in 2007 at Ocean Station Papa (50°N, 145°W). We use the data in a simple surface ocean, mass balance model of dissolved inorganic carbon (DIC) and alkalinity (Alk) to constrain the CaCO3: organic carbon (OC) production ratio to be approximately 0.5. A CaCO3 production rate of 8 mmol CaCO3 m-2 d-1 in the summer of 2007 (1.2 mol m-2 yr-1) is derived by combining the CaCO3: OC ratio with the a net organic carbon production rate (2.5 mol C m-2 yr-1) determined from in situ measurements of oxygen and nitrogen gas concentrations measured on the same mooring (Emerson and Stump, 2010). Carbonate chemistry data from a meridional hydrographic section in this area in 2008 indicate that isopycnal surfaces that outcrop in the winter in the subarctic Pacific and deepen southward into the subtropics are a much stronger source for alkalinity than vertical mixing. This pathway has a high enough Alk:DIC ratio to support the CaCO3:OC production rate implied by the fCO2 and pH data.

Imaging Catalytic Activation of CO 2 on Cu 2O (110): A First-Principles Study

DOE PAGES

Li, Liang; Zhang, Rui; Vinson, John; ...

2018-03-05

Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO 2 reduction. While photoreduction of CO 2 is a viable approach for fuel generation, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu 2O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO 2 and the Cu 2O surface is largely unknown, and detailed experimental measurements are lacking. In this study, density-functional-theory (DFT) calculations have been performed to identify the Cu 2O (110) surface stoichiometry that favors CO 2 reduction. To facilitate interpretation ofmore » scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO 2 reduction reaction on, and rational surface engineering of, Cu 2O (110). In conclusion, they also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.« less

Imaging Catalytic Activation of CO 2 on Cu 2O (110): A First-Principles Study

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

Li, Liang; Zhang, Rui; Vinson, John

Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO 2 reduction. While photoreduction of CO 2 is a viable approach for fuel generation, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu 2O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO 2 and the Cu 2O surface is largely unknown, and detailed experimental measurements are lacking. In this study, density-functional-theory (DFT) calculations have been performed to identify the Cu 2O (110) surface stoichiometry that favors CO 2 reduction. To facilitate interpretation ofmore » scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO 2 reduction reaction on, and rational surface engineering of, Cu 2O (110). In conclusion, they also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.« less

Adsorptive separation of CO 2 in sulfur-doped nanoporous carbons: Selectivity and breakthrough simulation

DOE PAGES

Saha, Dipendu; Orkoulas, Gerassimos; Chen, Jihua; ...

2017-03-01

In this research, we have synthesized two sulfur functionalized nanoporous carbons by post-synthesis modifications with sulfur bearing activating agents that simultaneously enhanced the surface area and introduced sulfur functionalities on the carbon surface. The Brunauer–Emmett–Teller (BET) surface areas of these materials were 2865 and 837 m 2/g with total sulfur contents of 8.2 and 12.9 %, respectively. The sulfur-functionalized carbons were characterized with pore textural properties, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and electron microscopy (SEM and TEM). In both the carbons, CO 2 adsorption isotherms and kinetics were measured in three different temperatures of 298, 288 and 278more » K and pressures up to 760 torr. The gravimetric CO 2 uptake followed the trend with BET surface area but the surface area-based uptake was reversed and it followed the trend of sulfur content. The heat of adsorption of CO 2 in low uptake was 60-65 kJ/mol, which is the highest for CO 2 adsorption in porous carbons. In order to investigate the adsorptive separation of CO 2, N 2 and CH 4 adsorption isotherms were also measured at 298 K and 760 torr. The selectivity of separation for CO 2/N 2 and CO 2/CH 4 was calculated based on the Ideal Adsorbed Solution Theory (IAST) and all the results demonstrated the high CO 2 selectivity for the carbon with higher sulfur content. The adsorption isotherms were combined with mass balances to calculate the breakthrough behavior of the binary mixtures of CO 2/N 2 and CO 2/CH 4. The simulation results demonstrated that the dimensionless breakthrough time is a decreasing function of the mole fraction of CO 2 in the feed stream. The overall results suggest that the sulfurfunctionalized carbons can be employed as potential adsorbents for CO 2 separation.« less

Decomposition mechanism of formic acid on Cu (111) surface: A theoretical study

NASA Astrophysics Data System (ADS)

Jiang, Zhao; Qin, Pei; Fang, Tao

2017-02-01

The study of formic acid decomposition on transition metal surfaces is important to obtain useful information for vapor phase catalysis involving HCOOH and for the development of direct formic acid fuel cells. In this study, periodic density functional theory calculations have been employed to investigate the dissociation pathways of HCOOH on Cu (111) surface. About adsorption, it is found that the adsorption of HCOO, COOH, HCO, CO, OH and H on Cu (111) are considered chemisorption, whereas HCOOH, CO2, H2O and H2 have the weak interaction with Cu (111) surface. Furthermore, the minimum energy pathways are analyzed for the decomposition of HCOOH to CO2 and CO through the scission of Hsbnd O, Csbnd H and Csbnd O bonds. It is found that HCOOH, HCOO and COOH prefer to dissociate in the related reactions rather than desorb. For the decomposition, it is indicated that HCO and COOH are the main dissociated intermediates of trans-HCOOH, CO2 is the main dissociated intermediates of bidentate-HCOO, and CO is the main dissociated product of cis-COOH. The co-adsorbed H atom is beneficial for the formation of CO2 from cis-COOH. Besides, it is found that the most favorable path for HCOOH decomposition on Cu (111) surface is HCOOH-HCO-CO (Path 5), where the step of CO formation from HCO dehydrogenation is considered to be the rate-determining step. The results also show that CO is preferentially formed as the dominant product of HCOOH on Cu (111) surface.

Ab Initio Cluster Calculations for the Adsorption of Small Molecules on Oxide Surfaces - from Single Molecules to Monolayers

NASA Astrophysics Data System (ADS)

Pykavy, M.; Staemmler, V.; Rittner, F.

2000-04-01

Quantum chemical ab initio cluster calculations were performed for the adsorption of small molecules on metal oxide surfaces. Two systems were studied in detail: The adsorption of N2 on the (110) surface plane of TiO2 (rutile) and the adsorption of CO on the polar (0001) surface of Cr2O3. In both cases a full five-dimensional potential for the interaction of a single molecule with the respective surface was calculated. For N2/TiO2 (110) the minimum was found for the end-on adsorption of N2 atop a coordinately unsaturated surface Ti atom, with an adsorption energy of (35 ± 5) kJ/mol. In the case of CO/Cr2O3 (0001) the CO molecule is adsorbed strongly tilted (almost side-on) along a line connecting two Cr3+ ions at the surface; the calculated adsorption energy is 22 kJ/mol. In conjunction with empirical pair potentials for the N2/N2 and CO/CO interaction in the gas phase, Monte Carlo simulations were carried out to determine adsorption isotherms and the geometric structure of adsorbed monolayers.

DFT analysis of the reaction paths of formaldehyde decomposition on silver.

PubMed

Montoya, Alejandro; Haynes, Brian S

2009-07-16

Periodic density functional theory is used to study the dehydrogenation of formaldehyde (CH(2)O) on the Ag(111) surface and in the presence of adsorbed oxygen or hydroxyl species. Thermodynamic and kinetic parameters of elementary surface reactions have been determined. The dehydrogenation of CH(2)O on clean Ag(111) is thermodynamically and kinetically unfavorable. In particular, the activation energy for the first C-H bond scission of adsorbed CH(2)O (25.8 kcal mol(-1)) greatly exceeds the desorption energy for molecular CH(2)O (2.5 kcal mol(-1)). Surface oxygen promotes the destruction of CH(2)O through the formation of CH(2)O(2), which readily decomposes to CHO(2) and then in turn to CO(2) and adsorbed hydrogen. Analysis of site selectivity shows that CH(2)O(2), CHO(2), and CHO are strongly bound to the surface through the bridge sites, whereas CO and CO(2) are weakly adsorbed with no strong preference for a particular surface site. Dissociation of CO and CO(2) on the Ag(111) surface is highly activated and therefore unfavorable with respect to their molecular desorption.