Chemical reaction mechanisms between Y2O3 stabilized ZrO2 and Gd doped CeO2 with PH3 in coal syngas

NASA Astrophysics Data System (ADS)

Chen, Gang; Kishimoto, Haruo; Yamaji, Katsuhiko; Kuramoto, Koji; Gong, Mingyang; Liu, Xingbo; Hackett, Gregory; Gerdes, Kirk; Horita, Teruhisa

2014-12-01

To clarify the chemical stability of the key materials exposed to coal syngas (CSG) containing PH3 contaminant atmosphere, exposure tests of Y2O3 8 mol.% stabilized ZrO2 (YSZ) and Gd doped CeO2 (GDC) are carried out in simulated CSG with different concentrations of PH3. Significant reaction between YSZ and 10 ppm PH3 in CSG atmosphere is confirmed, and no obvious reaction is detected on the surface of YSZ after exposed in CSG with 1 ppm PH3. YPO4, Zr2.25(PO4)3 and monoclinic Y partial stabilized ZrO2 (m-PSZ) are identified on the YSZ pellet surface after exposed in CSG with 10 ppm PH3. GDC reacted with PH3 even at 1 ppm concentration. A (Ce0.9Gd0.1)PO4 layer is formed on the surface of GDC pellet after exposure in CSG with 10 ppm PH3. Possible reaction mechanisms between YSZ and GDC with PH3 in CSG are clarified. Compared with GDC, YSZ exhibits sufficient phosphorus resistance for devices directly exposed to a coal syngas atmosphere containing low concentration of PH3.

n-type dopants in (001) β-Ga2O3 grown on (001) β-Ga2O3 substrates by plasma-assisted molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Han, Sang-Heon; Mauze, Akhil; Ahmadi, Elaheh; Mates, Tom; Oshima, Yuichi; Speck, James S.

2018-04-01

Ge and Sn as n-type dopants in (001) β-Ga2O3 films were investigated using plasma-assisted molecular beam epitaxy. The Ge concentration showed a strong dependence on the growth temperature, whereas the Sn concentration remains independent of the growth temperature. The maximum growth temperature at which a wide range of Ge concentrations (from 1017 to 1020 cm-3) could be achieved was 675 °C while the same range of Sn concentration could be achieved at growth temperature of 750 °C. Atomic force microscopy results revealed that higher growth temperature shows better surface morphology. Therefore, our study reveals a tradeoff between higher Ge doping concentration and high quality surface morphology on (001) β-Ga2O3 films grown by plasma-assisted molecular beam epitaxy. The Ge doped films had an electron mobility of 26.3 cm2 V-1 s-1 at the electron concentration of 6.7 × 1017 cm-3 whereas the Sn doped films had an electron mobility of 25.3 cm2 V-1 s-1 at the electron concentration of 1.1 × 1018 cm-3.

Acetone sensors based on microsheet-assembled hierarchical Fe2O3 with different Fe3+ concentrations

NASA Astrophysics Data System (ADS)

Wang, Han; Yan, Lei; Li, Shuo; Li, Yu; Liu, Li; Du, Liting; Duan, Haojie; Cheng, Yali

2018-02-01

Several different morphologies of microsheet-assembled Fe2O3 have been fabricated by hydrothermal method using diverse concentrations of Fe3+ precursor solutions (0.025, 0.020, 0.015, 0.010 mol/L Fe3+). The as-synthesized materials have been characterized by scanning electron microscope (SEM), X-ray powder diffraction (XRD), and energy-dispersive X-ray spectrometry (EDS). The SEM images reflect that the morphologies of as-synthesized materials are affected by the concentrations of Fe3+ in precursor solutions. The less concentration of Fe3+, the more porous of Fe2O3 microflowers, and thinner of slices distributed on the surface. Furthermore, gas sensors based on these Fe2O3 microflowers manufactured and tested to various common gases. The optimum response value to 100 ppm acetone is 52 at the working temperature of 220 °C. Meanwhile, the Fe2O3 microflower sensors possess ultrafast response-recovery speed, which are 8 and 19 s, respectively. The possible sensing mechanism was mainly attributed to the high surface area, three-dimensional porous structure.

Effective decolorization and adsorption of contaminant from industrial dye effluents using spherical surfaced magnetic (Fe{sub 3}O{sub 4}) nanoparticles

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

Suriyaprabha, R., E-mail: sooriyarajendran@gmail.com; Khan, Samreen Heena; Pathak, Bhawana

2016-04-13

Treatment of highly concentrated Industrial dye stuff effluents released in the environment is the major issue faced in the era of waste management as well as in water pollution. Though there is availability of conventional techniques in large numbers, there is a need of efficient and effective advance technologies. In account of that, Nanotechnology plays a prominent role to treat the heavy metals, organic and inorganic contaminants using smart materials in nano regime (1 -100 nm). Among these nanomaterials like Iron Oxide (Fe{sub 3}O{sub 4}, magnetic nanoparticle) is one of the most promising candidates to remove the heavy metals from themore » industrial effluent. Fe{sub 3}O{sub 4} is the widely used smart material with magnetic property having high surface area; high surface to volume ratio provides more surface for the chemical reaction for the surface adsorption. Fe{sub 3}O{sub 4} nanoparticles have been synthesized using sonochemical method using ultra frequency in aqueous solution under optimized conditions. The as-synthesized nanoparticle was analyzed using different characterization tool. The Transmission Electron microscope (TEM) images revealed 10-12 nm spherical shape nanoparticles; crystal phase and surface morphology was confirmed by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM), respectively. The functional group were identified by Fourier Transform-Infra Red Spectroscopy (FT-IR), revealed the bending and stretching vibrations associated with Iron Oxide nanoparticle. In present study, for the efficient removal of contaminants, different concentration (10-50 ppm) of dye stuff effluent has been prepared and subjected to adsorption and decolourization at definite time intervals with Fe{sub 3}O{sub 4} nanoparticles. The concentration of Iron oxide and the time (45 mins) was kept fixed for the reaction whereas the concentration of dye stuff effluent was kept varying. It was found that the spherical shaped Fe{sub 3}O{sub 4} proved to be the potential material for the adsorption of corresponding contaminants due to its highly active adsorbing surfaces. The result concluded that the effective adsorption and decolourization of contaminants is observed in different concentration with the maximum time period of 45 mins with the optimized concentration of Fe{sub 3}O{sub 4}.« 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...

Nitrous Oxide Emissions From Northern Forested and Harvested Ecosystems

NASA Astrophysics Data System (ADS)

Kavanaugh, K. M.; Kellman, L. M.

2005-12-01

Very little is known about how deforestation alters the soil subsurface production and surface emissions of N2O from northern forest soils. Soil N2O surface fluxes and subsurface concentrations from two 3 year old harvested and intact forest pairs of contrasting soil texture were monitored during the 2004 and 2005 growing seasons in the Acadian forest of Atlantic Canada in order to: 1) quantify N2O emissions associated with each land-use type, 2) examine spatial and temporal variations in subsurface concentrations and surface fluxes at each site, and 3) determine the suitability of a photoacoustic gas monitor (PGM) for in- situ field measurements vs. field sample collection and laboratory analysis on a gas chromatograph. Each site was instrumented with 11 permanent collars for surface flux measurements designed to capture the microsite variability at the sites. Subsurface soil gas samplers, designed to identify the important zones of N2O production in the vertical profile were installed at depths of 0, 10, 20 and 35 cm below the organic-mineral soil interface. Surface fluxes were measured with non-steady-state vented surface flux chambers with measurements of all surface flux and subsurface data made on a bi-weekly basis. Results suggest that spatial and temporal variability in surface emissions are very high and routinely close to zero. Subsurface profile concentration data shows vertical concentration profiles at intact forest sites with concentrations close to atmospheric, while harvested sites show a pattern of increasing N2O concentration with depth, reaching a maximum of approximately 27000ppb at 35cm.

Improvement in LPG sensing response by surface activation of ZnO thick films with Cr2O3

NASA Astrophysics Data System (ADS)

Hastir, Anita; Virpal, Kaur, Jasmeet; Singh, Gurpreet; Kohli, Nipin; Singh, Onkar; Singh, Ravi Chand

2015-05-01

Liquefied Petroleum Gas (LPG) sensing response of pure and Cr2O3 activated ZnO has been investigated in this study. Zinc oxide was synthesized by co-precipitation route and deposited as a thick film on an alumina substrate. The surface of ZnO sensor was activated by chromium oxide on surface oxidation by chromium chloride. The concentration of chromium chloride solution used to activate the ZnO sensor surface has been varied from 0 to 5 %. It is observed that response to LPG has improved as compared to pure ZnO.

Synthesis and luminescent properties of CaCO3:Eu3+@SiO2 phosphors with core-shell structure

NASA Astrophysics Data System (ADS)

Liu, Min; Kang, Ming; Chen, Kexu; Mou, Yongren; Sun, Rong

2018-03-01

Integrating the processes of preparation of CaCO3:Eu3+ and its surface-coating, core-shell structured CaCO3:Eu3+@SiO2 phosphors with red emission were synthesized by the carbonation method and surface precipitation procedure using sodium silicate as silica source. The phase structure, thermal stability, morphology and luminescent property of the as-synthesized samples were characterized by X-ray diffraction, Fourier transform infrared spectrum, thermal analysis, field-emission scanning electron microscopy, transmission electron microscope and photoluminescence spectra. The experimental results show that Eu3+ ions as the luminescence center are divided into two types: one is at the surface of the CaCO3 and the other inhabits the site of Ca2+. For CaCO3:Eu3+@SiO2 phosphors, the SiO2 layers are continuously coated on the surface of CaCO3:Eu3+ and show a typical core-shell structure. After coated with SiO2 layer, the luminous intensity and the compatibility with the rubber matrix increase greatly. Additionally, the luminous intensity increases with the increasing of Eu3+ ions concentration in CaCO3 core and concentration quenching occurs when Eu3+ ions concentration exceeds 7.0 mol%, while it is 5.0 mol% for CaCO3:Eu3+ phosphors. Therefore, preparation of CaCO3:Eu3+@SiO2 phosphors can not only simplify the experimental process through integrating the preparation of CaCO3:Eu3+ and SiO2 layer, but also effectively increase the luminous intensities of CaCO3:Eu3+ phosphors. The as-obtained phosphors may have potential applications in the fields of optical materials and functional polymer composite materials, such as plastics and rubbers.

Surface ozone at the Devils Postpile National Monument receptor site during low and high wildland fire years

Treesearch

Andrzej Bytnerowicz; Joel D. Burley; Ricardo Cisneros; Haiganoush K. Preisler; Susan Schilling; Donald Schweizer; John Ray; Deanna Dulen; Christopher Beck; Bianca Auble

2013-01-01

Surface ozone (O3) was measured at the Devils Postpile National Monument (DEPO), eastern Sierra Nevada Mountains, California, during the 2007 (low-fire) and 2008 (high-fire) summer seasons. While mean and median values of O3 concentrations for the 2007 and 2008 summer seasons were similar, maximum O3...

ZIF-8 derived hexagonal-like α-Fe2O3/ZnO/Au nanoplates with tunable surface heterostructures for superior ethanol gas-sensing performance

NASA Astrophysics Data System (ADS)

Chen, Ying; Li, Hui; Ma, Qian; Che, Quande; Wang, Junpeng; Wang, Gang; Yang, Ping

2018-05-01

A series of hexagonal-like α-Fe2O3/ZnO/Au nanoplate heterostructures with tunable morphologies and superior ethanol gas-sensing performance were successfully synthesized via the facile multi-step reaction processes. Hexagonal-like α-Fe2O3 nanoplates with uniform size around 150 nm are employed as new sensor substrates for loading the well-distributed ZnO and Au nanoparticles with adjustable size distribution on the different surfaces. Brunauer-EmmeQ-Teller (BET) surface areas of α-Fe2O3 and α-Fe2O3/ZnO samples are evaluated to be 37.94 and 61.27 m2/g, respectively, while α-Fe2O3/ZnO/Au composites present the highest value of 79.08 m2/g. These α-Fe2O3-based functional materials can exhibit outstanding sensing properties to ethanol. When the ethanol concentration is 100 ppm, the response value of α-Fe2O3/ZnO/Au composites can reach up to 170, which is 14.6 and 80.3 times higher than that of α-Fe2O3/ZnO and pure α-Fe2O3, respectively. The recycling stability and long-time effectiveness can be availably maintained within 30 days, as well as the response and recovery times are shortened to 4 and 5 s, respectively. Significantly, the response value of α-Fe2O3/ZnO/Au composite is still up to 63 at an operating temperature of 280 °C even though the ethanol concentration decreases to 10 ppm. The enhanced gas sensing mechanism would be focused on the synergistic effects of phase compositions, surface heterogeneous structures, large specific surface area, and the selective depositions of Au nanoparticles in α-Fe2O3/ZnO/Au sensors. The synergistic effect of different surface heterostructures referring to α-Fe2O3/Au and α-Fe2O3/ZnO/Au and their novel electron transport processes on the surfaces are first investigated and discussed in details. It is expected that hexagonal-like α-Fe2O3/ZnO/Au nanoplate heterostructures with excellent sensing performance can be the promising highly-sensitive materials in the actual application for monitoring and detecting ethanol.

Plasmachemical and heterogeneous processes in ozonizers with oxygen activation by a dielectric barrier discharge

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

Mankelevich, Yu. A., E-mail: ymankelevich@mics.msu.su; Voronina, E. N.; Poroykov, A. Yu.

Plasmachemical and heterogeneous processes of generation and loss of ozone in the atmosphericpressure dielectric barrier discharge in oxygen are studied theoretically. Plasmachemical and electronic kinetics in the stage of development and decay of a single plasma filament (microdischarge) are calculated numerically with and without allowance for the effects of ozone vibrational excitation and high initial ozone concentration. The developed analytical approach is applied to determine the output ozone concentration taking into account ozone heterogeneous losses on the Al{sub 2}O{sub 3} dielectric surface. Using the results of quantummechanical calculations by the method of density functional theory, a multistage catalytic mechanism ofmore » heterogeneous ozone loss based on the initial passivation of a pure Al{sub 2}O{sub 3} surface by ozone and the subsequent interaction of O{sub 3} molecules with the passivated surface is proposed. It is shown that the conversion reaction 2O{sub 3} → 3O{sub 2} of a gas-phase ozone molecule with a physically adsorbed ozone molecule can result in the saturation of the maximum achievable ozone concentration at high specific energy depositions, the nonstationarity of the output ozone concentration, and its dependence on the prehistory of ozonizer operation.« less

The effect of concentration ratio and type of functional group on synthesis of CNT-ZnO hybrid nanomaterial by an in situ sol-gel process

NASA Astrophysics Data System (ADS)

Hosseini Largani, Sekineh; Akbarzadeh Pasha, Mohammad

2017-12-01

In this research, MWCNT-ZnO hybrid nanomaterials were synthesized by a simple sol-gel process using Zn(CH3COO)2·2H2O and functionalized MWCNT with carboxyl(COOH) and hydroxyl(OH) groups. Three different mass ratios of MWCNT:ZnO = 3:1, 1:1 and 1:3 were examined. The prepared nanomaterials were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and Fourier transform infrared spectroscopy (FTIR). Successful growth of MWCNT-ZnO hybrids for both COOH and OH functional groups and all the three mass ratios were obtained. The ZnO nanoparticles attached on the surfaces of CNTs have rather spherical shapes and hexagonal crystal structure. By increasing the concentration of ZnO, the number and average size of ZnO nanoparticles decorated the body of CNTs in hybrid structures increase. By increasing the ZnO precursor, the distribution of ZnO nanoparticles that appeared on the surface of CNTs becomes more uniform. The SEM observation beside EDX analysis revealed that at the same concentration ratio the amount of ZnO loading on the surface of MWCNT-COOH is more than MWCNT-OH. Moreover, the average size of ZnO nanoparticles attached on the surface of COOH functionalized CNTs is relatively smaller than that of OH functionalized ones.

Soot Surface Oxidation in Laminar Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure. Appendix I

NASA Technical Reports Server (NTRS)

Xu, F.; El-Leathy, A. M.; Kim, C. H.; Faeth, G. M.; Yuan, Z.-G. (Technical Monitor); Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

2003-01-01

Soot surface oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round fuel jets burning in coflowing dry air considering acetylene-nitrogen, ethylene, propyiene-nitrogen, propane and acetylene-benzene-nitrogen in the fuel stream. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of major stable gas species (N2, H2O, H2, O2, CO, CO2, CH4, C2H2, C2H6, C3H6, C3H8, and C6H6) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by deconvoluted Li/LiOH atomic absorption and flow velocities by laser velocimetry. For present test conditions, it was found that soot surface oxidation rates were not affected by fuel type, that direct rates of soot surface oxidation by O2 estimated from Nagle and Strickland-Constable (1962) were small compared to observed soot surface oxidation rates because soot surface oxidation was completed near the flame sheet where O2 concentrations were less than 3% by volume, and that soot surface oxidation rates were described by the OH soot surface oxidation mechanism with a collision efficiency of 0.14 and an uncertainty (95% confidence) of +/- 0.04 when allowing for direct soot surface oxidation by O2, which is in reasonably good agreement with earlier observations of soot surface oxidation rates in both premixed and diffusion flames at atmospheric pressure.

Negative impact of surface Ti3+ defects on the photocatalytic hydrogen evolution activity of SrTiO3

NASA Astrophysics Data System (ADS)

Chen, Haidong; Zhang, Feng; Zhang, Weifeng; Du, Yingge; Li, Guoqiang

2018-01-01

Defects play an important and in many cases dominant role in the physical and chemical properties of many oxide materials. In this work, we show that the surface Ti3+ defects in SrTiO3 (STO), characterized by electron paramagnetic resonance and X-ray photoelectron spectroscopy, directly impact the photocatalytic activity of STO. O2 species are found to absorb preferentially on Ti3+ defect sites. Hydrogen evolution under ambient air diminishes with the increase in the concentration of surface Ti3+. This is explained by the over-accumulation of Pt cocatalysts on the site of surface Ti3+ defects after the removal of adsorbed O2.

Airborne measurements of tropospheric ozone destruction and particulate bromide formation in the Arctic

NASA Technical Reports Server (NTRS)

Schnell, Russell C.; Sheridan, Patrick J.; Peterson, Richard E.; Oltmans, S. J.

1988-01-01

Aircraft profiles of O3 concentrations over the Arctic ice pack in spring exhibit a depletion of O3 beneath the surface temperature inversion. One such profile from the NOAA WP-3D Arctic Gas and Aerosol Sampling Program (AGASP) flights in April, 1986 north of Alert, NWT (YLT, 82.5 N) is shown. The gradient of O3 across the temperature inversion, which is essentially a step function from tropospheric values (35 to 40 ppbv) to 0, is somewhat masked by a 1-min running mean applied to the data. Evidence is presented that O3 destruction beneath the Arctic temperature inversion is the result of a photochemical reaction between gaseous Br compounds and O3 to produce particulate Br aerosol. It is noted that in springtime, O3 at the Alert Baseline Station regularly decreases from 30 to 40 ppbv to near 0 over the period of a few hours to a day. At the same time, there is a production of particulate Br with a near 1.0 anti-correlation to O3 concentration. Surface concentrations of bromoform in the Arctic exhibit a rapid decrease following polar sunrise. AGASP aircraft measurements of filterable bromine particulates in the Arctic (March-April, 1983 and 1986) are shown. The greatest concentrations of Br aerosol (shown as enrichment factors relative to to Na in seawater, EFBR (Na)) were observed in samples collected beneath the surface temperature inversion over ice. Samples collected at the same altitude over open ocean (off Spitzbergen) labeled Marine did not exhibit similar Br enrichments. A second region of particulate Br enrichment was observed in the lower stratosphere, which regularly descends to below 500 mb (5.5 km) in the high Arctic. The NOAA WP-3D flew in the stratosphere on all AGASP flights and occasionally measured O3 concentrations in excess of 300 ppbv.

Interface Trap Density Reduction for Al2O3/GaN (0001) Interfaces by Oxidizing Surface Preparation prior to Atomic Layer Deposition.

PubMed

Zhernokletov, Dmitry M; Negara, Muhammad A; Long, Rathnait D; Aloni, Shaul; Nordlund, Dennis; McIntyre, Paul C

2015-06-17

We correlate interfacial defect state densities with the chemical composition of the Al2O3/GaN interface in metal-oxide-semiconductor (MOS) structures using synchrotron photoelectron emission spectroscopy (PES), cathodoluminescence and high-temperature capacitance-voltage measurements. The influence of the wet chemical pretreatments involving (1) HCl+HF etching or (2) NH4OH(aq) exposure prior to atomic layer deposition (ALD) of Al2O3 were investigated on n-type GaN (0001) substrates. Prior to ALD, PES analysis of the NH4OH(aq) treated surface shows a greater Ga2O3 component compared to either HCl+HF treated or as-received surfaces. The lowest surface concentration of oxygen species is detected on the acid etched surface, whereas the NH4OH treated sample reveals the lowest carbon surface concentration. Both surface pretreatments improve electrical characteristics of MOS capacitors compared to untreated samples by reducing the Al2O3/GaN interface state density. The lowest interfacial trap density at energies in the upper band gap is detected for samples pretreated with NH4OH. These results are consistent with cathodoluminescence data indicating that the NH4OH treated samples show the strongest band edge emission compared to as-received and acid etched samples. PES results indicate that the combination of reduced carbon contamination while maintaining a Ga2O3 interfacial layer by NH4OH(aq) exposure prior to ALD results in fewer interface traps after Al2O3 deposition on the GaN substrate.

Oxidant effect of La(NO3)3·6H2O solution on the crystalline characteristics of nanocrystalline ZrO2 films grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Oh, Nam Khen; Kim, Jin-Tae; Kang, Goru; An, Jong-Ki; Nam, Minwoo; Kim, So Yeon; Park, In-Sung; Yun, Ju-Young

2017-02-01

Nanocrystalline ZrO2 films were synthesized by atomic layer deposition method using CpZr[N(CH3)2]3 (Cp = C5H5) as the metal precursor and La(NO3)3·6H2O solution as the oxygen source. La element in the deposited ZrO2 films could not be detected as its content was below the resolution limit of the X-ray photoelectron spectroscopy. The alternative introduction of La(NO3)3·6H2O solution to conventionally used H2O as the oxidant effectively altered the crystalline structure, grain size, and surface roughness of the grown ZrO2 films. Specifically, the crystalline structure of the ZrO2 film changed from a mixture of tetragonal and monoclinic phases to monoclinic phase. The average grain size also increased, and the resulting film surface became rougher. The average grain sizes of the ZrO2 films prepared from La(NO3)3·6H2O solution at concentrations of 10, 20, 30, and 40% were 280, 256, 208, and 200 nm, respectively, whereas that prepared using H2O oxidant was 142 nm. However, the concentration of La(NO3)3·6H2O solution minimally influenced the crystalline characteristics of the nanocrystalline ZrO2 films i.e., the crystalline structure, grain size, and surface roughness except for crystallite size.

Experimental investigation of the influence of nanoparticles on water-based mud

NASA Astrophysics Data System (ADS)

Dhiman, Paritosh; Cheng, Yaoze; Zhang, Yin; Patil, Shirish

2018-03-01

This study has investigated the influence of nanoparticles including nanoparticle concentration, size, and type on water-based mud (WBM) properties including rheology, filtration, and lubricity through experimental tests, while the influence of temperature and aging on these properties have been investigated. It has been found that adding SiO2 nanoparticles increase the plastic viscosity and decrease the yield points and gel strengths with the increase of nanoparticle concentration. At fixed 0.5 wt%, the plastic viscosity decreases with the increase of TiO2 nanoparticle size, but the influence of TiO2 nanoparticle size on yield points and gel strengths is not monotonous. In general, adding negative charged SiO2 nanoparticles reduce the yield points and gel strengths, while adding positively charged TiO2, Al2O3, and Fe3O4 nanoparticles increase yield points and gel strengths. Adding lower concentrations (< 0.05 wt%) of SiO2 nanoparticles improved mud filtration and lubricity properties, but higher concentrations are adverse to these properties and adding 0.5 wt% TiO2, Al2O3 and Fe3O4 nanoparticles impaired these properties. Besides, it is found that there is no consistent influence of aging on mud properties and adding nanoparticles cannot improve aging resistance of mud. Although adding nanoparticles can significantly affect WBM properties, their influences are not consistency, depending on the integrated impact of the nanoparticle properties, such as surface electrical property, specific surface area, concentration, and size.

Investigation of hybrid plasma-catalytic removal of acetone over CuO/γ-Al2O3 catalysts using response surface method.

PubMed

Zhu, Xinbo; Tu, Xin; Mei, Danhua; Zheng, Chenghang; Zhou, Jinsong; Gao, Xiang; Luo, Zhongyang; Ni, Mingjiang; Cen, Kefa

2016-07-01

In this work, plasma-catalytic removal of low concentrations of acetone over CuO/γ-Al2O3 catalysts was carried out in a cylindrical dielectric barrier discharge (DBD) reactor. The combination of plasma and the CuO/γ-Al2O3 catalysts significantly enhanced the removal efficiency of acetone compared to the plasma process using the pure γ-Al2O3 support, with the 5.0 wt% CuO/γ-Al2O3 catalyst exhibiting the best acetone removal efficiency of 67.9%. Catalyst characterization was carried out to understand the effect the catalyst properties had on the activity of the CuO/γ-Al2O3 catalysts in the plasma-catalytic reaction. The results indicated that the formation of surface oxygen species on the surface of the catalysts was crucial for the oxidation of acetone in the plasma-catalytic reaction. The effects that various operating parameters (discharge power, flow rate and initial concentration of acetone) and the interactions between these parameters had on the performance of the plasma-catalytic removal of acetone over the 5.0 wt% CuO/γ-Al2O3 catalyst were investigated using central composite design (CCD). The significance of the independent variables and their interactions were evaluated by means of the Analysis of Variance (ANOVA). The results showed that the gas flow rate was the most significant factor affecting the removal efficiency of acetone, whilst the initial concentration of acetone played the most important role in determining the energy efficiency of the plasma-catalytic process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rapid increase of ozone concentrations in Xi'an, China: Anthropogenically or naturally?

NASA Astrophysics Data System (ADS)

Wu, J.; Li, G.; Junji, C.

2017-12-01

The air quality in the Guanzhong basin, China has deteriorated recently caused by growing industries, city expansions, and increasing transportation activity. We report here a substantial increasing trend of ozone (O3) concentrations in Xi'an, the largest city of the basin, and the average observed O3 concentration in the afternoon during summertime has increased by 39% from 2013 to 2016. There are two main possible reasons for the rapid O3 increase. Motor vehicle has been reported to increase by 35% in Xi'an, which enhances the O3 precursors emissions to facilitate the O3 formation. In addition, the surface solar radiation at the meteorological site in Xi'an has been observed to intensify by 30%, which increases the photolysis rates to expedite the O3 production. A persistent high O3 episode from 16 to 22 June 2016 in Xi'an has been simulated using the WRF-CHEM model to evaluate the contribution of the transportation emission and solar radiation enhancement on the O3 trend. The model generally performs reasonably well in simulating the temporal variation and spatial distribution of near-surface O3 and NO2 concentrations against measurements in Xi'an. Sensitivity studies have revealed that the enhancement of transportation emissions and the solar radiation explains about 70% of the O3 trend from 2013 to 2016. Considering that large amounts of biogenic emissions are released over the Qinling Mountains on the south of Xi'an, which can be delivered to Xi'an under favorable meteorological conditions, enhancing O3 formation. Therefore, future studies need to be performed to evaluate impacts of the solar radiation enhancement on the biogenic emissions and further the O3 formation in Xi'an.

Enhanced preferential cytotoxicity through surface modification: synthesis, characterization and comparative in vitro evaluation of TritonX-100 modified and unmodified zinc oxide nanoparticles in human breast cancer cell (MDA-MB-231).

PubMed

Kc, Biplab; Paudel, Siddhi Nath; Rayamajhi, Sagar; Karna, Deepak; Adhikari, Sandeep; Shrestha, Bhupal G; Bisht, Gunjan

2016-01-01

Nanoparticles (NPs) are receiving increasing interest in biomedical research owing to their comparable size with biomolecules, novel properties and easy surface engineering for targeted therapy, drug delivery and selective treatment making them a better substituent against traditional therapeutic agents. ZnO NPs, despite other applications, also show selective anticancer property which makes it good option over other metal oxide NPs. ZnO NPs were synthesized by chemical precipitation technique, and then surface modified using Triton X-100. Comparative study of cytotoxicity of these modified and unmodified NPs on breast cancer cell line (MDA-MB-231) and normal cell line (NIH 3T3) were carried out. ZnO NPsof average size 18.67 ± 2.2 nm and Triton-X modified ZnO NPs of size 13.45 ± 1.42 nm were synthesized and successful characterization of synthesized NPs was done by Fourier transform infrared spectroscopy (FT-IR), X-Ray diffraction (XRD), transmission electron microscopy (TEM) analysis. Surface modification of NPs was proved by FT-IR analysis whereas structure and size by XRD analysis. Morphological analysis was done by TEM. Cell viability assay showed concentration dependent cytotoxicity of ZnO NPs in breast cancer cell line (MDA-MB-231) whereas no positive correlation was found between cytotoxicity and increasing concentration of stress in normal cell line (NIH 3T3) within given concentration range. Half maximum effective concentration (EC50) value for ZnO NPs was found to be 38.44 µg/ml and that of modified ZnO NPs to be 55.24 µg/ml for MDA-MB-231. Crystal violet (CV) staining image showed reduction in number of viable cells in NPs treated cell lines further supporting this result. DNA fragmentation assay showed fragmented bands indicating that the mechanism of cytotoxicity is through apoptosis. Although use of surfactant decreases particle size, toxicity of modified ZnO NPs were still less than unmodified NPs on MDA-MB-231 contributed by biocompatible surface coating. Both samples show significantly less toxicity towards NIH 3T3 in concentration independent manner. But use of Triton-X, a biocompatible polymer, enhances this preferentiality effect. Since therapeutic significance should be analyzed through its comparative effect on both normal and cancer cells, possible application of biocompatible polymer modified nanoparticles as therapeutic agent holds better promise.Graphical abstractSurface coating, characterization and comparative in vitro cytotoxicity study on MDA-MB 231 and NIH 3T3 of ZnO NPs showing enhanced preferentiality by biocompatible surface modification.

Optimization of artificial neural network models through genetic algorithms for surface ozone concentration forecasting.

PubMed

Pires, J C M; Gonçalves, B; Azevedo, F G; Carneiro, A P; Rego, N; Assembleia, A J B; Lima, J F B; Silva, P A; Alves, C; Martins, F G

2012-09-01

This study proposes three methodologies to define artificial neural network models through genetic algorithms (GAs) to predict the next-day hourly average surface ozone (O(3)) concentrations. GAs were applied to define the activation function in hidden layer and the number of hidden neurons. Two of the methodologies define threshold models, which assume that the behaviour of the dependent variable (O(3) concentrations) changes when it enters in a different regime (two and four regimes were considered in this study). The change from one regime to another depends on a specific value (threshold value) of an explanatory variable (threshold variable), which is also defined by GAs. The predictor variables were the hourly average concentrations of carbon monoxide (CO), nitrogen oxide, nitrogen dioxide (NO(2)), and O(3) (recorded in the previous day at an urban site with traffic influence) and also meteorological data (hourly averages of temperature, solar radiation, relative humidity and wind speed). The study was performed for the period from May to August 2004. Several models were achieved and only the best model of each methodology was analysed. In threshold models, the variables selected by GAs to define the O(3) regimes were temperature, CO and NO(2) concentrations, due to their importance in O(3) chemistry in an urban atmosphere. In the prediction of O(3) concentrations, the threshold model that considers two regimes was the one that fitted the data most efficiently.

Effects of trans-Eurasian transport of air pollutants on surface ozone concentrations over Western China

NASA Astrophysics Data System (ADS)

Li, Xiaoyuan; Liu, Junfeng; Mauzerall, Denise L.; Emmons, Louisa K.; Walters, Stacy; Horowitz, Larry W.; Tao, Shu

2014-11-01

Due to a lack of industrialization in Western China, surface air there was, until recently, believed to be relatively unpolluted. However, recent measurements and modeling studies have found high levels of ozone (O3) there. Based on the state-of-the-science global chemical transport model MOZART-4, we identify the origin, pathway, and mechanism of trans-Eurasian transport of air pollutants to Western China in 2000. MOZART-4 generally simulates well the observed surface O3 over inland areas of China. Simulations find surface ozone concentrations over Western China on average to be about 10 ppbv higher than Eastern China. Using sensitivity studies, we find that anthropogenic emissions from all Eurasian regions except China contribute 10-15 ppbv surface O3 over Western China, superimposed upon a 35-40 ppbv natural background. Transport from European anthropogenic sources to Northwestern China results in 2-6 ppbv O3 enhancements in spring and summer. Indian anthropogenic sources strongly influence O3 over the Tibetan Plateau during the summer monsoon. Transport of O3 originating from emissions in the Middle East occasionally reach Western China and increase surface ozone there by about 1-4 ppbv. These influences are of similar magnitude as trans-Pacific and transatlantic transport of O3 and its precursors, indicating the significance of trans-Eurasian ozone transport in hemispheric transport of air pollution. Our study further indicates that mitigation of anthropogenic emissions from Europe, the Indian subcontinent, and the Middle East could benefit public health and agricultural productivity in Western China.

Effects of trans-Eurasian transport of anthropogenic pollutants on surface ozone concentrations over China

NASA Astrophysics Data System (ADS)

Liu, J.; Li, X.; Mauzerall, D. L.; Emmons, L. K.; Horowitz, L. W.; Guo, Y.; Tao, S.

2015-12-01

Due to a lack of industrialization in Western China, surface air there was, until recently, believed to be relatively unpolluted. However, recent measurements and modeling studies have found high levels of ozone (O3) there. Based on the state-of-the-science global chemical transport model MOZART-4, we identify the origin, pathway, and mechanism of trans-Eurasian transport of air pollutants to Western China in 2000. MOZART-4 generally simulates well the observed surface O3 over inland areas of China. Simulations find surface ozone concentrations over Western China on average to be about 10 ppbv higher than Eastern China. Using sensitivity studies as well as a fully-tagged approach, we find that anthropogenic emissions from all Eurasian regions except China contribute 10-15 ppbv surface O3 over Western China, superimposed upon a 35-40 ppbv natural background. Transport from European anthropogenic sources to Northwestern China results in 2-6 ppbv O3 enhancements in spring and summer. Indian anthropogenic sources strongly influence O3 over the Tibetan Plateau during the summer monsoon. Transport of O3 originating from emissions in the Middle East occasionally reach Western China and increase surface ozone there by about 1-4 ppbv. These influences are of similar magnitude as trans-Pacific and transatlantic transport of O3 and its precursors, indicating the significance of trans-Eurasian ozone transport in hemispheric transport of air pollution. Our study further indicates that mitigation of anthropogenic emissions from Europe, the Indian subcontinent, and the Middle East could benefit public health and agricultural productivity in Western China.

Effect of surfactant concentration on the ultraviolet sensing properties of ZnO-cellulose nanocomposites

NASA Astrophysics Data System (ADS)

Sahoo, Karunakar; Nayak, J.

2018-05-01

ZnO nanoparticles were grown, on cellulose fiber surfaces, at three different concentrations of hexamethylenetetramine by an aqueous chemical method. A typical ZnO-cellulose nanocomposite showed an enhanced UV sensing activity due to its large surface area. Due to illumination with ultraviolet light, the surface photocurrent of ZnO-cellulose nanocomposite pellet increased from 8.90 × 10‒7 A to 3.18 × 10‒5 A in 15 s. The UV ON to OFF (IUV/IDark) ratio for this sample was 35.73. Hence, an enhancement in the conductivity due to UV illumination shows that our ZnO-cellulose can be used for the fabrication of UV sensors.

Surface Raman scattering from effervescent magnetic peroxyborates

NASA Astrophysics Data System (ADS)

Walrafen, G. E.; Krishnan, P. N.; Griscom, D. L.; Munro, R.

1982-06-01

Surface Raman scattering using a spinning technique was investigated for solid NaBO3.4H2O and NaBO3.H2O as well as for electron bombarded peroxyborates heated for various times and at temperatures form 110-180 deg C, and for solid Na2O2 and BaO2. The Raman spectra indicate that the breakdown of peroxy groups is accompanied by the formation of trapped molecular O2. Quantitative Raman intensity data were also obtained as functions of heating time at 115 deg C for the 1556 cm-1 line from O2 and for the 890 and 705 cm-1 lines whose intensities scale with the peroxy concentration. These intensity data were treated by logistics theory, and they were found to be consistent with a second-order auto-catalyzed forward reaction dependent on the product of the peroxy and O2 concentrations, plus a first-order reverse reaction dependent only on the O2 concentration.

Surface Raman scattering from effervescent magnetic peroxyborates

NASA Astrophysics Data System (ADS)

Walrafen, G. E.; Krishnan, P. N.; Hokmabadi, M.; Griscom, D. L.; Munro, R. G.

1982-10-01

Surface Raman scattering using a spinning technique was investigated for solid NaBO3ṡ4H2O and NaBO3ṡH2O, as well as for electron bombarded peroxyborates, for peroxyborates heated for various times and at temperatures for 110-180 °C, and for solid Na2O2 and BaO2. The Raman spectra indicate that the breakdown of peroxy groups is accompanied by the formation of trapped molecular O2. Quantitative Raman intensity data were also obtained as functions of heating time at 115 °C for the 1556 cm-1 line from O2 and for the 890 and 705 cm-1 lines whose intensities scale with the peroxy concentration. These intensity data were treated by logistics theory, and they were found to be consistent with a second-order autocatalyzed forward reaction dependent on the product of the peroxy and O2 concentrations, plus a first-order reverse reaction dependent only on the O2 concentration.

X-Ray Photoelectron Spectroscopy Study of the Heating Effects on Pd/6H-SiC Schottky Structure

NASA Technical Reports Server (NTRS)

Chen, Liang-Yu; Hunter, Gary W.; Neudeck, Philip G.; Knight, Dak

1998-01-01

X-ray photoelectron spectroscopy is used to study the effects of heat treatment on the Pd/6H-SiC Schottky diode structure. After heating the structure at 425 C for 140 h, a very thin surface layer of PdO mixed with SiO(x) formed on the palladium surface of the Schottky structure. Heat treatment promoted interfacial diffusion and reaction which significantly broadened the interfacial region. In the interfacial region, the palladium concentration decreases with depth, and the interfacial products are Pd(x)Si (x = 1,2,3,4). In the high Pd concentration regions, Pd4Si is the major silicide component while gr and Pd2Si are major components in the low Pd concentration region. At the center of the interface, where the total palladium concentration equals that of silicon, the concentrations of palladium associated with various palladium silicides (Pd(x)Si, x= 1,2,3,4) are approximately equal. The surface passivation layer composed of PdO and SiO, may significantly affect the electronic and catalytic properties of the surface of the Schottky diode which plays a major role in gas detection. The electronic properties of the Schottky structure may be dominated by a (Pd+Pd(x)Si)/SiC interface. In order to stabilize the properties of the Schottky structure the surface and interface diffusion and reactions must be controlled.

Dependences of deposition rate and OH content on concentration of added trichloroethylene in low-temperature silicon oxide films deposited using silicone oil and ozone gas

NASA Astrophysics Data System (ADS)

Horita, Susumu; Jain, Puneet

2018-03-01

We investigated the dependences of the deposition rate and residual OH content of SiO2 films on the concentration of trichloroethylene (TCE), which was added during deposition at low temperatures of 160-260 °C with the reactant gases of silicone oil (SO) and O3. The deposition rate depends on the TCE concentration and is minimum at a concentration of ˜0.4 mol/m3 at 200 °C. The result can be explained by surface and gas-phase reactions. Experimentally, we also revealed that the thickness profile is strongly affected by gas-phase reaction, in which the TCE vapor was blown directly onto the substrate surface, where it mixed with SO and O3. Furthermore, it was found that adding TCE vapor reduces residual OH content in the SiO2 film deposited at 200 °C because TCE enhances the dehydration reaction.

Resveratrol increases phagocytosis and lipopolysaccharide-induced interleukin-1β production, but decreases surface expression of Toll-like receptor 2 in THP-1 monocytes.

PubMed

Zunino, Susan J; Hwang, Daniel H; Huang, Shurong; Storms, David H

2018-02-01

THP-1 monocytes were used to evaluate the effects of physiological levels of resveratrol aglycone, resveratrol-3-O-glucuronide, resveratrol-4'-O-glucuronide, and resveratrol-3-O-sulfate on phagocytosis, IL-1β, IL-1α, and IL-18 production, viability, and TLR2 and TLR4 expression. THP-1 cells were treated with 1, 5, 10, and 15μM resveratrol or metabolites. Resveratrol-3-O-glucuronide, resveratrol-4'-O-glucuronide, and resveratrol-3-O-sulfate had no effect on the functional parameters tested. Resveratrol aglycone increased phagocytosis at concentrations of 5, 10, and 15μM and LPS-induced IL-1β production at concentrations of 10 and 15μM. Expression of TLR4 increased slightly after resveratrol treatment, but surface expression of TLR2 was reduced as resveratrol concentrations increased. Our data suggest that resveratrol may be effective in modulating monocyte function in an environment where there is direct exposure to the aglycone, such as at the gut epithelium. Published by Elsevier Ltd.

Productions of Volatile Organic Compounds (VOCs) in Surface Waters from Reactions with Atmospheric Ozone

NASA Astrophysics Data System (ADS)

Hopkins, Frances; Bell, Thomas; Yang, Mingxi

2017-04-01

Ozone (O3) is a key atmospheric oxidant, greenhouse gas and air pollutant. In marine environments, some atmospheric ozone is lost by reactions with aqueous compounds (e.g. dissolved organic material, DOM, dimethyl sulfide, DMS, and iodide) near the sea surface. These reactions also lead to formations of volatile organic compounds (VOCs). Removal of O3 by the ocean remains a large uncertainty in global and regional chemical transport models, hampering coastal air quality forecasts. To better understand the role of the ocean in controlling O3 concentrations in the coastal marine atmosphere, we designed and implemented a series of laboratory experiments whereby ambient surface seawater was bubbled with O3-enriched, VOC-free air in a custom-made glass bubble equilibration system. Gas phase concentrations of a range of VOCs were monitored continuously over the mass range m/z 33 - 137 at the outflow of the bubble equilibrator by a proton transfer reaction - mass spectrometer (PTR-MS). Gas phase O3 was also measured at the input and output of the equilibrator to monitor the uptake due to reactions with dissolved compounds in seawater. We observed consistent productions of a variety of VOCs upon reaction with O3, notably isoprene, aldehydes, and ketones. Aqueous DMS is rapidly removed from the reactions with O3. To test the importance of dissolved organic matter precursors, we added increasing (milliliter) volumes of Emiliania huxleyi culture to the equilibrator filled with aged seawater, and observed significant linear increases in gas phase concentrations of a number of VOCs. Reactions between DOM and O3 at the sea-air interface represent a potentially significant source of VOCs in marine air and a sink of atmospheric O3.

Macroscopic and spectroscopic investigations on Eu(III) and Cm(III) sorption onto bayerite (β-Al(OH)3) and corundum (α-Al2O3).

PubMed

Kupcik, Tomas; Rabung, Thomas; Lützenkirchen, Johannes; Finck, Nicolas; Geckeis, Horst; Fanghänel, Thomas

2016-01-01

The interaction of trivalent Cm and Eu with the aluminum hydroxide bayerite (β-Al(OH)3) and the aluminum oxide corundum (α-Al2O3) was investigated by batch sorption experiments and time resolved laser fluorescence spectroscopy (TRLFS). The experimental methods for both polymorphs show similar pH dependent sorption behavior at trace metal ion concentrations (∼10(-7) M), i.e. similar Eu sorption edges and nearly identical Cm speciation between pH=3 and 13. In this pH range the Cm aquo ion as well as the Cm(III) surface species surface⋯Cm(OH)x(H2O)(5-x) (x=0, 1, 2) can be distinguished by TRLFS. The similar sorption data point to a (surface) transformation of the thermodynamically unstable Al2O3 surface into bayerite, in agreement with the similar isoelectric points obtained for both minerals (pH(IEP)=8.6-8.8). The pH dependent surface charge is most likely due to the protonation/deprotonation of singly coordinated Al-OH surface groups, prevailing on the edge planes of the rod-like bayerite crystals and the surface of the colloidal Al2O3 particles. These surface groups are also believed to act as ligands for lanthanide/actinide(III) surface complexation. In contrast to the similar sorption behavior at trace metal ion concentrations, discrepancies are observed at higher Eu levels. While similar sorption edges occur up to 7×10(-7) M Eu for corundum, the pH edge on bayerite is gradually shifted to higher pH values in this Eu concentration range. The latter behavior may be related either to the existence of multiple sorption sites with different sorption affinities, or to the influence of an additional amorphous Al-phase, forming in the course of the bayerite synthesis. Copyright © 2015 Elsevier Inc. All rights reserved.

DESIGN ARTIFACTS IN EULERIAN REGIONAL AIR QUALITY MODELS: EVALUATION OF THE EFFECTS OF LAYER THICKNESS AND VERTICAL PROFILE CORRECTION ON SURFACE OZONE CONCENTRATIONS

EPA Science Inventory

Evaluation studies of the Regional Acid Deposition Model (RADM) results have revealed that there exists high bias of surface SO2 and O3 concentrations by the model, especially during nighttime hours. omparison of the RADM results with surface measurements of hourly ozone concentr...

Direct observation of ozone formation on SiO2 surfaces in O2 discharges

NASA Astrophysics Data System (ADS)

Marinov, D.; Guaitella, O.; Booth, J. P.; Rousseau, A.

2013-01-01

Ozone production is studied in a pulsed O2 discharge at pressures in the range 1.3-6.7 mbar. Time-resolved absolute concentrations of O3 and O are measured in the post-discharge using UV absorption spectroscopy and two-photon absorption laser-induced fluorescence. In a bare silica discharge tube ozone is formed mainly by three-body gas-phase recombination. When the tube surface is covered by a high specific surface silica catalyst heterogeneous formation becomes the main source of ozone. The efficiency of this surface process increases with O2 pressure and is favoured by the presence of OH groups and adsorbed H2O on the surface. At p = 6.7 mbar ozone production accounts for up to 25% of the atomic oxygen losses on the surface.

Modulation of the operational characteristics of amorphous In-Ga-Zn-O thin-film transistors by In2O3 nanoparticles

NASA Astrophysics Data System (ADS)

Lee, Min-Jung; Lee, Tae Il; Park, Jee Ho; Kim, Jung Han; Chae, Gee Sung; Jun, Myung Chul; Hwang, Yong Kee; Baik, Hong Koo; Lee, Woong; Myoung, Jae-Min

2012-05-01

The structure of thin-film transistors (TFTs) based on amorphous In-Ga-Zn-O (a-IGZO) was modified by spin coating a suspension of In2O3 nanoparticles on a SiO2/p++ Si layered wafer surface prior to the deposition of IGZO layer by room-temperature sputtering. The number of particles per unit area (surface density) of the In2O3 nanoparticles could be controlled by applying multiple spin coatings of the nanoparticle suspension. During the deposition of IGZO, the In2O3 nanoparticles initially located on the substrate surface migrated to the top of the IGZO layer indicating that they were not embedded within the IGZO layer, but they supplied In to the IGZO layer to increase the In concentration in the channel layer. As a result, the channel characteristics of the a-IGZO TFT were modulated so that the device showed an enhanced performance as compared with the reference device prepared without the nanoparticle treatment. Such an improved device performance is attributed to the nano-scale changes in the structure of (InO)n ordering assisted by increased In concentration in the amorphous channel layer.

Seasonal variations and cycling of nitrous oxide using nitrogen isotopes and concentrations from an unsaturated zone of a floodplain

NASA Astrophysics Data System (ADS)

Bill, M.; Conrad, M. E.; Kolding, S.; Williams, K. H.; Tokunaga, T. K.

2014-12-01

Nitrous oxide (N2O) concentrations and isotope ratios of 15N to 14N of N2O in the vadose zone mainly depend on atmospheric deposition, symbiotic or non-symbiotic N2 fixation, and nitrification/denitrification processes in underlying groundwater. In an effort to quantify N2O seasonal variations, cycling and N budgets in an alluvial aquifer in western Colorado (Rifle, CO), the concentrations and nitrogen stable isotopes of N2O within the pore space of partially saturated sediments have been monitored over the 2013-2014 years. Vertically resolved profiles spanning from 0m to 3m depth were sampled at 0.5m increments at a periodicity of one month. At each of the profile locations, N2O concentrations decreased from 3m depth to the surface. The maximum concentrations were observed at the interface between the unsaturated zone and groundwater, with minimum values observed in the near surface samples. The d15N values tend to increase from the unsaturated zone/groundwater interface to the surface. Both variation of N2O concentrations and d15N values suggest that denitrification is the main contribution to N2O production and both parameters exhibited a strong seasonal variation. The maximum concentrations (~10ppmv) were observed at the beginning of summer, during the annual maximum in water table elevation. The minimum N2O concentrations were observed in the period from January to May and coincided with low water table elevations. Additionally, nitrogen concentrations and d15N values of the shallowest sediments within the vertical profiles do not show variation, suggesting that the main source of N2O is associated with groundwater denitrification, with the shallower, partially saturated sediments acting as a sink for N2O.

Impact of mine wastewaters on greenhouse gas emissions from northern peatlands used for mine water treatment

NASA Astrophysics Data System (ADS)

Palmer, Katharina; Ronkanen, Anna-Kaisa; Klöve, Björn; Hynynen, Jenna; Maljanen, Marja

2015-04-01

The amount of wastewaters generated during mining operations is increasing along with the increasing number of operation mines, which poses great challenges for mine water management and purification. Mine wastewaters contain high concentrations of nitrogen compounds such as nitrate (NO3-) and ammonium (NH4+) originating from remnant explosives as well as sulfate (SO42-) originating from the oxidation of sulfidic ores. At a mine site in Finnish Lapland, two natural peatlands have been used for cost-effective passive wastewater treatment. One peatland have been used for the treatment of drainage waters (TP 1), while the other has been used for the treatment of process-based wastewaters (TP 4). In this study, the impact of mine water derived nitrogen compounds as well as SO42- on the emission of the potent greenhouse gases methane (CH4) and nitrous oxide (N2O) from those treatment peatlands was investigated. Contaminant concentrations in the input and output waters of the treatment peatlands were monitored which allowed for the calculation of contaminant-specific retention efficiencies. Treatment peatlands showed generally good retention efficiencies for metals and metalloids (e.g. nickel, arsenic, antimony, up to 98% reduction in concentration) with rather low input-concentrations (i.e., in the μg/l-range). On the other hand, retention of contaminants with high input-concentrations (i.e., in mg/l-range) such as NO3-, NH4+ and SO42- was much lower (4-41%, 30-60% and -42-30%, respectively), indicating the limited capability of the treatment peatlands to cope with such high input concentrations. NO3- and NH4+ concentrations were determined in surface and pore water from TP 4 in July 2013 as well as in surface water from TP 1 and TP 4 in October 2013. Up to 720 μM NO3- and up to 600 μM NH4+ were detected in surface water of TP 4 in July 2013. NO3- and NH4+ concentrations in surface waters were highest near the mine wastewater distribution ditch and decreased with increasing distances from the ditch. NO3- concentrations were lower in pore water than in surface water, and the peak in NO3- concentration shifted further away from the distribution ditch with increasing depth. On the contrary, NH4+ concentrations were generally higher in pore water than in surface water, and peak concentrations increased with increasing depth. Highest NH4+ concentrations were detected in 30 to 60 cm depth near the outlet at the south end of TP 4. Fluxes of the greenhouse gases CH4 and N2O from 4 sampling points (2 from TP 4, 1 from TP 1, 1 from reference area) were measured on 7 different occasions 2013 and 2014. CH4 emissions were in the same range as measured in other northern pristine peatlands in the reference area, which is not influenced by mine wastewaters. Treatment peatlands showed only very minor CH4 emissions or even CH4 uptake. On the other hand, treatment peatlands showed high N2O emissions, which were in the same range as N2O emissions observed from northern peat soils used for agriculture. Highest emissions were generally observed near the wastewater distribution ditch of TP 4. N2O emissions from the reference area were negligible or even negative. NO3-, NH4+ and SO42- concentrations were determined from surface waters from each sampling point and sampling occasion. N2O emissions were positively correlated with NO3- concentrations, indicating denitrification-derived N2O production in treatment peatlands. On the other hand, CH4 emissions were negatively correlated with SO42- and NO3- concentrations, indicating that the presence of alternative electron acceptors in large amounts suppresses CH4 production in treatment peatlands. In conclusion, the study revealed that (i) treatment peatlands receive high loads of NO3-, NH4+ and SO42- which are not well retained in the peatlands, (ii) mine wastewaters positively and negatively affect N2O and CH4 emissions, respectively, (iii) N2O emissions are positively correlated with NO3- concentrations, and (iv) CH4 emissions are negatively correlated with NO3- and SO42- concentrations. This study thus illustrates the pronounced impacts of mine wastewaters on processes involved in greenhouse gas turnover in peatlands ecosystems.

Vertical profiles in NO3 and N2O5 measured from an aircraft: Results from the NOAA P-3 and surface platforms during the New England Air Quality Study 2004

NASA Astrophysics Data System (ADS)

Brown, Steven S.; Dubé, William P.; Osthoff, Hans D.; Stutz, Jochen; Ryerson, Thomas B.; Wollny, Adam G.; Brock, Charles A.; Warneke, Carsten; de Gouw, Joost A.; Atlas, Eliot; Neuman, J. Andrew; Holloway, John S.; Lerner, Brian M.; Williams, Eric J.; Kuster, William C.; Goldan, Paul D.; Angevine, Wayne M.; Trainer, Michael; Fehsenfeld, Frederick C.; Ravishankara, A. R.

2007-11-01

The nocturnal nitrogen oxides, NO3 and N2O5, are important to the chemical transformation and transport of NOx, O3 and VOC. Their concentrations, sources and sinks are known to be vertically stratified in the nighttime atmosphere. In this paper, we report vertical profiles for NO3 and N2O5 measured from an aircraft (the NOAA P-3) as part of the New England Air Quality Study in July and August 2004. The aircraft data are compared to surface measurements made in situ from a ship and by long-path DOAS. Consistent with previous, vertically resolved studies of NO3 and N2O5, the aircraft measurements show that these species occur at larger concentrations and are longer lived aloft than they are at the surface. The array of in situ measurements available on the P-3 allows for investigation of the mechanisms that give rise to the observed vertical gradients. Selected vertical profiles from this campaign illustrate the role of biogenic VOC, particularly isoprene and dimethyl sulfide, both within and above the nocturnal and/or marine boundary layer. Gradients in relative humidity and aerosol surface may also create a vertical gradient in the rate of N2O5 hydrolysis. Low-altitude intercepts of power plant plumes showed strong vertical stratification, with plume depths of 80 m. The efficiency of N2O5 hydrolysis within these plumes was an important factor determining the low-level NOx and O3 transport or loss at night. Averages of nocturnal O3, NO2, NO3 and N2O5 binned according to altitude were consistent with the trends from individual profiles. While production rates of NO3 peaked near the surface, lifetimes of NO3 and N2O5 were maximum aloft, particularly in the free troposphere. Variability in NO3 and N2O5 was large and exceeded that of NO2 or O3 because of inhomogeneous distribution of NOx emissions and NO3 and N2O5 sinks.

Surface enhanced Raman scattering activity of dual-functional Fe3O4/Au composites

NASA Astrophysics Data System (ADS)

Wang, Li-Ping; Huang, Yu-Bin; Lai, Ying-Huang

2018-03-01

There is a high demand for multifunctional materials that can integrate sample collection and sensing. In this study, magnetic Fe3O4 clusters were fabricated using a simple solvent-thermal method. The effect of the reductant (sodium citrate, SC) on the structure and morphology of Fe3O4 was examined by the variation in the reagent amount. The resulting Fe3O4 clusters were functionalized with 3-aminopropyltriethoxysilane (APTES) to anchor Au nanoparticles to its surface. The fabricated composites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and a superconducting quantum interference device (SQUID) magnetometer. Dual-functional Fe3O4/Au clusters were obtained, effectively combining magnetic and plasmonic optical properties. The magnetic Fe3O4 cluster cores permitted the adsorption of the probe molecules, while sample concentration and collection were carried out under an external magnetic field. In addition, 4-nitrothiophenol (4-NTP) was chosen as the probe molecule to examine the analyte concentration ability and surface-enhanced Raman scattering (SERS) activity of the Fe3O4/Au composites. The results indicated that the Fe3O4/Au clusters exhibit a prominent SERS effect. The best 4-NTP detection limit obtained was 1 × 10-8 M, with a corresponding SERS analytical enhancement factor (AEF) exceeding 2 × 105.

Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

NASA Astrophysics Data System (ADS)

Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

2014-12-01

The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

Synthesis of ZnO nanoparticles for oil-water interfacial tension reduction in enhanced oil recovery

NASA Astrophysics Data System (ADS)

Soleimani, Hassan; Baig, Mirza Khurram; Yahya, Noorhana; Khodapanah, Leila; Sabet, Maziyar; Demiral, Birol M. R.; Burda, Marek

2018-02-01

Nanoparticles show potential use in applications associated with upstream oil and gas engineering to increase the performance of numerous methods such as wettability alteration, interfacial tension reduction, thermal conductivity and enhanced oil recovery operations. Surface tension optimization is an important parameter in enhanced oil recovery. Current work focuses on the new economical method of surface tension optimization of ZnO nanofluids for oil-water interfacial tension reduction in enhanced oil recovery. In this paper, zinc oxide (ZnO) nanocrystallites were prepared using the chemical route and explored for enhanced oil recovery (EOR). Adsorption of ZnO nanoparticles (NPs) on calcite (111) surface was investigated using the adsorption locator module of Materials Studio software. It was found that ZnO nanoparticles show maximum adsorption energy of - 253 kcal/mol. The adsorption of ZnO on the rock surface changes the wettability which results in capillary force reduction and consequently increasing EOR. The nanofluids have been prepared by varying the concentration of ZnO nanoparticles to find the optimum value for surface tension. The surface tension (ST) was calculated with different concentration of ZnO nanoparticles using the pendant drop method. The results show a maximum value of ST 35.57 mN/m at 0.3 wt% of ZnO NPs. It was found that the nanofluid with highest surface tension (0.3 wt%) resulted in higher recovery efficiency. The highest recovery factor of 11.82% at 0.3 wt% is due to the oil/water interfacial tension reduction and wettability alteration.

Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

DOE PAGES

Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; ...

2016-05-30

Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al 2O 3 and α-Fe 2O 3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-hmore » exposure time, Pb(II) binds preferentially to the alpha-Al 2O 3 (1-102) and α-Fe 2O 3 (0001) surfaces at low Pb concentration ([Pb] = 10 –7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10 –6 to 10 –4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10 –7 to 10 –4 M). In comparison, the α-Al 2O 3 (0001) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al 2O 3 (0001) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al 2O 3 (1-102) and α-Fe 2O 3 (0001). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al 2O 3 (1-102) and α-Fe 2O 3 (0001) at [Me(II)] of 10 –7 M; at 10 –5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II) increasingly partition to the metal-oxide surfaces at [Me(II)] = 10 –5 M and pH 6.0, indicating possible reaction/diffusion-controlled sorption processes. Pb L-III-edge and Zn K-edge grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) measurements suggest that both Pb(II) and Zn(II) ions may be complexed by carboxyl groups in S. oneidensis biofilms after 3-h exposure at pH 6.0 and [Me(II)] = 10 –5 M. In contrast with Burkholderia cepacia, which was used in our previous studies of monolayer biofilm-coated metal-oxide surfaces (Templeton et al., 2001), S. oneidensis MR-1 forms relatively thick biofilm coatings (6-20 μm) that are rich in reactive functional groups and are expected to dominate metal-ion adsorption. Lastly, our results show that even thick and highly reactive biofilms like S. oneidensis do not cause much change in the intrinsic chemical reactivities of the underlying metal-oxide surfaces with respect to aqueous Pb(II) and Zn(II) and don't block reactive sites on the metal-oxide surfaces; instead they reduce the rate of Pb(II) and Zn(II) sorption onto these surfaces.« less

Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

NASA Astrophysics Data System (ADS)

Wang, Yingge; Gélabert, Alexandre; Michel, F. Marc; Choi, Yongseong; Gescher, Johannes; Ona-Nguema, Georges; Eng, Peter J.; Bargar, John R.; Farges, Francois; Spormann, Alfred M.; Brown, Gordon E.

2016-09-01

Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al2O3 and α-Fe2O3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-h exposure time, Pb(II) binds preferentially to the α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1) surfaces at low Pb concentration ([Pb] = 10-7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10-6 to 10-4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10-7 to 10-4 M). In comparison, the α-Al2O3 (0 0 0 1) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al2O3 (0 0 0 1) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1) at [Me(II)] of 10-7 M; at 10-5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II) increasingly partition to the metal-oxide surfaces at [Me(II)] = 10-5 M and pH 6.0, indicating possible reaction/diffusion-controlled sorption processes. Pb LIII-edge and Zn K-edge grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) measurements suggest that both Pb(II) and Zn(II) ions may be complexed by carboxyl groups in S. oneidensis biofilms after 3-h exposure at pH 6.0 and [Me(II)] = 10-5 M. In contrast with Burkholderia cepacia, which was used in our previous studies of monolayer biofilm-coated metal-oxide surfaces (Templeton et al., 2001), S. oneidensis MR-1 forms relatively thick biofilm coatings (6-20 μm) that are rich in reactive functional groups and are expected to dominate metal-ion adsorption. Our results show that even thick and highly reactive biofilms like S. oneidensis do not cause much change in the intrinsic chemical reactivities of the underlying metal-oxide surfaces with respect to aqueous Pb(II) and Zn(II) and don't block reactive sites on the metal-oxide surfaces; instead they reduce the rate of Pb(II) and Zn(II) sorption onto these surfaces.

Ex-Situ Synthesis of Polyvinyl alcohol(PVA)-coated Fe3O4 Nanoparticles by Coprecipitation-Ultrasonication Method

NASA Astrophysics Data System (ADS)

Riva'i, Imam; Oktavia Wulandari, Ika; Sulistyarti, Hermin; Sabarudin, Akhmad

2018-01-01

In this study, the synthesis of Fe3O4 nanoparticles was done with surface modification using PVA with coprecipitation-ultrasonication method. Time variations and PVA concentrations were added to determine the effect on crystallite size and lattice parameters on the synthesis of Fe3O4-PVA nanoparticles. Fe3O4 characterization was done using X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) instruments. FTIR was employed to determine PVA coating on the surface of Fe3O4 nanoparticles. The crystallite size and lattice parameters were analyzed using XRD. From the FTIR data, it is known that the interaction between PVA and Fe3O4 nanoparticles is characterized by Fe-O-C group at 1100 cm-1 region which is characteristic of Fe3O4-PVA nanoparticles, C-H groups of PVA in the range of 2950 cm-1 wave number, C-C of PVA regions of wave number 1405 cm-1, Fe3O4 and Fe3O4-PVA samples are in the range of 565 cm-1. In addition, the variation of ultrasonication time and the addition of PVA concentration have an effect on the crystallite size change and the lattice parameter observed from the XRD data. The use of ultrasonication time will affect the size of the crystallite become smaller and the grating lattice parameters obtained are wider. The effect of addition of PVA showed that higher concentration of PVA resulted in smaller crystallite size and larger lattice parameters. These results indicated that ultrasonication time and addition of PVA concentration greatly affect the characteristics of nanoparticles.

Direct absorption spectroscopy sensor for temperature and H2O concentration of flat flame burner

NASA Astrophysics Data System (ADS)

Duan, Jin-hu; Jin, Xing; Wang, Guang-yu; Qu, Dong-sheng

2016-01-01

A tunable diode laser absorption sensor, based on direct absorption spectroscopy and time division multiplexing scheme, was developed to measure H2O concentration and temperature of flat flame burner. At the height of 15mm from the furnace surface, temperature and concentration were measured at different equivalence ratios. Then the distance between the laser and the furnace surface was changed while the equivalence ratio was fixed at 1 and experiments were performed to measure temperature and H2O concentration at every height. At last flame temperatures and H2O concentrations were obtained by simulation and computational analysis and these combustion parameters were compared with the reference. The results showed that the experimental results were in accordance with the reference values. Temperature errors were less than 4% and H2O component concentration errors were less than 5%and both of them reached their maximum when the equivalent ratio was set at 1. The temperature and H2O concentration increased with the height from furnace surface to laser when it varied from 3mm to 9mm and it decreased when it varied from 9mm to 30mm and they reached their maximum at the height of 9mm. Keywords: tunable diode laser, direct absorption spectroscopy

Effect of Mg doping in ZnO buffer layer on ZnO thin film devices for electronic applications

NASA Astrophysics Data System (ADS)

Giri, Pushpa; Chakrabarti, P.

2016-05-01

Zinc Oxide (ZnO) thin films have been grown on p-silicon (Si) substrate using magnesium doped ZnO (Mg: ZnO) buffer layer by radio-frequency (RF) sputtering method. In this paper, we have optimized the concentration of Mg (0-5 atomic percent (at. %)) ZnO buffer layer to examine its effect on ZnO thin film based devices for electronic and optoelectronic applications. The crystalline nature, morphology and topography of the surface of the thin film have been characterized. The optical as well as electrical properties of the active ZnO film can be tailored by varying the concentration of Mg in the buffer layer. The crystallite size in the active ZnO thin film was found to increase with the Mg concentration in the buffer layer in the range of 0-3 at. % and subsequently decrease with increasing Mg atom concentration in the ZnO. The same was verified by the surface morphology and topography studies carried out with scanning electron microscope (SEM) and atomic electron microscopy (AFM) respectively. The reflectance in the visible region was measured to be less than 80% and found to decrease with increase in Mg concentration from 0 to 3 at. % in the buffer region. The optical bandgap was initially found to increase from 3.02 eV to 3.74 eV by increasing the Mg content from 0 to 3 at. % but subsequently decreases and drops down to 3.43 eV for a concentration of 5 at. %. The study of an Au:Pd/ZnO Schottky diode reveals that for optimum doping of the buffer layer the device exhibits superior rectifying behavior. The barrier height, ideality factor, rectification ratio, reverse saturation current and series resistance of the Schottky diode were extracted from the measured current voltage (I-V) characteristics.

[Responses of rice growth and development to elevated near-surface layer ozone (O3) concentration: a review].

PubMed

Yang, Lian-xin; Wang, Yu-long; Shi, Guang-yao; Wang, Yun-xia; Zhu, Jian-guo

2008-04-01

Ozone (O3) is recognized as one of the most important air pollutants. At present, the worldwide average tropospheric O3 concentration has been increased from an estimated pre-industrial level of 38 nl L(-1) (25-45 nl L(-1), 8-h summer seasonal average) to approximately 50 nl L(-1) in 2000, and to 80 nl L(-1) by 2100 based on most pessimistic projections. Oryza sativa L. (rice) is the most important grain crop in the world, and thus, to correctly evaluate how the elevated near-surface layer O3 concentration will affect the growth and development of rice is of great significance. This paper reviewed the chamber (including closed and open top chamber)-based studies about the effects of atmospheric ozone enrichment on the rice visible injury symptoms, photosynthesis, water relationship, phenology, dry matter production and allocation, leaf membrane protective system, and grain yield and its components. Further research directions in this field were discussed.

Selective Catalytic Reduction of NO by NH 3 with WO 3-TiO 2 Catalysts: Influence of Catalyst Synthesis Method

DOE PAGES

He, Yuanyuan; Ford, Michael E.; Zhu, Minghui; ...

2016-02-02

A series of supported WO 3/TiO 2 catalysts was prepared by a new synthesis procedure involving co-precipitation of an aqueous TiO(OH) 2 and (NH 4) 10W 12O 41*5H 2O slurry under controlled pH conditions. The morphological properties, molecular structures, surface acidity and surface chemistry of the supported WO 3/TiO 2 catalysts were determined with BET, in situ Raman, in situ IR and temperature-programmed surface reaction (TPSR) spectroscopy, respectively. Isotopic 18O- 16O exchange demonstrated that tungsten oxide was exclusively present as surface WO x species on the TiO 2 support with mono-oxo W=O coordination. In contrast to previous studies employing impregnationmore » synthesis that found only surface one mono-oxo O=WO 4 site on TiO 2, the co-precipitation procedure resulted in the formation of two distinct surface WO x species: mono-oxo O=WO 4 (~1010-1017 cm -1) on low defect density patches of TiO 2 and a second mono-oxo O=WO 4 (~983-986 cm -1) on high defect density patches of TiO 2. The concentration of the second WO x surface species increases as a function of solution pH. Both surface WOx sites, however, exhibited the same NO/NH 3 SCR reactivity. The co-precipitated WO 3-TiO 2 catalysts synthesized in alkaline solutions exhibited enhanced performance for the NO/NH 3 SCR reaction that is ascribed to the greater number of surface defects on the resulting TiO2 support. For the co-precipitated catalyst prepared at pH10, surface NH 4 + species on Br nsted acid sites were found to be more reactive than surface NH 3* species on Lewis acid sites for SCR of NO with NH 3.« less

Relationship between surface and free tropospheric ozone in the Western U.S.

PubMed

Jaffe, Dan

2011-01-15

Ozone is an important air pollutant that affects lung function. In the U.S., the EPA has reduced the allowable O(3) concentrations several times over the last few decades. This puts greater emphasis on understanding the interannual variability and the contributions to surface O(3) from all sources. We have examined O(3) data from 11 rural CASTNET sites in the western US for the period 1995-2009. The 11 surface sites show a similar seasonal cycle and generally a good correlation in the deseasonalized monthly means, indicating that there are large scale influences on O(3) that operate across the entire western US. These sites also show a good correlation between site elevation and annual mean O(3), indicating a significant contribution from the free troposphere. We examined the number of exceedance days for each site, defined as a day when the Maximum Daily 8-h Average (MDA8) exceeds a threshold value. Over this time period, more than half of these sites exceeded an MDA8 threshold of 70 ppbv at least 4 times per year, and all sites exceeded a threshold value of 65 ppbv at least 4 times per year. The transition to lower threshold values increases substantially the number of exceedance days, especially during spring, reflecting the fact that background O(3) peaks during spring. We next examined the correlation between surface O(3) and free tropospheric O(3) in the same region, as measured by routine balloon launches from Boulder, CO. Using ozone measured by the balloon sensor in the range of 3-6 km above sea level we find statistically significant correlations between surface and free tropospheric O(3) in spring and summer months using both monthly means, daily MDA8 values, and the number of surface exceedance days. We suggest that during spring this correlation reflects variations in the flux of O(3) transport from the free troposphere to the surface. In summer, free tropospheric and surface concentrations of O(3) and the number of exceedance days are all significantly correlated with emissions from biomass burning in the western US. This indicates that wildfires significantly increase the number of exceedance days across the western U.S.

Ti/IrO2/SnO2 anode for electrochemical degradation of chlorpyrifos in water: optimization and degradation performances

NASA Astrophysics Data System (ADS)

Pathiraja, G. C.; Wijesingha, M. S.; Nanayakkara, N.

2017-05-01

Chlorpyrifos, a widely used organophosphate pesticide which can be found in surface water bodies, is harmful for human body. Thus, treating water contaminated with chlorpyrifos is important. In our previous studies, novel Ti/IrO2-SnO2 anode was successfully developed for electrochemical degradation of chlorpyrifos in chloride free water. In this study, optimization of previously developed Ti/IrO2-SnO2 anode for mineralization of chlorpyrifos was successfully performed through response surface methodology. During the optimization study, two-level factorial design was used to determine the optimal coating solutions concentration for developing the Ti/IrO2-SnO2 anode. Cyclic voltammetry and open circuit potential were performed to investigate the electrochemically active surface area and stability of these anodes. The response surface and contour plots show that 0.3 M of [Ir] and 7.5 mM of [Sn] coated electrode has both highest anodic charge and stability. Scanning Electron Microscopic (SEM) images show the evidence of having both compact and porous regions in the surface of the thin film, resulting larger surface area. Within 6 h, the best result for mineralization (55.56%) of chlorpyrifos was obtained with 0.3 M of [Ir] and 7.5 mM of [Sn] coated anode using Total organic Carbon (TOC) analyzer. Therefore, the optimum coating concentration was found as 0.3 M of [Ir] and 7.5 mM of [Sn]. It would require an energy consumption of 6 kWhm-3.

The effects of cetyltrimethylammonium bromide surfactant on alumina modified zinc oxides

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

Gac, Wojciech, E-mail: wojciech.gac@umcs.lublin.pl; Zawadzki, Witold; Słowik, Grzegorz

Highlights: • Synthesis of novel ZnO−Al{sub 2}O{sub 3} oxides in the presence of CTAB surfactant. • Determination of the structural, surface and optical properties. • Nanocrystalline, high-surface area ZnO−Al{sub 2}O{sub 3} oxides. • ZnO-Al{sub 2}O{sub 3} materials of different gap energy. - Abstract: Novel alumina modified zinc oxide materials were prepared by co-precipitation method in the presence of different amounts of cetyltrimethylammonium bromide (CTAB) surfactant. X-ray diffraction, {sup 27}Al magic-angle spinning Nuclear Magnetic Resonance Spectroscopy, and transmission electron microscopy studies evidenced formation of 10–15 nm zinc oxide nanoparticles in the presence of the small amounts of surfactant. Amorphous alumina andmore » zinc aluminate phases of different coordination environment of Al sites were identified. An increase of surfactant concentration led to the elongation of nanoparticles and changes of the nature of hydroxyl groups. Precipitation in the high CTAB concentration conditions facilitated formation of mesoporous materials of high specific surface area. The materials were composed of very small (2–3 nm) zinc aluminate spinel nanoparticles. High concentration of CTAB induced widening of band gap energy.« less

Ultra-high sensitive substrates for surface enhanced Raman scattering, made of 3 nm gold nanoparticles embedded on SiO2 nanospheres

NASA Astrophysics Data System (ADS)

Phatangare, A. B.; Dhole, S. D.; Dahiwale, S. S.; Bhoraskar, V. N.

2018-05-01

The surface properties of substrates made of 3 nm gold nanoparticles embedded on SiO2 nanospheres enabled fingerprint detection of thiabendazole (TBZ), crystal violet (CV) and 4-Aminothiophenol (4-ATP) at an ultralow concentration of ∼10-18 M by surface enhanced Raman spectroscopy (SERS). Gold nanoparticles of an average size of ∼3 nm were synthesized and simultaneously embedded on SiO2 nanospheres by the electron irradiation method. The substrates made from the 3 nm gold nanoparticles embedded on SiO2 nanospheres were successfully used for recording fingerprint SERS spectra of TBZ, CV and 4-ATP over a wide range of concentrations from 10-6 M to 10-18 M using 785 nm laser. The unique features of these substrates are roughness near the surface due to the inherent structural defects of 3 nm gold nanoparticles, nanogaps of ≤ 1 nm between the embedded nanoparticles and their high number. These produced an abundance of nanocavities which act as active centers of hot-spots and provided a high electric field at the reporter molecules and thus an enhancement factor required to record the SERS spectra at ultra low concentration of 10-18 M. The SERS spectra recorded by the substrates of 4 nm and 6 nm gold nanoparticles are discussed.

Research on degradation of omethoate with Y2O3:Er3+ and TiO2

NASA Astrophysics Data System (ADS)

Liu, Zhiping; Mai, Yanling; Yan, Aiguo; Fan, Hailu; Yuan, Taidou

2018-06-01

Application of visible light excited photocatalytic degradation reagent of pesticide residues is not only suitable for the farmers, can also be used for city residents for daily use. Up conversion material Y2O3:Er3+ was prepared by sol gel method, then mixed with anatase TiO2 sol solution, to carry out the research of omethoate degradation under visible light. In order to get the higher degradability, it's important to study the technological parameters. Among so many parameters, four parameters were selected. They were vegetable surface omethoate concentration, photocatalytic degradation reagent dosage, pH value and degradation time. Utilizing orthogonal experimental design program, all parameters were optimized. The results showed that: the degradation rate was the largest concerned with the vegetable surface omethoate concentration, and then the degradation time.

Deposition of ozone to tundra

NASA Technical Reports Server (NTRS)

Jacob, D. J.; Fan, S.-M.; Wofsy, S. C.; Spiro, P. A.; Bakwin, P. S.; Ritter, J. A.; Browell, E. V.; Gregory, G. L.; Fitzjarrald, D. R.; Moore, K. E.

1992-01-01

Eddy correlation measurements of O3 deposition fluxes to tundra during the Arctic Boundary Layer Expedition (ABLE 3A) are reported. The mean O3 deposition velocity was 0.24 cm/s in the daytime and 0.12 cm/s at night. The day-to-day difference in deposition velocity was driven by both atmospheric stability and surface reactivity. The mean surface resistance to O3 deposition was 2.6 s/cm in the daytime and 3.4 s/cm at night. The relatively low surface resistance at night is attributed to light-insensitive uptake of O3 at dry upland tundra surfaces. The small day-tonight difference in surface resistance is attributed to additional stomatal uptake by wet meadow tundra plants in the daytime. The mean O3 deposition flux to the world north of 60 deg N in July-August is estimated at 8.2 x 10 exp 10 molecules/sq cm/s. Suppression of photochemical loss by small anthropogenic inputs of nitrogen oxides could have a major effect on O3 concentrations in the summertime Arctic troposphere.

Application of calcium oxide (CaO, heated scallop-shell powder) for the reduction of Listeria monocytogenes biofilms on eggshell surfaces.

PubMed

Park, S Y; Jung, S-J; Kang, I; Ha, S-D

2018-05-01

This study investigated bactericidal activity of 0.05 to 0.50% calcium oxide (CaO) against planktonic cells in tryptic soy broth (TSB) and biofilms of Listeria monocytogenes on eggshell surfaces. The bactericidal activity of CaO against planktonic cells and biofilms of L. monocytogens significantly (P < 0.05) increased log reductions with increasing concentrations of CaO. Exposure to 0.05 to 0.50% CaO for one min reduced planktonic cells in TSB cell suspensions by 0.47 to 3.86 log10CFU/mL and biofilm cells on the shell surfaces by 0.14 to 2.32 log10CFU/cm2. The Hunter colors of eggshells ("L" for lightness, "a" for redness, and "b" for yellowness), shell thickness (puncture force), and sensory quality (egg taste and yolk color) were not changed by 0.05 to 0.50% CaO treatment. The nonlinear Weibull model was used to calculate CR = 3 values as the CaO concentration of 3 log (99.9%) reduction for planktonic cells (R2 = 0.96, RMSE = 0.26) and biofilms (R2 = 0.95, RMSE = 0.18) of L. monocytogens. The CR = 3 value, 0.31% CaO for planktonic cells, was significantly (P < 0.05) lower than 0.57% CaO for biofilms. CaO could be an alternative disinfectant to reduce planktonic cells and biofilms L. monocytogenes on eggshell surface in egg processing plants.

The effect of skin moisture on the density distribution of OH and O close to the skin surface

NASA Astrophysics Data System (ADS)

Wu, F.; Li, J.; Liu, F.; Zhou, X.; Lu, X.

2018-03-01

OH radicals and O atoms are believed to be two of the most important reactive species in various biomedical applications of atmospheric pressure plasma jets. In this study, the effect of the skin moisture on the density distribution of OH and O close to the surface of the ex vivo pig skin is investigated by using laser-induced fluorescence technology. The skin moistures used in this study are 20%, 40%, 60%, and 80%, respectively. The experiment results indicate that, at a gas flow rate of 0.5 L/min, when the skin moisture is increased, the OH density close to the skin surface increases, while the O density decreases. On the other hand, when the gas flow rate is increased to 1 L/min, the OH density close to the skin surface is less sensitive with the moisture of the skin surface. Besides, when the skin moisture is 80%, the OH density increases with the increase in the concentration of H2O in the working gas and it reaches its maximum 7.9 × 1013 cm-3 when the concentration of H2O in the working gas is about 500 ppm. The OH density starts to decrease while the H2O concentration in the working gas keeps increasing. On the order hand, the O density shows a maximum 7.4 × 1014 cm-3 when the gas flow rate is 0.5 L/min with no O2 added and the skin moisture is 20%. But, when the gas flow rate is increased to about 1 to 2 L/min, the O density achieves its maximum when 0.5% of O2 is added to the working gas. The possible reasons for these observations are discussed.

Boosting surface charge-transfer doping efficiency and robustness of diamond with WO3 and ReO3

NASA Astrophysics Data System (ADS)

Tordjman, Moshe; Weinfeld, Kamira; Kalish, Rafi

2017-09-01

An advanced charge-transfer yield is demonstrated by employing single monolayers of transition-metal oxides—tungsten trioxide (WO3) and rhenium trioxide (ReO3)—deposited on the hydrogenated diamond surface, resulting in improved p-type sheet conductivity and thermal stability. Surface conductivities, as determined by Hall effect measurements as a function of temperature for WO3, yield a record sheet hole carrier concentration value of up to 2.52 × 1014 cm-2 at room temperature for only a few monolayers of coverage. Transfer doping with ReO3 exhibits a consistent narrow sheet carrier concentration value of around 3 × 1013 cm-2, exhibiting a thermal stability of up to 450 °C. This enhanced conductivity and temperature robustness exceed those reported for previously exposed surface electron acceptor materials used so far on a diamond surface. X-ray photoelectron spectroscopy measurements of the C1s core level shift as a function of WO3 and ReO3 layer thicknesses are used to determine the respective increase in surface band bending of the accumulation layers, leading to a different sub-surface two-dimensional hole gas formation efficiency in both cases. This substantial difference in charge-exchange efficiency is unexpected since both surface acceptors have very close work functions. Consequently, these results lead us to consider additional factors influencing the transfer doping mechanism. Transfer doping with WO3 reveals the highest yet reported transfer doping efficiency per minimal surface acceptor coverage. This improved surface conductivity performance and thermal stability will promote the realization of 2D diamond-based electronic devices facing process fabrication challenges.

Surface termination dependence of the reactivity of single crystal hematite with CCl 4

NASA Astrophysics Data System (ADS)

Camillone, Nicholas, III; Adib, Kaveh; Fitts, Jeffrey P.; Rim, Kwang T.; Flynn, George W.; Joyce, S. A.; Osgood, Richard M.

2002-06-01

We describe ultrahigh vacuum Auger electron spectrometric measurements of the uptake of chlorine following the room temperature exposure of single crystal hematite, α-Fe2O3, to CCl4. We compare the surface chemistry of two specific surface phases formed on the basal plane of α-Fe2O3: the Fe3O4(1 1 1)-(2×2) ;selvedge; and the α-Fe2O3/Fe1-xO ;biphase.; For Fe3O4(1 1 1)-(2×2) an estimated saturation level of Cl of ∼75% of a monolayer is readily attained. Carbon uptake is well below that expected for simple stoichiometric dissociative chemisorption, consistent with desorption of organic products during the surface reaction. Low energy electron diffraction measurements suggest that, dependent upon preparation procedures, at least two types of α-Fe2O3/Fe1-xO biphase structures can be formed. Surprisingly, upon exposure to CCl4, Cl uptake does not occur on either of these biphase surfaces, despite the fact that these surfaces are thought to have the same surface concentrations of iron and oxygen as Fe3O4(1 1 1). The dramatic difference between the reactivity of the Fe3O4 and biphase surfaces suggests that the active site for the dissociative adsorption of CCl4 on Fe3O4(1 1 1)-(2×2) comprises both an iron cation and an oxygen anion with a surface-normal-oriented dangling bond that is uncapped by iron cations. Electron stimulated and thermal desorption of Cl from the saturated Fe3O4(1 1 1)-(2×2) selvedge is also reported.

Energetics and magnetic properties of V-doped MgO bulk and (001) surface: A GGA, GGA+U , and hybrid density functional study

NASA Astrophysics Data System (ADS)

Århammar, C.; Moyses Araujo, C.; Rao, K. V.; Norgren, Susanne; Johansson, Börje; Ahuja, Rajeev

2010-10-01

In this work, a first-principles study of the energetic and magnetic properties of V-doped MgO is presented, where both the bulk and (001) surface were investigated. It is found that V assumes a high-spin state with a local moment of about 3μB . In the bulk, the interaction between these local moments is very short ranged and the antiferromagnetic (AFM) ordering is energetically more favorable. The formation of V-VMg-V defect clusters is found to weaken the antiferromagnetic coupling in bulk MgO, degenerating the AFM and ferromagnetic state. However, these clusters are high in energy and will not form at equilibrium conditions. By employing the GGA+U approach, with U=5eV , the V3d states on the (001) surface are shifted below the Fermi level, and a reasonable surface geometry was achieved. A calculation with the hybrid HSE03 functional, contradicts the GGA+U results, indicating that the V-MgO surface should be metallic at this concentration. From the energetics it is concluded that, at the modeled concentration, VxOy phases will limit the solubility of V in MgO at equilibrium conditions, which is in agreement with previous experimental findings. In order to achieve higher concentrations of V, an off-equilibrium synthesis method is needed. Finally, we find that the formation energy of V at the surface is considerably higher than in the bulk and V is thus expected to diffuse from the surface into the bulk of MgO.

Activating Aluminum Reactivity with Fluoropolymer Coatings for Improved Energetic Composite Combustion.

PubMed

McCollum, Jena; Pantoya, Michelle L; Iacono, Scott T

2015-08-26

Aluminum (Al) particles are passivated by an aluminum oxide (Al2O3) shell. Energetic blends of nanometer-sized Al particles with liquid perfluorocarbon-based oxidizers such as perfluoropolyethers (PFPE) excite surface exothermic reaction between fluorine and the Al2O3 shell. The surface reaction promotes Al particle reactivity. Many Al-fueled composites use solid oxidizers that induce no Al2O3 surface exothermicity, such as molybdenum trioxide (MoO3) or copper oxide (CuO). This study investigates a perfluorinated polymer additive, PFPE, incorporated to activate Al reactivity in Al-CuO and Al-MoO3. Flame speeds, differential scanning calorimetry (DSC), and quadrupole mass spectrometry (QMS) were performed for varying percentages of PFPE blended with Al/MoO3 or Al/CuO to examine reaction kinetics and combustion performance. X-ray photoelectron spectroscopy (XPS) was performed to identify product species. Results show that the performance of the thermite-PFPE blends is highly dependent on the bond dissociation energy of the metal oxide. Fluorine-Al-based surface reaction with MoO3 produces an increase in reactivity, whereas the blends with CuO show a decline when the PFPE concentration is increased. These results provide new evidence that optimizing Al combustion can be achieved through activating exothermic Al surface reactions.

Adsorption of CO on oxide and water ice surfaces - Implications for the Martian atmosphere

NASA Technical Reports Server (NTRS)

Leu, M.-T.; Blamont, J. E.; Anbar, A. D.; Keyser, L. F.; Sander, S. P.

1992-01-01

The adsorption of carbon monoxide (CO) on water ice and on the oxides Fe2O3, Fe3O4, Al2O3, SiO2, CaO, MgO, and TiO2 (rutile and anatase) has been investigated in a flow reactor. A mass spectrometer was employed as a detector to monitor the temporal concentrations of CO. Adsorption coefficients as large as 1 x 10 exp -4 were measured for CO on TiO2 solids in helium at 196 K. The fractional surface coverage for CO on TiO2 solids in helium was also determined to be approximately 10 percent at 196 K. The upper limits of the fractional surface coverage for the other oxides (Fe2O3, Fe3O4, Al2O3, SiO2, CaO, and MgO) and water ice were also measured to be less than 1 percent. The implications for the stability of CO2 in the Martian atmosphere and the 'CO hole' observed by the Phobos/ISM experiment are discussed.

Diurnal variation of surface ozone in mountainous areas: Case study of Mt. Huang, East China.

PubMed

Zhang, Lei; Jin, Lianji; Zhao, Tianliang; Yin, Yan; Zhu, Bin; Shan, Yunpeng; Guo, Xiaomei; Tan, Chenghao; Gao, Jinhui; Wang, Haoliang

2015-12-15

To explore the variations in atmospheric environment over mountainous areas, measurements were made from an intensive field observation at the summit of Mt. Huang (30.13°N, 118.15°E, 1841m above sea level), a rural site located in East China, from June to August 2011. The measurements revealed a diurnal change of surface O3 with low concentrations during the daytime and high concentrations during the nighttime. The causes of diurnal O3 variations over the mountain peak in East China were investigated by using a fairly comprehensive WRF-Chem and HYSPLIT4 modeling approach with observational analysis. By varying model inputs and comparing the results to a baseline modeling and actual air quality observations, it is found that nearby ozone urban/anthropogenic emission sources were contributing to a nighttime increase in mountaintop ozone levels due to a regional transport lag and residual layer effects. Positive correlation of measured O3 and CO concentrations suggested that O3 was associated with anthropogenic emissions. Sensitivity modeling experiments indicated that local anthropogenic emissions had little impact on the diurnal pattern of O3. The diurnal pattern of O3 was mainly influenced by regional O3 transport from the surrounding urban areas located 100-150km away from the summit, with a lag time of 10h for transport. Copyright © 2015 Elsevier B.V. All rights reserved.

Phenomenology of summer ozone episodes over the Madrid Metropolitan Area, central Spain

NASA Astrophysics Data System (ADS)

Querol, Xavier; Alastuey, Andrés; Gangoiti, Gotzon; Perez, Noemí; Lee, Hong K.; Eun, Heeram R.; Park, Yonghee; Mantilla, Enrique; Escudero, Miguel; Titos, Gloria; Alonso, Lucio; Temime-Roussel, Brice; Marchand, Nicolas; Moreta, Juan R.; Arantxa Revuelta, M.; Salvador, Pedro; Artíñano, Begoña; García dos Santos, Saúl; Anguas, Mónica; Notario, Alberto; Saiz-Lopez, Alfonso; Harrison, Roy M.; Millán, Millán; Ahn, Kang-Ho

2018-05-01

Various studies have reported that the photochemical nucleation of new ultrafine particles (UFPs) in urban environments within high insolation regions occurs simultaneously with high ground ozone (O3) levels. In this work, we evaluate the atmospheric dynamics leading to summer O3 episodes in the Madrid air basin (central Iberia) by means of measuring a 3-D distribution of concentrations for both pollutants. To this end, we obtained vertical profiles (up to 1200 m above ground level) using tethered balloons and miniaturised instrumentation at a suburban site located to the SW of the Madrid Metropolitan Area (MMA), the Majadahonda site (MJDH), in July 2016. Simultaneously, measurements of an extensive number of air quality and meteorological parameters were carried out at three supersites across the MMA. Furthermore, data from O3 soundings and daily radio soundings were also used to interpret atmospheric dynamics.The results demonstrate the concatenation of venting and accumulation episodes, with relative lows (venting) and peaks (accumulation) in O3 surface levels. Regardless of the episode type, the fumigation of high-altitude O3 (arising from a variety of origins) contributes the major proportion of surface O3 concentrations. Accumulation episodes are characterised by a relatively thinner planetary boundary layer (< 1500 m at midday, lower in altitude than the orographic features), light synoptic winds, and the development of mountain breezes along the slopes of the Guadarrama Mountain Range (located W and NW of the MMA, with a maximum elevation of > 2400 m a.s.l.). This orographic-meteorological setting causes the vertical recirculation of air masses and enrichment of O3 in the lower tropospheric layers. When the highly polluted urban plume from Madrid is affected by these dynamics, the highest Ox (O3+ NO2) concentrations are recorded in the MMA.Vertical O3 profiles during venting episodes, with strong synoptic winds and a deepening of the planetary boundary layer reaching > 2000 m a.s.l., were characterised by an upward gradient in O3 levels, whereas a reverse situation with O3 concentration maxima at lower levels was found during the accumulation episodes due to local and/or regional production. The two contributions to O3 surface levels (fumigation from high-altitude strata, a high O3 background, and/or regional production) require very different approaches for policy actions. In contrast to O3 vertical top-down transfer, UFPs are formed in the planetary boundary layer (PBL) and are transferred upwards progressively with the increase in PBL growth.

WOx supported on γ-Al2O3 with different morphologies as model catalysts for alkanol dehydration

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

Shi, Dachuan; Wang, Huamin; Kovarik, Libor

2018-04-21

The distinctive morphological and surface characteristics of platelet-like γ-Al2O3 were compared to a regular, commercial γ-Al2O3. γ-Al2O3 platelets display dominant (110) surface facets and higher densities of coordinative unsaturated penta-coordinate Al3+ (Al3+penta) sites than regular γ-Al2O3, as measured by solid-state magic-angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). Such Al3+penta sites are also the preferred surface anchoring sites for tungsten oxide (WOx) species consistent with NMR analysis indicating that these sites are consumed upon WOx adsorption. The higher Al3+penta density on γ-Al2O3 platelets leads to greater WOx dispersion (or smaller WOx clusters), as demonstrated by scanning transmission electron microscopy andmore » ultraviolet–visible spectroscopy, and WOx species at intermediate WOx surface concentration are the most active for the probe reaction of 2-butanol dehydration. WOx on γ-Al2O3 platelets approaches the highest turnover rates at higher surface densities than WOx on regular γ-Al2O3, yet with similar highest rate values for both series of catalysts. This indicates that different Al2O3 supports mainly affect the dispersion of supported WOx rather than the intrinsic reactivity of individual WOx clusters with similar size.« less

WO x supported on γ-Al 2 O 3 with different morphologies as model catalysts for alkanol dehydration

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

Shi, Dachuan; Wang, Huamin; Kovarik, Libor

The distinctive morphological and surface characteristics of platelet-like γ-Al2O3 were compared to a regular, commercial γ-Al2O3. γ-Al2O3 platelets display dominant (110) surface facets and higher densities of coordinative unsaturated penta-coordinate Al3+ (Al3+penta) sites than regular γ-Al2O3, as measured by solid-state magic-angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). Such Al3+penta sites are also the preferred surface anchoring sites for tungsten oxide (WOx) species consistent with NMR analysis indicating that these sites are consumed upon WOx adsorption. The higher Al3+penta density on γ-Al2O3 platelets leads to greater WOx dispersion (or smaller WOx clusters), as demonstrated by scanning transmission electron microscopy andmore » ultraviolet–visible spectroscopy, and WOx species at intermediate WOx surface concentration are the most active for the probe reaction of 2-butanol dehydration. WOx on γ-Al2O3 platelets approaches the highest turnover rates at higher surface densities than WOx on regular γ-Al2O3, yet with similar highest rate values for both series of catalysts. This indicates that different Al2O3 supports mainly affect the dispersion of supported WOx rather than the intrinsic reactivity of individual WOx clusters with similar size.« less

CO2 sensing of La0.875Ca0.125FeO3 in wet vapor: a comparison of experimental results and first-principles calculations.

PubMed

Wang, Xiaofeng; Chen, Yanping; Qin, Hongwei; Li, Ling; Shi, Changmin; Liu, Liang; Hu, Jifan

2015-05-28

Experimental results show that with an increase of relative humidity, the resistance of La0.875Ca0.125FeO3 decreases at room temperature but increases at higher temperatures (140-360 °C). The humid effect at room temperature is due to the movement of H(+) or H3O(+) inside of the condensed water layer on the surface of La0.875Ca0.125FeO3. Regarding the humid effect at high temperatures, the density functional theory (DFT) calculations show that H2O can be adsorbed onto the La0.875Ca0.125FeO3 surface in the molecular and dissociative adsorption configurations, where the La0.875Ca0.125FeO3 surface gains some electrons from H2O or its dissociative products, consistent with our observation. Experimental results also show that CO2 sensing response at high temperatures decreases with an increase of room-temperature relative humidity. DFT calculations indicate that CO2 adsorbed onto the La0.875Ca0.125FeO3(010) surface, where high concentration oxygen adsorption occurs without water adsorption nearby, releases some electrons into the semiconductor surface, playing the role of a donor. The interaction between CO2 and the local La0.875Ca0.125FeO3(010) surface with pre-adsorption of H2O nearby results in some electron transfer from the La0.875Ca0.125FeO3 surface to CO2, which is responsible for the weakening of CO2 response at high temperatures for La0.875Ca0.125FeO3 with an increase of room-temperature relative humidity.

Nitrate loading and CH4 and N2O Flux from headwater streams

NASA Astrophysics Data System (ADS)

Sousa, C. H. R. D.; Hilker, T.; Hall, F. G.; Moura, Y. M.; McAdam, E.

2014-12-01

Freshwater ecosystems transport and process significant amounts of terrestrial carbon and can be considerable sources of CO2, CH4, and N2O. A great deal of uncertainty, however, remains in both global estimates and our understanding of drivers of freshwater greenhouse gas emissions. Furthermore, small headwater streams have received insufficient attention to date and may contribute disproportionately to global GHG flux. Our objective was to quantify GHG flux and assess the impact of changes in DOC and NO3 concentrations in surface and subsurface water on flux rates in three streams in the Lamprey River watershed in New Hampshire, USA, that contrast in surface water DOC:NO3. We measured DOC, NO3 and dissolved gas concentrations in surface waters of each stream monthly from May 2011 to April 2012. Empirical measurements of reaeration coefficients were used to convert dissolved gas concentrations to fluxes. We found higher GHG concentrations and fluxes in the two streams with high DOC concentrations, particularly gases produced by anaerobic metabolism (CH4, N2O from methanogenesis and denitrification, respectively). The stream with high DOC and high NO3 showed high N2O and low CH4 flux, while the high DOC, low NO3 stream showed high CH4 and low N2O flux. Our results are consistent with a model in which C inputs drive total GHG production, while NO3 input regulates the relative importance of CH4 and N2O by suppressing methanogenesis and stimulating denitrification. The magnitude of GHG fluxes suggests that streams in this region are likely to be small sources of CO2, but potentially important sources of CH4 and N2O. Since CH4 and N2O are many times more powerful than CO2 at trapping heat in the atmosphere, freshwater emissions of these gases have the potential to offset a significant proportion of the climate benefits of the terrestrial carbon sink, a possibility that has not been sufficiently incorporated into climate models.

Nitrate loading and CH4 and N2O Flux from headwater streams

NASA Astrophysics Data System (ADS)

Schade, J. D.; Bailio, J.; McDowell, W. H.

2015-12-01

Freshwater ecosystems transport and process significant amounts of terrestrial carbon and can be considerable sources of CO2, CH4, and N2O. A great deal of uncertainty, however, remains in both global estimates and our understanding of drivers of freshwater greenhouse gas emissions. Furthermore, small headwater streams have received insufficient attention to date and may contribute disproportionately to global GHG flux. Our objective was to quantify GHG flux and assess the impact of changes in DOC and NO3 concentrations in surface and subsurface water on flux rates in three streams in the Lamprey River watershed in New Hampshire, USA, that contrast in surface water DOC:NO3. We measured DOC, NO3 and dissolved gas concentrations in surface waters of each stream monthly from May 2011 to April 2012. Empirical measurements of reaeration coefficients were used to convert dissolved gas concentrations to fluxes. We found higher GHG concentrations and fluxes in the two streams with high DOC concentrations, particularly gases produced by anaerobic metabolism (CH4, N2O from methanogenesis and denitrification, respectively). The stream with high DOC and high NO3 showed high N2O and low CH4 flux, while the high DOC, low NO3 stream showed high CH4 and low N2O flux. Our results are consistent with a model in which C inputs drive total GHG production, while NO3 input regulates the relative importance of CH4 and N2O by suppressing methanogenesis and stimulating denitrification. The magnitude of GHG fluxes suggests that streams in this region are likely to be small sources of CO2, but potentially important sources of CH4 and N2O. Since CH4 and N2O are many times more powerful than CO2 at trapping heat in the atmosphere, freshwater emissions of these gases have the potential to offset a significant proportion of the climate benefits of the terrestrial carbon sink, a possibility that has not been sufficiently incorporated into climate models.

Efficient adsorption concentration and photolysis of acetaldehyde on titania-mesoporous silica composite

NASA Astrophysics Data System (ADS)

Yamaguchi, Satoshi; Matsumoto, Akihiko

2017-07-01

Titania-mesoporous silica composite (TiO2/MCM) was prepared by hydrolysis of titaniumtetraisopropoxide (TTIP) with the presence of mesoporous silica MCM-41. The TiO2/MCM samples consisted of highly dispersed TiO2 on the surface of MCM-41. Dynamic adsorption and photocatalytic decomposition features for acetaldehyde (CH3CHO) were measured by flow method. The amount of CH3CHO decomposition on TiO2/MCM-41 increased with the TiO2 amount, suggesting that a large amount of CH3CHO was adsorbed on mesopores of MCM-41 of the TiO2/MCM and was efficiently decomposed on finely dispersed TiO2 surface by ultraviolet irradiation.

What is Eating Ozone? Thermal Reactions between SO2 And O3: Implications for Icy Environments

NASA Technical Reports Server (NTRS)

Loeffler, Mark J.; Hudson, Reggie L.

2016-01-01

Laboratory studies are presented, showing for the first time that thermally driven reactions in solid H2O+SO2+O3 mixtures can occur below 150 K, with the main sulfur-containing product being bisulfate (HSO4(-)). Using a technique not previously applied to the low-temperature kinetics of either interstellar or solar system ice analogs, we estimate an activation energy of 32 kJ per mol for HSO4(-) formation. These results show that at the temperatures of the Jovian satellites, SO2 and O3 will efficiently react making detection of these molecules in the same vicinity unlikely. Our results also explain why O3 has not been detected on Callisto and why the SO2 concentration on Callisto appears to be highest on that world's leading hemisphere. Furthermore, our results predict that the SO2 concentration on Ganymede will be lowest in the trailing hemisphere, where the concentration of O3 is the highest. Our work suggests that thermal reactions in ices play a much more important role in surface and sub-surface chemistry than generally appreciated, possibly explaining the low abundance of sulfur-containing molecules and the lack of ozone observed in comets and interstellar ices.

Direct charge carrier injection into Ga2O3 thin films using an In2O3 cathode buffer layer: their optical, electrical and surface state properties

NASA Astrophysics Data System (ADS)

Cui, W.; Zhao, X. L.; An, Y. H.; Guo, D. Y.; Qing, X. Y.; Wu, Z. P.; Li, P. G.; Li, L. H.; Cui, C.; Tang, W. H.

2017-04-01

Conductive Ga2O3 thin films with an In2O3 buffer layer have been prepared on c-plane sapphire substrates using a laser molecular beam epitaxy technique. The effects of the In2O3 buffer layer on the structure and optical, electrical and surface state properties of the Ga2O3 films have been studied. The change in conductivity of the thin films is attributed to different thicknesses of the In2O3 buffer layer, which determine the concentration of charge carriers injected into the upper Ga2O3 layer from the interface of the bilayer thin films. In addition, the increase in flat band voltage shift and capacitance values as the In2O3 buffer layer thickens are attributed to the increase in surface state density, which also contributes to the rapid shrinkage of the optical band gap of the Ga2O3. With transparency to visible light, high n-type conduction and the ability to tune the optical band gap and surface state density, we propose that Ga2O3/In2O3 bilayer thin film is an ideal n-type semiconductor for fabrication of transparent power devices, solar cell electrodes and gas sensors.

Spatiotemporal trends in ground-level ozone concentrations and metrics in France over the time period 1999-2012.

PubMed

Sicard, Pierre; Serra, Romain; Rossello, Philippe

2016-08-01

The hourly ozone (O3) data from 332 background monitoring stations, spread in France, were analyzed over the period 1999-2012 and short-term trends were calculated. In the current climate change context, the calculation of human health- and vegetation-relevant metrics, and of associated trends, provides a consistent method to establish proper and effective policies to reduce the adverse O3 effects. The generation of optimal O3 maps, for risk and exposure assessment, is challenging. To overcome this issue, starting from a set of stations, a hybrid regression-interpolation approach was proposed. Annual surface O3 metrics, O3 human health metrics (number of exceedances of daily maximum 8-h values greater than 60 ppb and SOMO35) and O3 vegetation impact metrics (AOT40 for vegetation and forests) were investigated at individual sites. Citizens are more exposed to high O3 levels in rural areas than people living in the cities. The annual mean concentrations decreased by -0.12ppbyear(-1) at rural stations, and the significant reduction at 67% of stations, particularly during the warm season, in the number of episodic high O3 concentrations (e.g. 98th percentile, -0.19ppbyear(-1)) can be associated with the substantial reductions in NOx and VOCs emissions in the EU-28 countries since the early 1990s Inversely, the O3 background level is rising at 76% of urban sites (+0.14ppbyear(-1)), particularly during the cold period. This rise can be attributed to increases in imported O3 by long-range transport and to a low O3 titration by NO due to the reduction in local NOx emissions. The decrease in health-related and vegetation-relevant O3 metrics, at almost all stations, is driven by decreases in regional photochemical O3 formation and in peak O3 concentrations. The short-term trends highlight that the threat to population and vegetation declined between 1999 and 2012 in France, demonstrating the success of European control strategies over the last 20 years. However, for all exposure metrics, the issue of non-attainment of the target value for O3 persists in comparison with the objectives of air quality directives. The region at highest O3 risk is the South-eastern France. This study contains new information on the i) spatial distribution of surface O3 concentration, ii) exceedances and iii) trends to define more suitable standards for human health and environmental protection in France. Copyright © 2016 Elsevier Inc. All rights reserved.

Rapid Detection of Tetrodotoxin Using Surface-Enhanced Raman Spectroscopy and Fe3O4/SiO2/Au Gold/Magnetic Nanoparticles

NASA Astrophysics Data System (ADS)

Neng, Jing; Wang, Xujun; Jia, Kan; Sun, Peilong

2018-03-01

Fe3O4 nanoparticles were first modified with tetraethoxylsilane to form Fe3O4/SiO2 nanoparticles, followed by the addition of 3-aminopropyltriethoxysilane and 3-thiolpropyltriethoxysilane to introduce -NH2 and -SH groups to the surface of Fe3O4/SiO2 nanoparticles. Gold nanoparticles were further assembled on the surface of Fe3O4/SiO2 via the electrostatic adsorption of -NH2 and the Au-S bond to produce stable core-shell Fe3O4/SiO2/Au gold/magnetic nanoparticles. These Fe3O4/SiO2/Au gold/magnetic nanoparticles were characterized by a variety of techniques such as transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX), and afterwards conjugated with tetrodotoxin antibodies (Ab) and used as a Raman active substrate (Fe3O4/SiO2/Au-Ab) with Rhodamine B (RhB)-labeled tetrodotoxin antibody as a Raman reporter (Ab-RhB). Upon mixing these reagents with tetrodotoxin (TTX), a sandwich complex [Fe3O4/SiO2/Au-Ab···TTX···Ab-RhB] was generated due to the specific antibody-antigen interactions. The immunocomplex was subsequently separated by an externally applied magnetic source and concentrated into a pellet point, where the laser interrogation of the pellet produced a strong signal characteristic of RhB. The logarithmic intensity of the signal was found to be proportional to the concentration of TTX with a limit of detection of 0.01 μg/mL and a detection linearity range of 0.01-0.5 μg/mL. The established method eliminates the complicated procedures of traditional centrifuging, column separation, and incubation and achieves a rapid detection of tetrodotoxin with improved detection sensitivity.

Quantitative determination of oxygen defects, surface lewis acidity, and catalytic properties of mesoporous MoO3/SBA-15 catalysts

NASA Astrophysics Data System (ADS)

González, Julio; Wang, Jin An; Chen, Lifang; Manríquez, Maria; Salmones, José; Limas, Roberto; Arellano, Ulises

2018-07-01

A set of MoO3/SBA-15 mesoporous catalysts were characterized with a variety of spectroscopic techniques and their crystalline structures were refined with Rietveld method. Oxygen defect concentration, crystallite size, phase composition, surface acidity, mesoporous regularity, and textural properties were reported. Both α-MoO3 and β-MoO3 phases coexisted but α-MoO3 was predominated. Oxygen defects were created in the orthorhombic structure and its concentration decreased from 3.08% for the 20 wt%MoO3/SBA-15 to 0.55% for the 25 wt%MoO3/SBA-15. All the MoO3/SBA-15 catalysts chiefly contained a big number of Lewis acid sites originating from oxygen defects in MoO3 crystals. In the absence of formic acid, the oxidation of 4,6-dibenzothiophene (4,6-DMDBT) in a model diesel was almost proportional to the number of Lewis acid sites. In the presence of formic acid, 4,6-DMDBT oxidation was significantly affected by the formation of surface peroxometallic complex and Lewis acidity. Formic acid addition could improve the ODS efficiency by promoting peroxometallic complex formation and enhancing oxidant stability. Under the optimal reaction condition using the best 15 and 20 wt%MoO3/SBA-15 catalysts, more than 99% 4,6-DMDBT could be removed at 70 °C within 30 min. This work confirmed that 4,6-DMDBT oxidation is a texture and particle size sensitive and Lewis acidity dependent reaction. This work also shows that crystalline structure refinement combination with experiments can gain new insights in the design of heterogeneous nanocatalysts and help to better understand the catalytic behavior in the oxidative desulfurization reactions.

Emulsifying properties and oil/water (O/W) interface adsorption behavior of heated soy proteins: effects of heating concentration, homogenizer rotating speed, and salt addition level.

PubMed

Cui, Zhumei; Chen, Yeming; Kong, Xiangzhen; Zhang, Caimeng; Hua, Yufei

2014-02-19

The adsorption of heat-denatured soy proteins at the oil/water (O/W) interface during emulsification was studied. Protein samples were prepared by heating protein solutions at concentrations of 1-5% (w/v) and were then diluted to 0.3% (w/v). The results showed that soy proteins that had been heated at higher concentrations generated smaller droplet size of emulsion. Increase in homogenizer rotating speed resulted in higher protein adsorption percentages and lower surface loads at the O/W interface. Surface loads for both unheated and heated soy proteins were linearly correlated with the unadsorbed proteins' equilibrium concentration at various rotating speeds. With the rise in NaCl addition level, protein adsorption percentage and surface loads of emulsions increased, whereas lower droplet sizes were obtained at the ionic strength of 0.1 M. The aggregates and non-aggregates displayed different adsorption behaviors when rotating speed or NaCl concentration was varied.

Role of oxygen defects on the magnetic properties of ultra-small Sn1-xFexO2 nanoparticles

NASA Astrophysics Data System (ADS)

Dodge, Kelsey; Chess, Jordan; Eixenberger, Josh; Alanko, Gordon; Hanna, Charles B.; Punnoose, Alex

2013-05-01

Although the role of oxygen defects in the magnetism of metal oxide semiconductors has been widely discussed, it is been difficult to directly measure the oxygen defect concentration of samples to verify this. This work demonstrates a direct correlation between the photocatalytic activity of Sn1-xFexO2 nanoparticles and their magnetic properties. For this, a series of ˜2.6 nm sized, well characterized, single-phase Sn1-xFexO2 crystallites with x = 0-0.20 were synthesized using tin acetate, urea, and appropriate amounts of iron acetate. X-ray photoelectron spectroscopy confirmed the concentration and 3+ oxidation state of the doped Fe ions. The maximum magnetic moment/Fe ion, μ, of 1.6 × 10-4 μB observed for the 0.1% Fe doped sample is smaller than the expected spin-only contribution from either high or low spin Fe3+ ions, and μ decreases with increasing Fe concentration. This behavior cannot be explained by the existing models of magnetic exchange. Photocatalytic studies of pure and Fe-doped SnO2 were used to understand the roles of doped Fe3+ ions and of the oxygen vacancies and defects. The photocatalytic rate constant k also showed an increase when SnO2 nanoparticles were doped with low concentrations of Fe3+, reaching a maximum at 0.1% Fe, followed by a rapid decrease of k for further increase in Fe%. Fe doping presumably increases the concentration of oxygen vacancies, and both Fe3+ ions and oxygen vacancies act as electron acceptors to reduce e--h+ recombination and promote transfer of electrons (and/or holes) to the nanoparticle surface, where they participate in redox reactions. This electron transfer from the Fe3+ ions to local defect density of states at the nanoparticle surface could develop a magnetic moment at the surface states and leads to spontaneous ferromagnetic ordering of the surface shell under favorable conditions. However, at higher doping levels, the same Fe3+ ions might act as recombination centers causing a decrease of both k and magnetic moment μ.

Reduced reactivity to air on HF-treated YBa2Cu3O(7-x)surfaces

NASA Technical Reports Server (NTRS)

Vasquez, R. P.; Hunt, B. D.; Foote, M. C.

1989-01-01

Treatment of YBa2Cu3O(7-x) films with a nonaqueous solution of HF in absolute ethanol results in the formation of an oxyfluoride with relative Y:Ba:Cu concentrations of 1:4:3 on the surface, as determined by X-ray photoelectron spectroscopy. The passivation properties of chemically treated films were tested by monitoring the growth of the high binding energy O 1s peak, associated with nonsuperconducting surface species, as a function of air exposure time, for both HF-treated and untreated films. The native oxyfluoride is shown to reduce the reactivity of the superconductor to air.

Effects of different surface modifying agents on the cytotoxic and antimicrobial properties of ZnO nanoparticles.

PubMed

Esparza-González, S C; Sánchez-Valdés, S; Ramírez-Barrón, S N; Loera-Arias, M J; Bernal, J; Meléndez-Ortiz, H Iván; Betancourt-Galindo, R

2016-12-01

Zinc oxide (ZnO) nanoparticles (NPs) have received considerable attention in the medical field because of their antibacterial properties, primarily for killing and reducing the activity of numerous microorganisms. The purpose of this study was to determine whether surface-modified ZnO NPs exhibit different properties compared with unmodified ZnO. The antimicrobial and cytotoxic properties of modified ZnO NPs as well as their effects on inflammatory cytokine production were evaluated. ZnO NPs were prepared using a wet chemical method. Then, the surfaces of these NPs were modified using 3-aminopropyltriethoxysilane (APTES) and dimethyl sulfoxide (DMSO) as modifying agents via a chemical hydrolysis method. According to infrared spectroscopy analysis (FTIR), the structure of the ZnO remained unchanged after modification. Antibacterial assays demonstrated that APTES modification is more effective at inducing an antimicrobial effect against Gram-negative bacteria than against Gram-positive bacteria. Cytotoxicity studies showed that cell viability was dose-dependent; moreover, pristine and APTES-modified ZnO exhibited low cytotoxicity, whereas DMSO-modified ZnO exhibited toxicity even at a low NP concentration. An investigation of inflammatory cytokine production demonstrated that the extent of stimulation was related to the ZnO NP concentration but not to the surface modification, except for IFN-γ and IL-10, which were not detected even at high NP concentrations. Copyright © 2016 Elsevier B.V. All rights reserved.

Modeling the oxidative capacity of the atmosphere of the south coast air basin of California. 1. Ozone formation metrics.

PubMed

Griffin, Robert J; Revelle, Meghan K; Dabdub, Donald

2004-02-01

Metrics associated with ozone (O3) formation are investigated using the California Institute of Technology (CIT) three-dimensional air-quality model. Variables investigated include the O3 production rate (P(O3)), O3 production efficiency (OPE), and total reactivity (the sum of the reactivity of carbon monoxide (CO) and all organic gases that react with the hydroxyl radical). Calculations are spatially and temporally resolved; surface-level and vertically averaged results are shown for September 9, 1993 for three Southern California locations: Central Los Angeles, Azusa, and Riverside. Predictions indicate increasing surface-level O3 concentrations with distance downwind, in line with observations. Surface-level and vertically averaged P(O3) values peak during midday and are highest downwind; surface P(O3) values are greater than vertically averaged values. Surface OPEs generally are highest downwind and peak during midday in downwind locations. In contrast, peaks occur in early morning and late afternoon in the vertically averaged case. Vertically averaged OPEs tend to be greater than those for the surface. Total reactivities are highest in upwind surface locations and peak during rush hours; vertically averaged reactivities are smaller and tend to be more uniform temporally and spatially. Total reactivity has large contributions from CO, alkanes, alkenes, aldehydes, unsubstituted monoaromatics, and secondary organics. Calculations using estimated emissions for 2010 result in decreases in P(O3) values and reactivities but increases in OPEs.

Attack polish for nickel-base alloys and stainless steels

DOEpatents

Steeves, Arthur F.; Buono, Donald P.

1983-01-01

A chemical attack polish and polishing procedure for use on metal surfaces such as nickel base alloys and stainless steels. The chemical attack polish comprises Fe(NO.sub.3).sub.3, concentrated CH.sub.3 COOH, concentrated H.sub.2 SO.sub.4 and H.sub.2 O. The polishing procedure includes saturating a polishing cloth with the chemical attack polish and submicron abrasive particles and buffing the metal surface.

Method of polishing nickel-base alloys and stainless steels

DOEpatents

Steeves, Arthur F.; Buono, Donald P.

1981-01-01

A chemical attack polish and polishing procedure for use on metal surfaces such as nickel base alloys and stainless steels. The chemical attack polish comprises Fe(NO.sub.3).sub.3, concentrated CH.sub.3 COOH, concentrated H.sub.2 SO.sub.4 and H.sub.2 O. The polishing procedure includes saturating a polishing cloth with the chemical attack polish and submicron abrasive particles and buffing the metal surface.

Surface plasmon resonance study on the optical sensing properties of tin oxide (SnO2) films to NH3 gas

NASA Astrophysics Data System (ADS)

Paliwal, Ayushi; Sharma, Anjali; Tomar, Monika; Gupta, Vinay

2016-04-01

Surface plasmon resonance (SPR) technique is an easy and reliable method for detecting very low concentration of toxic gases at room temperature using a gas sensitive thin film layer. In the present work, a room temperature operated NH3 gas sensor has been developed using a laboratory assembled SPR measurement setup utilising a p-polarized He-Ne laser and prism coupling technique. A semiconducting gas sensitive tin oxide (SnO2) layer has been deposited under varying growth conditions (i.e., by varying deposition pressure) over the gold coated prism (BK-7) to excite the surface plasmon modes in Kretschmann configuration. The SPR reflectance curves for prism/Au/SnO2/air system for SnO2 thin films prepared at different sputtering pressure were measured, and the SnO2 film deposited at 10 mT pressure is found to exhibit a sharp SPR reflectance curve with minimum reflectance (0.32) at the resonance angle of 44.7° which is further used for sensing NH3 gas of different concentration at room temperature. The SPR reflectance curve shows a significant shift in resonance angle from 45.05° to 58.55° on interacting with NH3. The prepared sensor is found to give high sensing response (0.11) with high selectivity towards very low concentration of NH3 (0.5 ppm) and quick response time at room temperature.

Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

DOE PAGES

Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; ...

2016-06-13

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less

Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

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

Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less

Influence of regional-scale anthropogenic activity in northeast Asia on seasonal variations of surface ozone and carbon monoxide observed at Oki, Japan

NASA Astrophysics Data System (ADS)

Pochanart, Pakpong; Hirokawa, Jun; Kajii, Yoshizumi; Akimoto, Hajime; Nakao, Makoto

1999-02-01

Surface O3 and CO measurements were carried out at Oki, Japan during March 1994 to February 1996 in order to elucidate the processes determining temporal variations of O3 and CO in the northeast Asian Pacific rim region. The isentropic trajectory analysis was applied to sort out the influences of the air mass exchange under the Asian monsoon system and the regional-scale photochemical buildup of O3. The trajectories were categorized into five groups which cover background and regionally polluted air masses. The seasonal cycles of O3 and CO in the background continental air mass revealed spring maximum-summer minimum with averaged concentrations ranging from 32 and 120 ppb to 45 and 208 ppb, respectively. In contrast, O3 concentrations in the regionally polluted continental air mass ranged from 44 to 57 ppb and showed a winter minimum and a spring-summer-autumn broad maximum, which was characterized by photochemical O3 production due to anthropogenic activities in northeast Asia. CO concentrations in the same air mass showed a spring maximum of 271 ppb and a summer-autumn minimum of 180 ppb. The photochemical buildup of O3 resulting from anthropogenic activities in this region was estimated to be 21 ppb in summer, while its production was insignificant, an average 3 ppb, in winter. A comparison between data in northeast Asia and in Europe shows many similarities, supporting the contention that photochemical buildup of O3 from large-scale precursor emissions in both regions is very significant.

Aqueous reactive species induced by a PCB surface micro-discharge air plasma device: a quantitative study

NASA Astrophysics Data System (ADS)

Chen, Chen; Li, Fanying; Chen, Hai-Lan; Kong, Michael G.

2017-11-01

This paper presents a quantitative investigation on aqueous reactive species induced by air plasma generated from a printed circuit board surface micro-discharge (SMD) device. Under the conditions amenable for proliferation of mammalian cells, concentrations of ten types of reactive oxygen and nitrogen species (RONS) in phosphate buffering solution (PBS) are measured by chemical fluorescent assays and electron spin resonance spectroscopy (ESR). Results show that concentrations of several detected RNS (NO2- , NO3- , peroxynitrites, and NO2\\centerdot ) are higher than those of ROS (H2O2, O2\\centerdot - , and 1O2) in the air plasma treated solution. Concentrations of NO3- can reach 150 times of H2O2 with 60 s plasma treatment. For short-lived species, the air plasma generates more copious peroxynitrite than other RONS including NO2\\centerdot , O2\\centerdot - , 1O2, and N{{O}\\centerdot } in PBS. In addition, the existence of reaction between H2O2 and NO2- /HNO2 to produce peroxynitrite is verified by the chemical scavenger experiments. The reaction relations between detected RONS are also discussed.

Bactericidal Effect of Calcium Oxide (Scallop-Shell Powder) Against Pseudomonas aeruginosa Biofilm on Quail Egg Shell, Stainless Steel, Plastic, and Rubber.

PubMed

Jung, Soo-Jin; Park, Shin Young; Kim, Seh Eun; Kang, Ike; Park, Jiyong; Lee, Jungwon; Kim, Chang-Min; Chung, Myung-Sub; Ha, Sang-Do

2017-07-01

The aim of this study was to evaluate the bactericidal effect of calcium oxide (CaO) against Pseudomonas aeruginosa biofilms on quail eggshells and major egg contacting surfaces (stainless steel, plastic, and rubber). The samples were subjected to CaO treatments (0%, 0.01%, 0.05%, 0.10%, 0.15%, 0.20%, 0.25%, and 0.30%) for 1 min. All the CaO treatments significantly reduced P. aeruginosa biofilms on all tested surfaces as compared to controls. In comparison of biofilm stability, the strongest and most resistant biofilm was formed on eggshell against the CaO treatment, followed by rubber, stainless steel, and plastic. In evaluation of bactericidal effect, the largest reduction (3.16 log CFU) was observed in plastic even at the lowest concentration of CaO (0.01%), whereas the least reduction was found in eggshells, regardless of CaO concentration. In addition, stainless steel showed a significant reduction in biofilm formation at all concentrations except 0.10% to 0.15% CaO. At 0.30% CaO, the reduction of P. aeruginosa in biofilms on stainless steel, plastic, rubber, and eggshell were 5.48, 6.37, 4.87, and 3.14 log CFU/cm 2 (CFU/egg), respectively. Biofilm reduction after CaO treatment was also observed by field emission scanning electron microscopy (FE-SEM). Based on the FE-SEM images, we observed that P. aeruginosa biofilms formed compact aggregations on eggshell surfaces with CaO treatments up to 0.30%. More specifically, a 0.20% CaO treatment resulted in the reductions of 3 to 6 log CFU in all materials. © 2017 Institute of Food Technologists®.

Preparation and catalytic activities of LaFeO3 and Fe2O3 for HMX thermal decomposition.

PubMed

Wei, Zhi-Xian; Xu, Yan-Qing; Liu, Hai-Yan; Hu, Chang-Wen

2009-06-15

Perovskite-type LaFeO(3) and alpha-Fe(2)O(3) with high specific surface areas were directly prepared with appropriate stearic acid-nitrates ratios by a novel stearic acid solution combustion method. The obtained powders were characterized by XRD, FT-IR and XPS techniques. The catalytic activities of perovskite-type LaFeO(3) and alpha-Fe(2)O(3) for the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) were investigated by TG and TG-EGA techniques. The experimental results show that the catalytic activity of perovskite-type LaFeO(3) was much higher than that of alpha-Fe(2)O(3) because of higher concentration of surface-adsorbed oxygen (O(ad)) and hydroxyl of LaFeO(3). The study points out a potential way to develop new and more active perovskite-type catalysts for the HMX thermal decomposition.

Effect of biofilm coatings at metal-oxide/water interfaces II: Competitive sorption between Pb(II) and Zn(II) at Shewanella oneidensis/metal-oxide/water interfaces

DOE PAGES

Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; ...

2016-05-07

Competitive sorption of Pb(II) and Zn(II) on Shewanella oneidensis MR-1 biofilm-coated single-crystal α-Al 2O 3 (1 –1 0 2) and α-Fe 2O 3 (0 0 0 1) surfaces was investigated using long-period X-ray standing wave-florescence yield (LP-XSW-FY) spectroscopy. In situ partitioning of aqueous Pb(II) and Zn(II) between the biofilms and underlying metal-oxide substrates was probed following exposure of these complex interfaces to equi-molar Pb and Zn solutions (0.01 M NaNO 3 as background electrolyte, pH = 6.0, and 3-h equilibration time). At higher Pb and Zn concentrations (≥10 –5 M), more than 99% of these ions partitioned into the biofilmsmore » at S. oneidensis/α-Al 2O 3 (1 –1 0 2)/water interfaces, which is consistent with the partitioning behavior of both Pb(II) or Zn(II) in single-metal-ion experiments. Furthermore, no apparent competitive effects were found in this system at these relatively high metal-ion concentrations. However, at lower equi-molar concentrations (≤10 –6 M), Pb(II) and Zn(II) partitioning in the same system changed significantly compared to the single-metal-ion systems. The presence of Zn(II) decreased Pb(II) partitioning onto α-Al 2O 3 (1 –1 0 2) substantially (~52% to ~13% at 10 –7 M, and ~23% to ~5% at 10–6 M), whereas the presence of Pb(II) caused more Zn(II) to partition onto α-Al 2O 3 (1 –1 0 2) surfaces (~15% to ~28% at 10 –7 M, and ~1% to ~7% at 10 –6 M) .The higher observed partitioning of Zn(II) (~28%) at the α-Al 2O 3 (1 –1 0 2) surfaces compared to Pb(II) (~13%) in the mixed-metal-ion systems at the lowest concentration (10 –7 M) suggests that Zn(II) is slightly favored over Pb(II) for sorption sites on α-Al 2O 3 (1 –1 0 2) surfaces under our experimental conditions.« less

Formation of hydroxyapatite onto glasses of the CaO-MgO-SiO2 system with B2O3, Na2O, CaF2 and P2O5 additives.

PubMed

Agathopoulos, S; Tulyaganov, D U; Ventura, J M G; Kannan, S; Karakassides, M A; Ferreira, J M F

2006-03-01

New bioactive glasses with compositions based on the CaO-MgO-SiO(2) system and additives of B(2)O(3), P(2)O(5), Na(2)O, and CaF(2) were prepared. The in vitro mineralization behaviour was tested by immersion of powders or bulk glasses in simulated body fluid (SBF). Monitoring of ionic concentrations in SBF and scanning electron microscopy (SEM) observations at the surface of the glasses were conducted over immersion time. Raman and infrared (IR) spectroscopy shed light on the structural evolution occurring at the surface of the glasses that leads to formation of hydroxyapatite.

Concentrations of Reactive Trace Gases In The Interstitial Air of Surface Snow

NASA Astrophysics Data System (ADS)

Jacobi, H.-W.; Honrath, R. E.; Peterson, M. C.; Lu, Y.; Dibb, J. E.; Arsenault, M. A.; Swanson, A. L.; Blake, N. J.; Bales, R. C.; Schrems, O.

Several measurements at Arctic and Antarctic sites have demonstrated that unexpected photochemical reactions occur in irradiated surface snow influencing the composi- tion of the boundary layer over snow-covered areas. The results of these reactions are probably most obvious in the interstitial air of the surface snow since it constitutes the interface between the surface snow and the boundary layer. Therefore, measurements of concentrations of nitrogen oxide and dioxide, nitrous acid, formaldehyde, hydro- gen peroxide, formic acid, acetic acid, and other organic compounds were performed in the interstitial air of the surface snow of the Greenland ice sheet. Concentrations were measured at variable depths between - 10 cm and - 50 cm during the summer field season in 2000 at the Summit Environmental Observatory. At shallow depths, the system NO-NO2-O3 exhibits large deviations from the calculated photostationary state. Using steady-state analyses applied to OH-HO2-CH3O2 cycling indicated the presence of high concentrations of OH and peroxy radicals in the firn air. Maximum concentrations calculated for a depth of - 10 cm are in the order of 6 105 molecules cm-3 and 1.4 * 107 molecules cm-3 for OH and HO2, respectively, although radia- tion levels at - 10 cm are reduced by approximately 50 % compared to levels above the snow surface. By far the most important OH source is the photolysis of HONO while the photolysis of ozone contributes less than 2 % to the overall production of OH in the firn air.

Gd{sup 3+} incorporated ZnO nanoparticles: A versatile material

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

Kumar, Surender, E-mail: surender40@gmail.com; Sahare, P.D.

Graphical abstract: - Highlights: • Chemically synthesized Gd{sup 3+} doped ZnO nanoparticles. • The broad visible emission of the ZnO is dependent on the surface defects and can be tailored by Gd{sup 3+} doing. • PL and magnetic properties are modified by Gd{sup 3+} doping. • Photocatalysis experiment reveals that the ZnO: Gd{sup 3+} degrades the Rh B dye faster than the undoped ZnO. - Abstract: Gd{sup 3+} doped ZnO nanoparticles are synthesized by wet chemical route method and investigated through structural, optical, magnetic and photocatalytic properties. Transmission Electron Microscopy technique has been performed on undoped and Gd{sup 3+} dopedmore » ZnO nanoparticles. X-ray diffraction, X-ray photoelectron spectroscopy and Raman analyses are carried out in order to examine the desired phase formation and substitution of Gd{sup 3+} in the ZnO matrix. Gd{sup 3+} doped ZnO nanoparticles show enhanced photoluminescent and ferromagnetic properties as compared to undoped ZnO. The broad visible emission of ZnO is found to be largely dependent on the surface defects and these surface defects can be tailored by Gd{sup 3+} doping concentration. Furthermore, Gd{sup 3+} doped ZnO nanoparticles also show improved photocatalytic properties as compared with undoped ZnO nanoparticles under ultraviolet irradiation.« less

N2O production and consumption from stable isotopic and concentration data in the Peruvian coastal upwelling system

NASA Astrophysics Data System (ADS)

Bourbonnais, Annie; Letscher, Robert T.; Bange, Hermann W.; Échevin, Vincent; Larkum, Jennifer; Mohn, Joachim; Yoshida, Naohiro; Altabet, Mark A.

2017-04-01

The ocean is an important source of nitrous oxide (N2O) to the atmosphere, yet the factors controlling N2O production and consumption in oceanic environments are still not understood nor constrained. We measured N2O concentrations and isotopomer ratios, as well as O2, nutrient and biogenic N2 concentrations, and the isotopic compositions of nitrate and nitrite at several coastal stations during two cruises off the Peru coast ( 5-16°S, 75-81°W) in December 2012 and January 2013. N2O concentrations varied from below equilibrium values in the oxygen deficient zone (ODZ) to up to 190 nmol L-1 in surface waters. We used a 3-D-reaction-advection-diffusion model to evaluate the rates and modes of N2O production in oxic waters and rates of N2O consumption versus production by denitrification in the ODZ. Intramolecular site preference in N2O isotopomer was relatively low in surface waters (generally -3 to 14‰) and together with modeling results, confirmed the dominance of nitrifier-denitrification or incomplete denitrifier-denitrification, corresponding to an efflux of up to 0.6 Tg N yr-1 off the Peru coast. Other evidence, e.g., the absence of a relationship between ΔN2O and apparent O2 utilization and significant relationships between nitrate, a substrate during denitrification, and N2O isotopes, suggest that N2O production by incomplete denitrification or nitrifier-denitrification decoupled from aerobic organic matter remineralization are likely pathways for extreme N2O accumulation in newly upwelled surface waters. We observed imbalances between N2O production and consumption in the ODZ, with the modeled proportion of N2O consumption relative to production generally increasing with biogenic N2. However, N2O production appeared to occur even where there was high N loss at the shallowest stations.

Natural emissions under future climate condition and their effects on surface ozone in the Yangtze River Delta region, China

NASA Astrophysics Data System (ADS)

Xie, Min; Shu, Lei; Wang, Ti-jian; Liu, Qian; Gao, Da; Li, Shu; Zhuang, Bing-liang; Han, Yong; Li, Meng-meng; Chen, Pu-long

2017-02-01

The natural emissions of ozone precursors (NOx and VOCs) are sensitive to climate. Future climate change can impact O3 concentrations by perturbing these emissions. To better estimate the variation of natural emissions under different climate conditions and understand its effect on surface O3, we model the present and the future air quality over the Yangtze River Delta (YRD) region by running different simulations with the aid of the WRF-CALGRID model system that contains a natural emission module. Firstly, we estimate the natural emissions at present and in IPCC A1B scenario. The results show that biogenic VOC emission and soil NOx emission over YRD in 2008 is 657 Gg C and 19.1 Gg N, respectively. According to climate change, these emissions in 2050 will increase by 25.5% and 11.5%, respectively. Secondly, the effects of future natural emissions and meteorology on surface O3 are investigated and compared. It is found that the variations in meteorological fields can significantly alter the spatial distribution of O3 over YRD, with the increases of 5-15 ppb in the north and the decreases of -5 to -15 ppb in the south. However, only approximately 20% of the surface O3 increases caused by climate change can be attributed to the natural emissions, with the highest increment up to 2.4 ppb. Finally, Ra (the ratio of impacts from NOx and VOCs on O3 formation) and H2O2/HNO3 (the ratio between the concentrations of H2O2 and HNO3) are applied to study the O3 sensitivity in YRD. The results show that the transition value of H2O2/HNO3 will turn from 0.3 to 0.5 in 2008 to 0.4-0.8 in 2050. O3 formation in the YRD region will be insensitive to VOCs under future climate condition, implying more NOx need to be cut down. Our findings can help us understand O3 variation trend and put forward the reasonable and effective pollution control policies in these famous polluted areas.

Magnetite nanoparticle-induced fluorescence quenching of adenosine triphosphate-BODIPY Conjugates: application to adenosine triphosphate and pyrophosphate sensing.

PubMed

Yu, Cheng-Ju; Wu, Su-Mei; Tseng, Wei-Lung

2013-09-17

We report that magnetite nanoparticles (Fe3O4 NPs) act as an efficient quencher for boron dipyrromethene-conjugated adenosine 5'-triphosphate (BODIPY-ATP) that is highly fluorescent in bulk solution. BODIPY-ATP molecules attached to the surface of Fe3O4 NPs through the coordination between the triphosphate group of BODIPY-ATP and Fe(3+)/Fe(2+) on the NP surface. The formed complexes induced an apparent reduction in the BODIPY-ATP fluorescence resulting from an oxidative-photoinduced electron transfer (PET) from the BODIPY-ATP excited state to an unfilled d shell of Fe(3+)/Fe(2+) on the NP surface. A comparison of the Stern-Volmer quenching constant between Fe(3+) and Fe(2+) suggests that Fe(3+) on the NP surface dominantly controls this quenching process. The efficiency for Fe3O4 NP-induced fluorescence quenching of the BODIPY-ATP was enhanced by increasing the concentration of Fe3O4 NPs and lowering the pH of the solution to below 6.0. We found that pyrophosphate and ATP compete with BODIPY-ATP for binding to Fe3O4 NPs. Thus, we amplified BODIPY-ATP fluorescence in the presence of increasing the pyrophosphate and ATP concentration; the detection limits at a signal-to-noise ratio of 3 for pyrophosphate and ATP were determined to be 7 and 30 nM, respectively. The Fe3O4 NP-based competitive binding assay detected ATP and pyrophosphate in only 5 min. The selectivity of this assay for ATP over metal ions, amino acids, and adenosine analogues is particularly high. The practicality of using the developed method to determine ATP in a single drop of blood is also validated.

Influence of surface roughness on the oxidation behavior of a Ni-4.0Cr-5.7Al single crystal superalloy

NASA Astrophysics Data System (ADS)

Pei, Haiqing; Wen, Zhixun; Li, Zhenwei; Zhang, Yamin; Yue, Zhufeng

2018-05-01

The high-temperature oxidation dynamics and mechanisms of a Ni-based single crystal superalloy with four kinds of surface roughnesses were investigated by virtue of XRD, OM, SEM and EDS at 1000 °C. In the initial oxidation stage, outer (Ni, Co)O was mainly produced on the surfaces of the samples with Ra = 90 nm and 19 nm. Correspondingly, outer Cr2O3 and transient θ-Al2O3 were mainly formed on the surfaces with Ra = 509 nm and 182 nm. After 180 min oxidation, the values of instantaneous parabolic mass gain coefficients (kp) of the samples with all surface roughnesses were gradually consistent with the data of the growth parabolic coefficient of α-Al2O3. The oxidation mechanisms of Ni-based superalloy with different surface roughnesses were discussed by a model. The external diffusion flux of Al (DAl) increases with the increases of surface roughness. Thus, the required Al concentration decreases with the increases of surface roughness when the selective oxidation of Al occurrs to form a protective single α-Al2O3 film.

[Distributions and air-sea fluxes of dissolved nitrous oxide in the Yangtze River estuary and its adjacent marine area in spring and summer].

PubMed

Wang, Lan; Zhang, Gui-ling; Sun, Ming-shuang; Ren, Jing-ling

2014-12-01

Distributions and air-sea fluxes of nitrous oxide (N2O) in the seawaters of the Yangtze River estuary and its adjacent marine area were investigated during two cruises in March and July 2012. Dissolved N2O concentrations in surface waters ranged from 9.34 to 49.08 nmol x L(-1) with an average of (13.27 ± 6.40) nmol x L(-1) in spring and ranged from 7.27 to 27.81 nmol x L(-1) with an average of (10.62 ± 5.03) nmol x L(-1) in summer. There was no obvious difference between surface and bottom N2O concentrations. N2O concentrations in both surface and bottom waters decreased along the freshwater plume from the river mouth to the open sea. High values of dissolved N2O were found in turbidity maximum zone, which suggests that maximal turbidity enhances nitrification. Temperature had dual effects on dissolved N2O concentrations. N2O saturations in surface waters ranged from 86.9% to 351.3% with an average of (111.5 ± 41.4)% in spring and ranged from 111.7% to 396.0% with an average of (155.9 ± 68.4)% in summer. N2O were over-saturated at most stations. The sea-to-air fluxes of N2O were estimated to be (3.2 ± 10.9), (5.5 ± 19.3) and (12.2 ±52.3) μmol x (m2 x d)(-1) in spring and (7.3 ± 12.4), (12.7 ± 20.4) and (20.4 ± 35.9) μmol x (m2 x d)(-1) in summer using the LM86, W92 and RC01 relationships, respectively. The annual emissions of N2O from the Yangtze River estuary and its adjacent marine area were estimated to be 0.6 x 10(-2) Tg x a(-1) (LM86), 1.1 x 10(-2) Tg x a(-1) (W92) and 2.0 x 10(-2) Tg x a(-1) (RC01). Although the area of the Yangtze River estuary and its adjacent marine area only accounts for 0.02% of the total area of the world's oceans, their emission of N2O accounts for 0.06% of global oceanic N2O emission, indicating that the Yangtze River estuary and its adjacent marine area is an active area to produce and emit N2O.

Surface characterization of implant materials c.p. Ti, Ti-6Al-7Nb and Ti-6Al-4V with different pretreatments.

PubMed

Sittig, C; Textor, M; Spencer, N D; Wieland, M; Vallotton, P H

1999-01-01

The biocompatibility of commercially pure titanium and its alloys is closely related to their surface properties, with both the composition of the protecting oxide film and the surface topography playing an important role. Surfaces of commercially pure titanium and of the two alloys Ti-6Al-7Nb and Ti-6Al-4V (wt %) have been investigated following three different pretreatments: polishing, nitric acid passivation and pickling in nitric acid-hydrogen fluoride. Nitric acid treatment is found to substantially reduce the concentration of surface contaminants present after polishing. The natural 4-6 nm thick oxide layer on commercially pure titanium is composed of titanium oxide in different oxidation states (TiO2, Ti2O3 and TiO), while for the alloys, aluminium and niobium or vanadium are additionally present in oxidized form (Al2O3, Nb2O5 or V-oxides). The concentrations of the alloying elements at the surface are shown to be strongly dependent on the pretreatment process. While pickling increases the surface roughness of both commercially pure titanium and the alloys, different mechanisms appear to be involved. In the case of commercially pure titanium, the dissolution rate depends on grain orientation, whereas in the case of the two alloys, selective alpha-phase dissolution and enrichment of the beta-phase appears to occur. Copyright 1999 Kluwer Academic Publishers

Air pollution and associated human mortality: The role of air pollutant emissions, climate change and methane concentration increases during the industrial period

NASA Astrophysics Data System (ADS)

Fang, Y.; Naik, V.; Horowitz, L. W.; Mauzerall, D. L.

2012-12-01

Increases in surface ozone (O3) and fine particulate matter (≤ 2.5μm aerodynamic diameter, PM2.5) are associated with excess premature human mortalities. Here we estimate changes in surface O3 and PM2.5 since preindustrial (1860) times and the global present-day (2000) premature human mortalities associated with these changes. We go beyond previous work to analyze and differentiate the contribution of three factors: changes in emissions of short-lived air pollutants, climate change, and increased methane (CH4) concentrations, to air pollution levels and the associated premature mortalities. We use a coupled chemistry-climate model in conjunction with global population distributions in 2000 to estimate exposure attributable to concentration changes since 1860 from each factor. Attributable mortalities are estimated using health impact functions of long-term relative risk estimates for O3 and PM2.5 from the epidemiology literature. We find global mean surface PM2.5 and health-relevant O3 (defined as the maximum 6-month mean of 1-hour daily maximum O3 in a year) have increased by 8±0.16 μg/m3 and 30±0.16 ppbv, respectively, over this industrial period as a result of combined changes in emissions of air pollutants (EMIS), climate (CLIM) and CH4 concentrations (TCH4). EMIS, CLIM and TCH4 cause global average PM2.5 (O3) to change by +7.5±0.19 μg/m3 (+25±0.30 ppbv), +0.4±0.17 μg/m3 (+0.5±0.28 ppbv), and -0.02±0.01 μg/m3 (+4.3±0.33 ppbv), respectively. Total changes in PM2.5 are associated with 1.5 (95% confidence interval, CI, 1.0-2.5) million all-cause mortalities annually and in O3 are associated with 375 (95% CI, 129-592) thousand respiratory mortalities annually. Most air pollution mortality is driven by changes in emissions of short-lived air pollutants and their precursors (95% and 85% of mortalities from PM2.5 and O3 respectively). However, changing climate and increasing CH4 concentrations also increased premature mortality associated with air pollution globally up to 5% and 15%, respectively. In some regions, the contribution of climate change and increased CH4 together are responsible for more than 20% of the respiratory mortality associated with O3 exposure. We find the interaction between climate change and atmospheric chemistry has influenced atmospheric composition and human mortality associated with industrial air pollution. In addition to driving 13% of the total historical changes in surface O3 and 15% of the associated mortalities, CH4 is the dominant factor driving changes in atmospheric OH and H2O2 since preindustrial time. Our study highlights the benefits to air quality and human health of CH4 mitigation as a component of future air pollution control policy.

Visible photoassisted room-temperature oxidizing gas-sensing behavior of Sn2S3 semiconductor sheets through facile thermal annealing.

PubMed

Liang, Yuan-Chang; Lung, Tsai-Wen; Wang, Chein-Chung

2016-12-01

Well-crystallized Sn 2 S 3 semiconductor thin films with a highly (111)-crystallographic orientation were grown using RF sputtering. The surface morphology of the Sn 2 S 3 thin films exhibited a sheet-like feature. The Sn 2 S 3 crystallites with a sheet-like surface had a sharp periphery with a thickness in a nanoscale size, and the crystallite size ranged from approximately 150 to 300 nm. Postannealing the as-synthesized Sn 2 S 3 thin films further in ambient air at 400 °C engendered roughened and oxidized surfaces on the Sn 2 S 3 thin films. Transmission electron microscopy analysis revealed that the surfaces of the Sn 2 S 3 thin films transformed into a SnO 2 phase, and well-layered Sn 2 S 3 -SnO 2 heterostructure thin films were thus formed. The Sn 2 S 3 -SnO 2 heterostructure thin film exhibited a visible photoassisted room-temperature gas-sensing behavior toward low concentrations of NO 2 gases (0.2-2.5 ppm). By contrast, the pure Sn 2 S 3 thin film exhibited an unapparent room-temperature NO 2 gas-sensing behavior under illumination. The suitable band alignment at the interface of the Sn 2 S 3 -SnO 2 heterostructure thin film and rough surface features might explain the visible photoassisted room-temperature NO 2 gas-sensing responses of the heterostructure thin film on exposure to NO 2 gas at low concentrations in this work.

Overview of surface ozone variability in East Asia-North Pacific region during IGAC/APARE (1994--1996).

PubMed

Lam, K S; Wang, T J; Wang, T; Tang, J; Kajii, Y; Liu, C M; Shim, S G

2004-01-01

Surface ozone (O3) was measured at Oki Island (Japan), Cheju Island (South Korea), Lanyu Island (Taiwan Province, China), Cape D'Aguilar (Hong Kong SAR) and Lin'an, Longfenshan, Waliguan (China mainland) during January 1994--December 1996 as a component of IGAC/APARE (International Global Atmospheric Chemistry/East Asia-North Pacific Regional Experiment). This paper gave a joint discussion on the observational results at these stations over the study region. Investigations showed that the average of surface O3 mixing ratios at the seven sites are 47.9+/-15.8, 48.1+/-17.9, 30.2+/-16.4, 31.6+/-17.5, 36.3+/-17.5, 34.8+/-11.5 and 48.2+/-9.5 ppbv, respectively. Significant diurnal variations of surface O3 have been observed at Oki, Cheju, D'Aguilar, Lin'an and Longfenshan. Their annual averaged diurnal differences range from 8 to 23 ppbv and differ in each season. Surface O3 at Lanyu and Waliguan do not show strong diurnal variability. Seasonal cycles of surface O3 showed difference at the temperate and the subtropical remote sites. Oki has a summer minimum-spring maximum, while Lanyu has a summer minimum-autumn maximum. The suburban sites at D'Aguilar and Lin'an report high-level O3 in autumn and low level O3 in summer. Surface O3 remains-high in autumn and low in winter at the rural site Longfenshan. For the global background station Waliguan, surface O3 exhibits a broad spring-summer maximum and autumn-winter minimum. The backward air trajectories to these sites have shown different pathways of long-range transport of air pollution from East Asia Continent to North Pacific Ocean. Surface O3 was found to be strongly and positively correlated with CO at Oki and Lanyu, especially in spring and autumn, reflecting the substantial photochemical buildup of O3 on a regional scale. It is believed that the regional sources of pollution in East Asia have enhanced the average surface O3 concentrations in the background atmosphere of North Pacific.

Atmospheric transport of ozone between Southern and Eastern Asia.

PubMed

Chakraborty, T; Beig, G; Dentener, F J; Wild, O

2015-08-01

This study describes the effect of pollution transport between East Asia and South Asia on tropospheric ozone (O3) using model results from the Task Force on Hemispheric Transport of Air Pollution (TF HTAP). Ensemble mean O3 concentrations are evaluated against satellite-data and ground observations of surface O3 at four stations in India. Although modeled surface O3 concentrations are 1020ppb higher than those observed, the relative magnitude of the seasonal cycle of O3 is reproduced well. Using 20% reductions in regional anthropogenic emissions, we quantify the seasonal variations in pollution transport between East Asia and South Asia. While there is only a difference of 0.05 to 0.1ppb in the magnitudes of the regional contributions from one region to the other, O3 from East Asian sources affects the most densely populated parts of South Asia while Southern Asian sources only partly affect the populated parts of East Asia. We show that emission changes over East Asia between 2000 and 2010 had a larger impact on populated parts of South Asia than vice versa. This study will help inform future decisions on emission control policy over these regions. Copyright © 2015 Elsevier B.V. All rights reserved.

The colorimetric detection of Pb2+ by using sodium thiosulfate and hexadecyl trimethyl ammonium bromide modified gold nanoparticles.

PubMed

Zhang, Yujie; Leng, Yumin; Miao, Lijing; Xin, Junwei; Wu, Aiguo

2013-04-21

A simple, rapid colorimetric detection method for Pb(2+) in aqueous solution has been developed by using sodium thiosulfate (Na2S2O3) and hexadecyl trimethyl ammonium bromide (CTAB) modified gold nanoparticles (Au NPs). Na2S2O3 was added into the Au NP solution and thiosulfate ions (S2O3(2-)) were adsorbed on the surface of the Au NPs due to electrostatic interactions. Au atoms on the surface of the Au NPs were then oxidized to Au(i) by the O2 that existed in the solution in presence of thiosulfate. The addition of Pb(2+) (the final concentration was lower than 10 μM), accelerated the leaching of the Au NPs, and Pb-Au alloys also formed on the surface of the Au NPs. There was an obvious decrease in the surface plasmon resonance (SPR) absorption of the Au NPs. The lowest concentration for Pb(2+) that could be detected by the naked eye was 0.1 μM and using UV-vis spectroscopy was 40 nM. This is lower than the lead toxic level defined by the US Environmental Protection Agency (US EPA), which is 75 nM. In this method, CTAB, as a stabilizing agent for Au NPs, can accelerate the adsorption of S2O3(2-) on the surface of the Au NPs, which shortened the detection time to within 30 min. Moreover, this detection method is simple, cheap and environmentally friendly.

In Situ Groundwater Denitrification in the Riparian Zone of a Short-Rotation Woody Crop Experimental Watershed

NASA Astrophysics Data System (ADS)

Jeffers, J. B.; Jackson, C. R.; Rau, B.; Pringle, C. M.; Matteson, C.

2017-12-01

The southeastern United States has potential to become a major producer of short rotation woody crops (SRWC) for the production of biofuels, but this will require converting to more intensive forest management practices that will increase nitrate (NO3-) loading and alter nitrogen cycling in nearby freshwater ecosystems. Water quality monitoring in an experimental short-rotation woody crop watershed in the Coastal Plain of South Carolina has shown increased concentrations of NO3- in groundwater but no evidence of increased NO3- in riparian groundwater or surface waters. Forested riparian areas established as streamside management zones (SMZ) are known to act as buffers to surface water bodies by mitigating nutrients. The objectives of this study were to quantify denitrification by measuring dinitrogen (N2) and nitrous oxide (N2O) concentrations along groundwater flow paths and analyze relationships between denitrification estimates, nutrients, and water chemistry parameters. A network of piezometers has been established in the Fourmile Experimental Watershed at the Department of Energy - Savannah River Site. Water samples were collected monthly and were analyzed for concentrations of nutrients (temperature, specific conductivity, dissolved oxygen, pH, dissolved organic carbon) and dissolved gases (N2, Ar, N2O). Preliminary data showed greater dissolved N2O concentrations than dissolved N2 concentrations in groundwater. The ratios of N2O to combined end products of denitrification (N2O / N2O+N2) ranged from 0.33 to 0.99. Mean N2O+N2 concentrations were greater in groundwater samples in the SRWC plot and along the SMZ boundary than along the ephemeral stream within the riparian zone. Correlations between water chemistry parameters and N2 concentrations are indicative of known biogeochemical driving factors of denitrification. Continued monthly sampling will be coupled with analysis of nutrient concentrations (NO3-, NH4+, TN) to help determine transport and processing of NO3- and production of dissolved gases within the groundwater system. Use of hydrologic models combined with dissolved gas concentrations will provide estimates of denitrification rates and indirect gaseous emissions.

One-dimensional magnetic nanocomposites with attapulgites as templates: Growth, formation mechanism and magnetic alignment

NASA Astrophysics Data System (ADS)

Fu, Meng; Li, Xiangming; Jiang, Rui; Zhang, Zepeng

2018-05-01

Magnetic nanocomposite composed of attapulgite and Fe3O4 was synthesized by a simple and facile co-precipitation method. Its structure and morphology was verified using X-ray diffraction, transmission electron microscopy, scanning electron microscopy and Fourier transform infrared spectroscopy. Although the difficulty of forming uniform Fe3O4 on the attapulgite surface was discussed in detail in this study, one-dimensional magnetic nanorod with attapulgites as core and Fe3O4 as uniform shell was implemented for the first time using a cationic polymer surfactant, polyethylenimine. Polyethylenimine concentration, Fe3+/Fe2+ concentration and temperature were controlled to investigate the morphological evolutions of this nanocomposite. It was found that a uniform shell could be available with thickness tuning from 10 nm to 40 nm when Fe3+ concentration ranged from 0.01 mol/L to 0.03 mol/L meanwhile the polyethylenimine concentration was kept at 0.2 mg/mL and the temperature was kept at 60-80 °C. Finally, a possible mechanism for the formation of the Fe3O4 shell was suggested. The polyethylenimine on the surface of the attapulgites first adsorbed Fe3+/Fe2+ and then released under the action of alkali. It acted as a linker for the Fe3O4 nanoparticles nucleation in situ. The synthesized one-dimensional nanocomposites exhibit the superparamagnetism and fast response to an external magnetic field. The alignment of attapulgite-Fe3O4 one-dimensional nanocomposite along the external magnetic field was demonstrated. It provides promising candidates for building blocks and functional devices, which are low cost, non-toxic and eco-friendly, and opens the door for the application of attapulgite as one-dimensional nanomaterials.

Antibacterial activity of resin composites containing surface pre-reacted glass-ionomer (S-PRG) filler.

PubMed

Miki, Saeki; Kitagawa, Haruaki; Kitagawa, Ranna; Kiba, Wakako; Hayashi, Mikako; Imazato, Satoshi

2016-09-01

A surface pre-reacted glass-ionomer (S-PRG) filler is a technology of interest for providing bio-functions to restorative materials. Resin composites containing S-PRG filler have been reported to show less plaque accumulation and reduced bacterial attachment. In this study, experimental resin composites containing S-PRG filler at various concentrations were fabricated, and the inhibitory effects on bacterial growth on their surface and the association of ions released from S-PRG filler with antibacterial activity were evaluated. Five kinds of experimental resin composites containing S-PRG filler at 0, 13.9, 27.3, 41.8, or 55.9 (vol.%) were fabricated. Streptococcus mutans was cultured on the cured discs for 18h to examine the growth of bacteria in contact with the surface of the experimental resins. The concentrations of Al(3+), BO3(3-), F(-), Na(+), SiO3(2-), or Sr(2+) released from each experimental resin into water were measured. The standardized solutions of each ion were prepared at the concentrations determined to be released from the experimental resin, and their inhibitory effects of single ion species on S. mutans growth were evaluated by using each standardized solution. Resin composites containing S-PRG filler at 13.9 (vol.%) or greater inhibited S. mutans growth on their surface. When S. mutans was incubated in the presence of six kinds of ions at the concentrations released from the resin composite containing S-PRG filler at 55.9 (vol.%), a significant reduction in bacterial number was observed for BO3(3-), F(-), Al(3+), and SiO3(2-). Among these four ions, BO3(3-) and F(-) demonstrated the strongest inhibitory effect on S. mutans growth. Our findings suggest that resin composites containing S-PRG filler inhibit the growth of S. mutans on their surface. BO3(3-), F(-), Al(3+) and SiO3(2-) released from S-PRG filler have the ability to inhibit S. mutans growth, and the inhibitory effects are mainly attributed to release of BO3(3-) and F(-). Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effects of Northern Hemisphere Sea Surface Temperature Changes on the Global Air Quality

NASA Astrophysics Data System (ADS)

Yi, K.; Liu, J.

2017-12-01

The roles of regional sea surface temperature (SST) variability on modulating the climate system and consequently the air quality are investigated using the Community Earth System Model (CESM). Idealized, spatially uniform SST anomalies of +/- 1 °C are superimposed onto the North Pacific, North Atlantic, and North Indian Oceans individually. Ignoring the response of natural emissions, our simulations suggest large seasonal and regional variability of surface O3 and PM2.5 concentrations in response to SST anomalies, especially during boreal summers. Increasing the SST by 1 °C in one of the oceans generally decreases the surface O3 concentrations from 1 to 5 ppbv while increases the anthropogenic PM2.5 concentrations from 0.5 to 3 µg m-3. We implement the integrated process rate (IPR) analysis in CESM and find that meteorological transport in response to SST changes is the key process causing air pollutant perturbations in most cases. During boreal summers, the increase in tropical SST over different ocean basins enhances deep convection, which significantly increases the air temperature over the upper troposphere and trigger large-scale subsidence over nearby and remote regions. These processes tend to increase tropospheric stability and suppress rainfall at lower mid-latitudes. Consequently, it reduces the vertical transport of O3 to the surface while facilitating the accumulation of PM2.5 concentrations over most regions. In addition, this regional SST warming may also considerably suppress intercontinental transport of air pollution as confirmed with idealized CO-like tracers. Our findings indicate a robust linkage between basin-scale SST variability and regional air quality, which can help local air quality management.

Ozone air quality simulations with WRF-Chem (v3.5.1) over Europe: model evaluation and chemical mechanism comparison

NASA Astrophysics Data System (ADS)

Mar, Kathleen A.; Ojha, Narendra; Pozzer, Andrea; Butler, Tim M.

2016-10-01

We present an evaluation of the online regional model WRF-Chem over Europe with a focus on ground-level ozone (O3) and nitrogen oxides (NOx). The model performance is evaluated for two chemical mechanisms, MOZART-4 and RADM2, for year-long simulations. Model-predicted surface meteorological variables (e.g., temperature, wind speed and direction) compared well overall with surface-based observations, consistent with other WRF studies. WRF-Chem simulations employing MOZART-4 as well as RADM2 chemistry were found to reproduce the observed spatial variability in surface ozone over Europe. However, the absolute O3 concentrations predicted by the two chemical mechanisms were found to be quite different, with MOZART-4 predicting O3 concentrations up to 20 µg m-3 greater than RADM2 in summer. Compared to observations, MOZART-4 chemistry overpredicted O3 concentrations for most of Europe in the summer and fall, with a summertime domain-wide mean bias of +10 µg m-3 against observations from the AirBase network. In contrast, RADM2 chemistry generally led to an underestimation of O3 over the European domain in all seasons. We found that the use of the MOZART-4 mechanism, evaluated here for the first time for a European domain, led to lower absolute biases than RADM2 when compared to ground-based observations. The two mechanisms show relatively similar behavior for NOx, with both MOZART-4 and RADM2 resulting in a slight underestimation of NOx compared to surface observations. Further investigation of the differences between the two mechanisms revealed that the net midday photochemical production rate of O3 in summer is higher for MOZART-4 than for RADM2 for most of the domain. The largest differences in O3 production can be seen over Germany, where net O3 production in MOZART-4 is seen to be higher than in RADM2 by 1.8 ppb h-1 (3.6 µg m-3 h-1) or more. We also show that while the two mechanisms exhibit similar NOx sensitivity, RADM2 is approximately twice as sensitive to increases in anthropogenic VOC emissions as MOZART-4. Additionally, we found that differences in reaction rate coefficients for inorganic gas-phase chemistry in MOZART-4 vs. RADM2 accounted for a difference of 8 µg m-3, or 40 % of the summertime difference in O3 predicted by the two mechanisms. Differences in deposition and photolysis schemes explained smaller differences in O3. Our results highlight the strong dependence of modeled surface O3 over Europe on the choice of gas-phase chemical mechanism, which we discuss in the context of overall uncertainties in prediction of ground-level O3 and its associated health impacts (via the health-related metrics MDA8 and SOMO35).

Soot Oxidation in Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure. Appendix K

NASA Technical Reports Server (NTRS)

Xu, F.; El-Leathy, A. M.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

2001-01-01

Soot oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round jets burning in coflowing air considering acetylene, ethylene, propylene and propane as fuels. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation mainly occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of stable major gas species (N2, H2O, H2, O2, CO, CO2, CH4, C2H2,C2H4, C2H6, C3H6, and C3H8) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by the deconvoluted Li/LiOH atomic absorption technique and flow velocities by laser velocimetry. It was found that soot surface oxidation rates are not particularly affected by fuel type for laminar diffusion flames and are described reasonably well by the OH surface oxidation mechanism with a collision efficiency of 0.10, (standard deviation of 0.07) with no significant effect of fuel type in this behavior; these findings are in good agreement with the classical laminar premixed flame measurements of Neoh et al. Finally, direct rates of surface oxidation by O2 were small compared to OH oxidation for present conditions, based on estimated O2 oxidation rates due to Nagle and Strickland-Constable (1962), because soot oxidation was completed near the flame sheet where O2 concentrations were less than 1.2% by volume.

Surface reaction characteristics at low temperature synthesis BaTiO 3 particles by barium hydroxide aqueous solution and titanium tetraisopropoxide

NASA Astrophysics Data System (ADS)

Zeng, Min

2011-05-01

Well-crystallized cubic phase BaTiO 3 particles were prepared by heating the mixture of barium hydroxide aqueous solution and titania derived from the hydrolysis of titanium isopropoxide (TTIP) at 328 K, 348 K or 368 K for 24 h. The morphology and size of obtained particles depended on the reaction temperature and the Ba(OH) 2/TTIP molar ratio. By the direct hydrolytic reaction of titanium tetraisopropoxide, the high surface area titania (TiO 2) was obtained. The surface adsorption characteristics of the titania particles had been studied with different electric charges OH - ions or H + ions. The formation mechanism and kinetics of BaTiO 3 were examined by measuring the concentration of [Ba 2+] ions in the solution during the heating process. The experimental results showed that the heterogeneous nucleation of BaTiO 3 occurred on the titania surface, according to the Avrami's equation.

Direct Observation of Surface Potential Distribution in Insulation Resistance Degraded Acceptor-Doped BaTiO3 Multilayered Ceramic Capacitors

NASA Astrophysics Data System (ADS)

Hong, Kootak; Lee, Tae Hyung; Suh, Jun Min; Park, Jae-Sung; Kwon, Hyung-Soon; Choi, Jaeho; Jang, Ho Won

2018-05-01

Insulation resistance (IR) degradation in BaTiO3 is a key issue for developing miniaturized multilayer ceramic capacitors (MLCCs) with high capacity. Despite rapid progress in BaTiO3-based MLCCs, the mechanism of IR degradation is still controversial. In this study, we demonstrate the Al doping effect on IR degradation behavior of BaTiO3 MLCCs by electrical measurements and scanning Kelvin probe microscopy (SKPM). As the Al doping concentration in BaTiO3 increases, IR degradation of MLCCs seems to be suppressed from electrical characterization results. However, SKPM results reveal that the conductive regions near the cathode become lager with Al doping after IR degradation. The formation of conducting regions is attributed to the migration of oxygen vacancies, which is the origin of IR degradation in BaTiO3, in dielectric layers. These results imply that acceptor doping in BaTiO3 solely cannot suppress the IR degradation in MLCC even though less asymmetric IR characteristics and IR degradation in MLCCs with higher Al doping concentration are observed from electrical characterization. Our results strongly suggest that observing the surface potential distribution in IR degraded dielectric layers using SKPM is an effective method to unravel the mechanism of IR degradation in MLCCs.

Sea-urchin-like Fe3O4@C@Ag particles: an efficient SERS substrate for detection of organic pollutants

NASA Astrophysics Data System (ADS)

Ye, Yingjie; Chen, Jin; Ding, Qianqian; Lin, Dongyue; Dong, Ronglu; Yang, Liangbao; Liu, Jinhuai

2013-06-01

Ag-coated sea-urchin-like Fe3O4@C core-shell particles can be synthesized by a facile one-step solvothermal method, followed by deposition of high-density Ag nanoparticles onto the carbon surface through an in situ growth process, respectively. The as-synthesized Ag-coated Fe3O4@C particles can be used as a surface-enhanced Raman scattering (SERS) substrate holding reproducible properties under an external magnetic force. The magnetic function of the particles allows concentrating the composite particles into small spatial regions, which can be exploited to decrease the amount of material per analysis while improving its SERS detection limit. In contrast to the traditional SERS substrates, the present Fe3O4@C@Ag particles hold the advantages of enrichment of organic pollutants for improving SERS detection limit and recycled utilization.Ag-coated sea-urchin-like Fe3O4@C core-shell particles can be synthesized by a facile one-step solvothermal method, followed by deposition of high-density Ag nanoparticles onto the carbon surface through an in situ growth process, respectively. The as-synthesized Ag-coated Fe3O4@C particles can be used as a surface-enhanced Raman scattering (SERS) substrate holding reproducible properties under an external magnetic force. The magnetic function of the particles allows concentrating the composite particles into small spatial regions, which can be exploited to decrease the amount of material per analysis while improving its SERS detection limit. In contrast to the traditional SERS substrates, the present Fe3O4@C@Ag particles hold the advantages of enrichment of organic pollutants for improving SERS detection limit and recycled utilization. Electronic supplementary information (ESI) available: Additional XRD patterns and SEM images of Fe3O4@C particles, SERS spectra of 4-ATP and 4-MPY using Fe3O4@C@Ag particles as the active substrates, magnetic behaviour of Fe3O4@C and Fe3O4@C@Ag particles. See DOI: 10.1039/c3nr01273e

In situ study of emerging metallicity on ion-bombarded SrTiO3 surface

NASA Astrophysics Data System (ADS)

Gross, Heiko; Bansal, Namrata; Kim, Yong-Seung; Oh, Seongshik

2011-10-01

We report how argon bombardment induces metallic states on the surface of insulating SrTiO3 at different temperatures by combining in situ conductance measurements and model calculations. At cryogenic temperatures, ionic bombardment created a thin-but much thicker than the argon-penetration depth-steady-state oxygen-vacant layer, leading to a highly-concentric metallic state. Near room temperatures, however, significant thermal diffusion occurred and the metallic state continuously diffused into the bulk, leaving only low concentration of electron carriers on the surface. Analysis of the discrepancy between the experiments and the models also provided evidence for vacancy clustering, which seems to occur during any vacancy formation process and affects the observed conductance.

The Response of Phanerozoic Surface Temperature to Variations in Atmospheric Oxygen Concentration

NASA Astrophysics Data System (ADS)

Payne, R. C.; Britt, A. V.; Chen, H.; Kasting, J. F.; Catling, D. C.

2016-12-01

Recently, Poulsen et al. (2015) suggested that O2 has played a major role in climate forcing during the Phanerozoic. Specifically, they argued that decreased O2 levels during the Cenomanian stage of the mid-Cretaceous (94-100 Ma) could help explain the extremely warm climate during that time. The postulated warming mechanism involves decreased Rayleigh scattering by a thinner atmosphere, which reduces the planetary albedo and allows greater surface warming. This warming effect is then amplified by cloud feedbacks within their 3-D climate model. This increase in shortwave surface forcing, in their calculations, exceeds any decrease in the greenhouse effect caused by decreased O2, so that surface temperature increases by 2.1 K with low oxygen. Here, we use a 1-D radiative-convective climate model (with no cloud feedbacks) to check their results. We also include a self-consistent calculation of the change in atmospheric ozone and its effect on climate. Our results are opposite to those of Poulsen et al.: we find that the climate warms by 1.4 K at 35% O2 concentrations as a result of increased pressure broadening of CO2 and H2O absorption lines, and cools by 0.8 K at 10% O2 as a result of decreased pressure broadening. The surface temperature changes are only about 1 K either way, though, for reasonable variations in Phanerozoic O2 concentrations (10% - 35% by volume), and the Poulsen et al. (2016) results appear to be largely driven by cloud feedbacks in their model. Hence, it seems unlikely that changes in atmospheric O2 account for the warm climate of the Cenomanian. Other factors, such as a higher-than-expected sensitivity of climate to increased CO2 concentrations, may be required to obtain agreement with the paleoclimate data.

Balloon-Borne Measurements of CLO, NO and O3 in a Volcanic Cloud: An Analysis of Heterogeneous Chemistry between 20 and 30 KM

NASA Technical Reports Server (NTRS)

Dessler, A. E.; Stimpfle, R. M.; Daube, B. C.; Salawitch, R. J.; Weinstock, E. M.; Judah, D. M.; Burley, J. D.; Munger, J. W.; Wofsy, S. C.; Anderson, J. G.;

Mechanical writing of n-type conductive layers on the SrTiO3 surface in nanoscale

PubMed Central

Wang, Yuhang; Zhao, Kehan; Shi, Xiaolan; Li, Geng; Xie, Guanlin; Lai, Xubo; Ni, Jun; Zhang, Liuwan

2015-01-01

The fabrication and control of the conductive surface and interface on insulating SrTiO3 bulk provide a pathway for oxide electronics. The controllable manipulation of local doping concentration in semiconductors is an important step for nano-electronics. Here we show that conductive patterns can be written on bare SrTiO3 surface by controllable doping in nanoscale using the mechanical interactions of atomic force microscopy tip without applying external electric field. The conductivity of the layer is n-type, oxygen sensitive, and can be effectively tuned by the gate voltage. Hence, our findings have potential applications in oxide nano-circuits and oxygen sensors. PMID:26042679

Allocating emissions to 4 km and 1 km horizontal spatial resolutions and its impact on simulated NOx and O3 in Houston, TX

NASA Astrophysics Data System (ADS)

Pan, Shuai; Choi, Yunsoo; Roy, Anirban; Jeon, Wonbae

2017-09-01

A WRF-SMOKE-CMAQ air quality modeling system was used to investigate the impact of horizontal spatial resolution on simulated nitrogen oxides (NOx) and ozone (O3) in the Greater Houston area (a non-attainment area for O3). We employed an approach recommended by the United States Environmental Protection Agency to allocate county-based emissions to model grid cells in 1 km and 4 km horizontal grid resolutions. The CMAQ Integrated Process Rate analyses showed a substantial difference in emissions contributions between 1 and 4 km grids but similar NOx and O3 concentrations over urban and industrial locations. For example, the peak NOx emissions at an industrial and urban site differed by a factor of 20 for the 1 km and 8 for the 4 km grid, but simulated NOx concentrations changed only by a factor of 1.2 in both cases. Hence, due to the interplay of the atmospheric processes, we cannot expect a similar level of reduction of the gas-phase air pollutants as the reduction of emissions. Both simulations reproduced the variability of NASA P-3B aircraft measurements of NOy and O3 in the lower atmosphere (from 90 m to 4.5 km). Both simulations provided similar reasonable predictions at surface, while 1 km case depicted more detailed features of emissions and concentrations in heavily polluted areas, such as highways, airports, and industrial regions, which are useful in understanding the major causes of O3 pollution in such regions, and to quantify transport of O3 to populated communities in urban areas. The Integrated Reaction Rate analyses indicated a distinctive difference of chemistry processes between the model surface layer and upper layers, implying that correcting the meteorological conditions at the surface may not help to enhance the O3 predictions. The model-observation O3 bias in our studies (e.g., large over-prediction during the nighttime or along Gulf of Mexico coastline), were due to uncertainties in meteorology, chemistry or other processes. Horizontal grid resolution is unlikely the major contributor to these biases.

Effect of precursor concentration and film thickness deposited by layer on nanostructured TiO2 thin films

NASA Astrophysics Data System (ADS)

Affendi, I. H. H.; Sarah, M. S. P.; Alrokayan, Salman A. H.; Khan, Haseeb A.; Rusop, M.

2018-05-01

Sol-gel spin coating method is used in the production of nanostructured TiO2 thin film. The surface topology and morphology was observed using the Atomic Force Microscopy (AFM) and Field Emission Scanning Electron Microscopy (FESEM). The electrical properties were investigated by using two probe current-voltage (I-V) measurements to study the electrical resistivity behavior, hence the conductivity of the thin film. The solution concentration will be varied from 14.0 to 0.01wt% with 0.02wt% interval where the last concentration of 0.02 to 0.01wt% have 0.01wt% interval to find which concentrations have the highest conductivity then the optimized concentration's sample were chosen for the thickness parameter based on layer by layer deposition from 1 to 6 layer. Based on the result, the lowest concentration of TiO2, the surface becomes more uniform and the conductivity will increase. As the result, sample of 0.01wt% concentration have conductivity value of 1.77E-10 S/m and will be advanced in thickness parameter. Whereas in thickness parameter, the 3layer deposition were chosen as its conductivity is the highest at 3.9098E9 S/m.

Stoichiometric control for heteroepitaxial growth of smooth ɛ-Ga2O3 thin films on c-plane AlN templates by mist chemical vapor deposition

NASA Astrophysics Data System (ADS)

Tahara, Daisuke; Nishinaka, Hiroyuki; Morimoto, Shota; Yoshimoto, Masahiro

2017-07-01

Epitaxial ɛ-Ga2O3 thin films with smooth surfaces were successfully grown on c-plane AlN templates by mist chemical vapor deposition. Using X-ray diffraction 2θ-ω and φ scans, the out-of-plane and in-plane epitaxial relationship was determined to be (0001) ɛ-Ga2O3 [10\\bar{1}0] ∥ (0001)AlN[10\\bar{1}0]. The gallium/oxygen ratio was controlled by varying the gallium precursor concentration in the solution. While scanning electron microscopy showed the presence of large grains on the surfaces of the films formed for low concentrations of oxygen species, no large grains were observed under stoichiometric conditions. Cathodoluminescence measurements showed a deep-level emission ranging from 1.55-3.7 eV; however, no band-edge emission was observed.

Highly sensitive hydrogen detection of catalyst-free ZnO nanorod networks suspended by lithography-assisted growth.

PubMed

Huh, Junghwan; Park, Jonghyurk; Kim, Gyu Tae; Park, Jeong Young

2011-02-25

We have successfully demonstrated a ZnO nanorod-based 3D nanostructure to show a high sensitivity and very fast response/recovery to hydrogen gas. ZnO nanorods have been synthesized selectively over the pre-defined area at relatively low temperature using a simple self-catalytic solution process assisted by a lithographic method. The conductance of the ZnO nanorod device varies significantly as the concentration of the hydrogen is changed without any additive metal catalyst, revealing a high sensitivity to hydrogen gas. Its superior performance can be explained by the porous structure of its three-dimensional network and the enhanced surface reaction of the hydrogen molecules with the oxygen defects resulting from a high surface-to-volume ratio. It was found that the change of conductance follows a power law depending on the hydrogen concentration. A Langmuir isotherm following an ideal power law and a cross-over behavior of the activation energy with respect to hydrogen concentration were observed. This is a very novel and intriguing phenomenon on nanostructured materials, which suggests competitive surface reactions in ZnO nanorod gas sensors.

Application of headspace analysis to the study of sorption of hydrophobic organic chemicals to α-Al2O3

USGS Publications Warehouse

Pelinger, Judith A.; Eisenreich, Steven J.; Capel, Paul D.

1993-01-01

The sorption of hydrophobic organic chemicals (HOCs) to ??-Al2O3 was investigated with a headspace analysis method. The semiautomated headspace analyzer gave rapid, precise, and accurate results for a homologous series alkylbenzenes even at low percentages of solute mass sorbed (3-50%). Sorption experiments carried out with benzene alone indicated weak interactions with well-characterized aluminum oxide, and a solids concentration effect was observed. When the sorption coefficients for benzene alone obtained by headspace analysis were extrapolated up to the solids concentrations typically used in batch sorption experiments, the measured sorption coefficients agreed with reported sorption coefficients for HOCs and sediments of low fractional organic carbon content. Sorbed concentrations increased exponentially with aqueous concentration in isotherms with mixtures of alkylbenzenes, indicating solute-solute interactions at the mineral surface. Sorption was, however, greater than predicted for partitioning of a solute between its pure liquid phase and water, indicating additional influences of the surface and/or the structured liquid near the mineral surface. ?? 1993 American Chemical Society.

Surface NH2-rich nanoparticles: Solidifying ionic-liquid electrolytes and improving the performance of dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Fang, Yanyan; Ma, Pin; Fu, Nianqing; Zhou, Xiaowen; Fang, Shibi; Lin, Yuan

2017-12-01

The surface properties of nanoparticles have a significant influence on the properties of the gel electrolytes. Herein, the surface NH2-rich nanoparticle (A-SiO2), with a tightening network, is synthesized by silanizing SiO2 nanoparticles with pre-polymerized aminopropyltriethoxysilane, which is further employed to prepare ionic-liquid gel electrolytes for dye-sensitized solar cells. The addition of a small amount of A-SiO2 can effectively solidify the ionic-liquid, whereas a large number of NH2 groups on the SiO2 surface leads to a large negative shift of the TiO2 conduction band edge, and can react with I3- in the form of a Lewis complex, resulting in an increase in the concentration of I- and a decrease in the concentration of I3- in the electrolyte. In addition, the ionic-liquid gel electrolyte possesses thixotropic behavior, which allows it to easily penetrate into the inner part of the TiO2 mesoporous film. As a result, large improvements of the photovoltage from 695 mV to 785 mV and of the photocurrent from 13.3 mA cm-2 to 14.9 mA cm-2 are achieved. This leads to significant enhancement of the power conversion efficiency, from 6.2% to 8.1%, for the cell with A-SiO2 compared to that of the pristine ionic-liquid electrolyte.

Attack polish for nickel-base alloys and stainless steels

DOEpatents

Not Available

1980-05-28

A chemical attack polish and polishing procedure for use on metal surfaces such as nickel base alloys and stainless steels is described. The chemical attack polich comprises FeNO/sub 3/, concentrated CH/sub 3/COOH, concentrated H/sub 2/SO/sub 4/ and H/sub 2/O. The polishing procedure includes saturating a polishing cloth with the chemical attack polish and submicron abrasive particles and buffing the metal surface.

Degradation of sulfamethazine using Fe3O4-Mn3O4/reduced graphene oxide hybrid as Fenton-like catalyst.

PubMed

Wan, Zhong; Wang, Jianlong

2017-02-15

In this paper, Fe 3 O 4 -Mn 3 O 4 /reduced graphene oxide (RGO) hybrid was synthesized through polyol process and impregnation method and used as heterogeneous Fenton-like catalyst for degradation of sulfamethazine (SMT) in aqueous solution. The hybrid catalyst had higher catalytic efficiency compared with Fe 3 O 4 -Mn 3 O 4 and Mn 3 O 4 as catalyst for degradation of SMT . The effects of pH value, H 2 O 2 concentration, catalyst dosage, initial SMT concentration and temperature on SMT degradation were investigated. The removal efficiency of SMT was about 98% at following optimal conditions: pH=3, T=35°C, Fe 3 O 4 /Mn 3 O 4 -RGO composites=0.5g/L, H 2 O 2 =6mM. The inhibitor experiments indicated that the main active species was hydroxyl radicals (·OH) on catalyst surface. At last, the possible catalytic mechanism was proposed. Copyright © 2016 Elsevier B.V. All rights reserved.

Investigating Sources of Ozone over California Using AJAX Airborne Measurements and Models: Assessing the Contribution from Long Range Transport

NASA Technical Reports Server (NTRS)

Ryoo, Ju-Mee; Johnson, Matthew S.; Iraci, Laura T.; Yates, Emma L.; Gore, Warren

2017-01-01

High ozone (O3) concentrations at low altitudes (1.5e4 km) were detected from airborne Alpha Jet Atmospheric eXperiment (AJAX) measurements on 30 May 2012 off the coast of California (CA). We investigate the causes of those elevated O3 concentrations using airborne measurements and various models. GEOS-Chem simulation shows that the contribution from local sources is likely small. A back trajectory model was used to determine the air mass origins and how much they contributed to the O3 over CA. Low-level potential vorticity (PV) from Modern Era Retrospective analysis for Research and Applications 2 (MERRA-2) reanalysis data appears to be a result of the diabatic heating and mixing of airs in the lower altitudes, rather than be a result of direct transport from stratospheric intrusion. The Q diagnostic, which is a measure of the mixing of the air masses, indicates that there is sufficient mixing along the trajectory to indicate that O3 from the different origins is mixed and transported to the western U.S.The back-trajectory model simulation demonstrates the air masses of interest came mostly from the mid troposphere (MT, 76), but the contribution of the lower troposphere (LT, 19) is also significant compared to those from the upper troposphere/lower stratosphere (UTLS, 5). Air coming from the LT appears to be mostly originating over Asia. The possible surface impact of the high O3 transported aloft on the surface O3 concentration through vertical and horizontal transport within a few days is substantiated by the influence maps determined from the Weather Research and Forecasting Stochastic Time Inverted Lagrangian Transport (WRF-STILT) model and the observed increases in surface ozone mixing ratios. Contrasting this complex case with a stratospheric-dominant event emphasizes the contribution of each source to the high O3 concentration in the lower altitudes over CA. Integrated analyses using models, reanalysis, and diagnostic tools, allows high ozone values detected by in-situ measurements to be attributed to multiple source processes.

Lack of enhanced photocatalytic formation of iodine on particulate semiconductor mixtures.

PubMed

Karunakaran, C; Anilkumar, P; Vinayagamoorthy, P

2012-12-01

Under UV-A light illumination, formation of iodine from iodide ion on the surfaces of anatase TiO(2), ZnO, Fe(2)O(3), CeO(2), MoO(3), Bi(2)O(3), and Nb(2)O(5) increases with the concentration of iodide ion, airflow rate and light intensity and conform to the Langmuir-Hinshelwood kinetic model. Measurement of the particle size of the semiconductor oxides by light scattering method and deduction of the same from the determined specific surface area show that the oxide particles agglomerate in suspension. However, mixtures of any two listed particulate semiconductors do not show enhanced photocatalytic formation of iodine indicating absence of interparticle charge transfer. The results are rationalized. Copyright © 2012 Elsevier B.V. All rights reserved.

Influence of Water Vapors and Hydrogen on the Energy Band Bending in the SnO2 Microcrystals of Polycrystalline Tin Dioxide Films

NASA Astrophysics Data System (ADS)

Gaman, V. I.; Almaev, A. V.; Sevast'yanov, E. Yu.; Maksimova, N. K.

2015-06-01

The results of studying the dependence of the energy band bending at the interface of contacting SnO2 microcrystals in the polycrystalline tin dioxide film on the humidity level of clean air and hydrogen concentration in the gas mixture of clean air + H2 are presented. The experimental results showed that the bending of energy bands in SnO2 is decreased under exposure to the water vapors and molecular hydrogen. The presence of two types of the adsorption centers for water molecules on the surface of SnO2 is found. It is shown that at the absolute humidity of the gas mixture above 12 g/m3, the H2O and H2 molecules are adsorbed on the same centers, whose surface density is of 1012 сm-2 at a concentration of donor impurity in SnO2 equal to 1018 сm-3.

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

Park, R.; Hong, Seungkyu K.; Kwon, Hyoung-Ahn

We used a 3-D regional atmospheric chemistry transport model (WRF-Chem) to examine processes that determine O3 in East Asia; in particular, we focused on O3 dry deposition, which is an uncertain research area due to insufficient observation and numerical studies in East Asia. Here, we compare two widely used dry deposition parameterization schemes, Wesely and M3DRY, which are used in the WRF-Chem and CMAQ models, respectively. The O3 dry deposition velocities simulated using the two aforementioned schemes under identical meteorological conditions show considerable differences (a factor of 2) due to surface resistance parameterization discrepancies. The O3 concentration differed by upmore » to 10 ppbv for the monthly mean. The simulated and observed dry deposition velocities were compared, which showed that the Wesely scheme model is consistent with the observations and successfully reproduces the observed diurnal variation. We conduct several sensitivity simulations by changing the land use data, the surface resistance of the water and the model’s spatial resolution to examine the factors that affect O3 concentrations in East Asia. As shown, the model was considerably sensitive to the input parameters, which indicates a high uncertainty for such O3 dry deposition simulations. Observations are necessary to constrain the dry deposition parameterization and input data to improve the East Asia air quality models.« less

Surface ozone and NOx trends observed over Kannur, a South Indian coastal location of weak industrial activities

NASA Astrophysics Data System (ADS)

Kumar, Satheesh Mk; T, Nishanth; M, Praseeed K.

South India is a peninsular region surrounded by the three belts of Arabian Sea, Bay of Bengal and Indian Ocean. Usually, coastal regions experience relatively high air quality compared to that of the interior land masses owing to the abundance of OH over ocean surface which acts as detergent in the atmosphere. Kannur (11.9 N, 75.4E, 5 m AMSL) is a coastal location along the Arabian Sea which is located in the northern district of Kerala State with fairly low industrial activities. A continuous observation of surface ozone (O3), NOx and OX (NO2+ O3) which has been initiated at this coastal site since 2009 reveals the enhancement in the concentrations of these trace species quite significantly. It is observed that surface O3 mixing ratio is increased at a rate of 1.51 ± 0.5 ppbv/year during the four year period from 2009 at Kannur. The enhancement rate in the mixing ratios of NOx is 1.01 ± 0.4 ppbv/year and OX is 1.49±0.42 ppbv/year respectively. The increase of O3 may be attributed due to the increase in methane and non-methane organic emissions from the wet lands and vehicles may enhance O3 production and fairly low rate of change of NO concentration at this site. This paper describes the rate of changes of O3, NOx and OX during the period of observation in detail. Likewise, the increase in nighttime concentrations of O3 and PM10 observed during the festival occasions in the summer month of April in all years is explained. Being a weak industrialized location, the main source of pollution is by vehicular emissions and the increase in these trace gases in the context of rapid enhancement in the number of vehicles is well correlated. These results may be helpful for improving government policies to control the photochemical formation of secondary air pollutants in the rural coastal sites that has a significant influence on the onset of monsoon and the outcome of this study have significant relevance for gradual transformation of pristine locations into polluted sites.

Improved passivation effect in multicrystalline black silicon by chemical solution pre-treatment

NASA Astrophysics Data System (ADS)

Jiang, Ye; Shen, Honglie; Pu, Tian; Zheng, Chaofan

2018-04-01

Though black silicon has excellent anti-reflectance property, its passivation is one of the main technical bottlenecks due to its large specific surface area. In this paper, multicrystalline black silicon is fabricated by metal assisted chemical etching, and is rebuilt in low concentration alkali solution. Different solution pre-treatment is followed to make surface modification on black silicon before Al2O3 passivation by atomic layer deposition. HNO3 and H2SO4 + H2O2 solution pre-treatment makes the silicon surface become hydrophilic, with contact angle decrease from 117.28° to about 30°. It is demonstrated that when the pre-treatment solution is nitric acid, formed ultrathin SiO x layer between Al2O3 layer and black silicon is found to increase effective carrier lifetime to 72.64 µs, which is obviously higher than that of the unpassivated black silicon. The passivation stacks of SiO x /Al2O3 are proved to be effective double layers for nanoscaled multicrystalline silicon surface.

Application of response surface methodology for optimization of natural organic matter degradation by UV/H2O2 advanced oxidation process

PubMed Central

2014-01-01

Background In this research, the removal of natural organic matter from aqueous solutions using advanced oxidation processes (UV/H2O2) was evaluated. Therefore, the response surface methodology and Box-Behnken design matrix were employed to design the experiments and to determine the optimal conditions. The effects of various parameters such as initial concentration of H2O2 (100–180 mg/L), pH (3–11), time (10–30 min) and initial total organic carbon (TOC) concentration (4–10 mg/L) were studied. Results Analysis of variance (ANOVA), revealed a good agreement between experimental data and proposed quadratic polynomial model (R2 = 0.98). Experimental results showed that with increasing H2O2 concentration, time and decreasing in initial TOC concentration, TOC removal efficiency was increased. Neutral and nearly acidic pH values also improved the TOC removal. Accordingly, the TOC removal efficiency of 78.02% in terms of the independent variables including H2O2 concentration (100 mg/L), pH (6.12), time (22.42 min) and initial TOC concentration (4 mg/L) were optimized. Further confirmation tests under optimal conditions showed a 76.50% of TOC removal and confirmed that the model is accordance with the experiments. In addition TOC removal for natural water based on response surface methodology optimum condition was 62.15%. Conclusions This study showed that response surface methodology based on Box-Behnken method is a useful tool for optimizing the operating parameters for TOC removal using UV/H2O2 process. PMID:24735555

Surface ozone and carbon monoxide levels observed at Oki, Japan: regional air pollution trends in East Asia.

PubMed

Sikder, Helena Akhter; Suthawaree, Jeeranut; Kato, Shungo; Kajii, Yoshizumi

2011-03-01

Simultaneous ground-based measurements of ozone and carbon monoxide were performed at Oki, Japan, from January 2001 to September 2002 in order to investigate the O(3) and CO characteristics and their distributions. The observations revealed that O(3) and CO concentrations were maximum in springtime and minimum in the summer. The monthly averaged concentrations of O(3) and CO were 60 and 234 ppb in spring and 23 and 106 ppb in summer, respectively. Based on direction, 5-day isentropic backward trajectory analysis was carried out to determine the transport path of air masses, preceding their arrival at Oki. Comparison between classified results from present work and results from the year 1994-1996 was carried out. The O(3) and CO concentration results of classified air masses in our analysis show similar concentration trends to previous findings; highest in the WNW/W, lowest in N/NE and medium levels in NW. Moreover, O(3) levels are higher and CO levels are lower in the present study in all categories. Copyright © 2010 Elsevier Ltd. All rights reserved.

Changes in local surface structure and Sr depletion in Fe-implanted SrTiO3 (001)

NASA Astrophysics Data System (ADS)

Lobacheva, O.; Yiu, Y. M.; Chen, N.; Sham, T. K.; Goncharova, L. V.

2017-01-01

Local surface structure of single crystal strontium titanate SrTiO3 (001) samples implanted with Fe in the range of concentrations between 2 × 1014 to 2 × 1016 Fe/cm2 at 30 keV has been investigated. In order to facilitate Fe substitution (doping), implanted samples were annealed in oxygen at 350 °C. Sr depletion was observed from the near-surface layers impacted by the ion-implantation process, as revealed by Rutherford Backscattering Spectrometry (RBS), X-ray photoelectron spectroscopy (XPS), X-ray Absorption Near Edge Spectroscopy (XANES), and Atomic Force Microscopy (AFM). Hydrocarbon contaminations on the surface may contribute to the mechanisms of Sr depletion, which have important implications for Sr(Ti1-xFex)O3-δ materials in gas sensing applications.

Tropospheric ozone measurements at the equatorial region (1980-1988)

NASA Technical Reports Server (NTRS)

Ilyas, Mohammad

1994-01-01

Results from surface ozone measurements at Penang (5.5 deg N, 100 deg E) over 1980-88 period are presented. The study indicates the ozone concentrations undergoing significant diurnal and seasonal variations. The peak concentration are observed at around mid-day (up to 35 nb) but the O3 concentration generally drops to zero level in the early evening and remains unchanged until mid-morning. Monthly-averaged daily 1-h average concentrations are generally small (4-13 nb) and decrease continually from the early part of the year to the end. Frequently, varying local weather conditions seem to influence the O3 concentrations.

Impacts of enhanced fertilizer applications on tropospheric ozone and crop damage over sub-Saharan Africa

NASA Astrophysics Data System (ADS)

Huang, Yaoxian; Hickman, Jonathan E.; Wu, Shiliang

2018-05-01

Fertilizer-induced nitrogen oxides (NOx) emissions in sub-Saharan Africa are expected to increase substantially in the coming decades, driven by increasing application of fertilizers to increase crop yields in an effort to attain food security across the continent. In many parts of sub-Saharan Africa, surface ozone (O3) is sensitive to increasing atmospheric concentrations of NOx. In this study, we employ the GEOS-Chem chemical transport model to conduct a preliminary investigation of the impacts on O3 air quality and the consequential crop damage associated with increasing fertilizer-induced NOx emissions in sub-Saharan Africa. Our simulation results, constrained by field NO flux measurements for the years 2011 and 2012 in response to a variety of fertilizer application rates in western Kenya, show that the enhancements in NO flux with fertilizer application rate of 150 kg N ha-1 can increase surface NOx and O3 concentrations by up to 0.36 and 2.8 ppbv respectively during the growing season. At the same time, accumulated O3 exposure during the crop growing season (expressed as AOT40 values) could increase by up to 496 ppb h, leading to crop yield decline of about 0.8% for O3-sensitive crops. Our results suggest that, when accounting for the consequential impacts on surface O3 air quality and crop damage over sub-Saharan Africa, agricultural intensification is possible without substantial impacts on crop productivity because the relatively small decline of crop yield resulting from O3 damage appears unlikely to outweigh the gain in crop yield from fertilization.

Defect induced ferromagnetism in MgO nanoparticles studied by optical and positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Kumar, Nitesh; Sanyal, D.; Sundaresan, A.

2009-08-01

Positron annihilation spectroscopy has been used to explore the nature of defects and to estimate the defect concentrations in ferromagnetic MgO nanoparticles. Our experimental results show that Mg vacancies or Mg vacancy concentration are present approximately at the concentration of 3.4 × 10 16 cm -3 in the nano-crystalline MgO which is twice the value that obtained for bulk sample. This is in correlation with the decrease of the intensity of blue luminescence and the saturation magnetic moment with increasing particle size. These results clearly demonstrate that the origin of magnetic moment and thus the ferromagnetism in MgO nanoparticles is due to Mg related vacancies at the surface of the particles.

Evolution of the surface species of the V 2O 5-WO 3 catalysts

NASA Astrophysics Data System (ADS)

Najbar, M.; Brocławik, E.; Góra, A.; Camra, J.; Białas, A.; Wesełucha-Birczyńska, A.

2000-07-01

Vanadia-related species formed as a result of vanadium segregation at the surface of V-W oxide bronze crystallites were investigated. The structures of these species and their transformations induced by oxygen removal and oxygen adsorption were monitored using photoelectron spectroscopy and the FT Raman technique. Assignments of the MeO vibrational bands, based on the results of DFT calculations for model clusters, have been proposed. Two kinds of surface species are dominant depending on the tungsten content: V 4+-O-W 6+ at low tungsten content and V 5+-O-W 5+ at higher tungsten concentration.

Comparison of O2 and H2O as oxygen source for homoepitaxial growth of β-Ga2O3 layers by halide vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Konishi, Keita; Goto, Ken; Togashi, Rie; Murakami, Hisashi; Higashiwaki, Masataka; Kuramata, Akito; Yamakoshi, Shigenobu; Monemar, Bo; Kumagai, Yoshinao

2018-06-01

Homoepitaxial growth of β-Ga2O3 layers by halide vapor phase epitaxy (HVPE) using O2 or H2O as an oxygen source was investigated by thermodynamic analysis, and compared with measured properties after growth. The thermodynamic analysis revealed that Ga2O3 growth is expected even at 1000 °C using both oxygen sources due to positive driving forces for Ga2O3 deposition. The experimental results for homoepitaxial growth on (0 0 1) β-Ga2O3 substrates showed that the surfaces of the layers grown with H2O were smoother than those grown with O2, although the growth rate with H2O was approximately half that with O2. However, in the homoepitaxial layer grown using H2O, incorporation of Si impurities with a concentration almost equal to the effective donor concentration (2 × 1016 cm-3) was confirmed, which was caused by decomposition of the quartz glass reactor due to the presence of hydrogen in the system.

Removal of elemental mercury by TiO₂doped with WO₃ and V₂O₅ for their photo- and thermo-catalytic removal mechanisms.

PubMed

Shen, Huazhen; Ie, Iau-Ren; Yuan, Chung-Shin; Hung, Chung-Hsuang; Chen, Wei-Hsiang

2016-03-01

The catalytic removal of Hg(0) was investigated to ascertain whether the catalysts could simultaneously possess both thermo- and photo-catalytic reactivity. The immobilized V2O5/TiO2 and WO3/TiO2 catalysts were synthesized by sol-gel method and then coated on the surface of glass beads for catalytic removal of Hg(0). They were also characterized by SEM, BET, XRD, UV-visible, and XPS analysis, and their catalytic reactivity was tested under 100-160 °C under the near-UV irradiation. The results indicated that V2O5/TiO2 solely possessed the thermo-catalytic reactivity while WO3/TiO2 only had photo-catalytic reactivity. Although the synthesis catalytic reactivity has not been found for these catalysts up to date, but compared with TiO2, the removal efficiencies of Hg(0) at 140 and 160 °C were enhanced; particularly, the efficiency was improved from 20 % at 160 °C by TiO2 to nearly 90 % by WO3/TiO2 under the same operating conditions. The effects of doping amount of V2O5 and WO3 were also investigated, and the results showed that 10 % V2O5 and 5 % WO3/TiO2 were the best immobilized catalysts for thermo- and photo-catalytic reactivity, respectively. The effect of different influent concentrations of Hg(0) was demonstrated that the highest concentration of Hg(0) led to the best removal efficiencies for V2O5/TiO2 and WO3/TiO2 at 140 and 160 °C, because high Hg(0) concentration increased the mass transfer rate of Hg(0) toward the surface of catalysts and drove the reaction to proceed. At last, the effect of single gas component on the removal of Hg(0) was also investigated.

Quantifying the Contribution of Thermally Driven Recirculation to a High-Ozone Event Along the Colorado Front Range Using Lidar

NASA Technical Reports Server (NTRS)

Sullivan, John T.; McGee, Thomas J.; Langford, Andrew O.; Alvarez, Raul J., II; Senff, Christoph; Reddy, Patrick J.; Thompson, Anne M.; Twigg, Laurence W.; Sumnicht, Grant K.; Lee, Pius;

Spatial variability in groundwater N2 and N2O in the San Joaquin River

NASA Astrophysics Data System (ADS)

Hinshaw, S.; Dahlgren, R. A.

2010-12-01

The San Joaquin River is surrounded by nearly 2 million acres of irrigated agricultural land. Groundwater inputs from agricultural areas can have severe negative effects on water quality with high nitrate concentrations being a major concern. Riparian zones are important ecological habitats that mitigate nitrogen loading from groundwater discharging into rivers primarily by denitrification. Denitrification is a permanent removal of nitrate by anaerobic microbial communities via the reduction to NO, N2O and N2. However, previous studies have shown that these areas can be source of N2O emissions. Although removal of nitrate through denitrification is advantageous from a water quality perspective, N2O is a harmful greenhouse gas. This study aimed to investigate nitrogen dynamics and dissolved N gases in surface and groundwater of the riparian zones of the San Joaquin River. Excess N2 and N2O concentrations were measured in surface and groundwater at 4 locations along a 33 km reach of the river. Samples were collected within bank sediments and 5 transect points across the river at depth intervals between 2-3 cm and 150 cm. Dissolved N2 and Ar were measured by membrane inlet mass spectrometry and used to estimate excess dissolved N2 concentrations. Dissolved N2O concentrations were measured using the headspace equilibrium technique and analyzed with a gas chromatograph. Both N2 uptake and excess N2 were present, ranging from -3.40 to 8.65 N2 mg/L with a median concentration of 1.20 N2 mg/L. Significantly lower concentrations of N2O were present ranging from 0.0 to 0.12 N2O mg/L. Deeper groundwater sites had significantly higher N2 and N2O concentrations coinciding with decreased O2. The presence of excess N2 and low N2O concentrations documents the importance of denitrification in removing nitrate from groundwater. Further investigation will examine N2O emissions from riparian soils and benthic sediments using static chambers and focus on nitrogen pathways that contribute to high ammonium concentrations with increasing depth.

A modeling study on the effect of urban land surface forcing to regional meteorology and air quality over South China

NASA Astrophysics Data System (ADS)

Zhu, Kuanguang; Xie, Min; Wang, Tijian; Cai, Junxiong; Li, Songbing; Feng, Wen

2017-03-01

The change of land-use from natural to artificial surface induced by urban expansion can deeply impact the city environment. In this paper, the model WRF/Chem is applied to explore the effect of this change on regional meteorology and air quality over South China, where people have witnessed a rapid rate of urbanization. Two sets of urban maps are adopted to stand for the pre-urbanization and the present urban land-use distributions. Month-long simulations are conducted for January and July, 2014. The results show that urban expansion can obviously change the weather conditions around the big cities of South China. Especially in the Pearl River Delta region (PRD), the urban land-use change can increase the sensible heat flux by 40 W/m2 in January and 80 W/m2 in July, while decrease the latent heat flux about -50 W/m2 in January and -120 W/m2 in July. In the consequent, 2-m air temperature (T2) increases as much as 1 °C and 2 °C (respective to January and July), planetary boundary layer height (PBLH) rises up by 100-150 m and 300 m, 10-m wind speed (WS10) decreases by -1.2 m/s and -0.3 m/s, and 2-m specific humidity is reduced by -0.8 g/kg and -1.5 g/kg. Also, the precipitation in July can be increased as much as 120 mm, with more heavy rains and rainstorms. These variations of meteorological factors can significantly impact the spatial and vertical distribution of air pollutants as well. In PRD, the enhanced updraft can reduce the surface concentrations of PM10 by -40 μg/m3 (30%) in January and -80 μg/m3 (50%) in July, but produce a correlating increase in the concentrations at higher atmospheric layers. However, according to the increase in T2 and the decrease in surface NO, the surface concentrations of O3 in PRD can increase by 2-6 ppb in January and 8-12 ppb in July. Meanwhile, there is a significant increase in the O3 concentrations at upper layers above PRD, which should be attributed to the increase in air temperature and the enhanced upward transport of O3 and its precursors. As for some relative small cities, such as Haikou, there is very little variation in surface PM10 and O3 in both months, implying less urbanization in these areas. Moreover, the depletion of O3 by NO may be the main cause of the reduction of O3 at upper layers in these small cities.

Widespread and persistent ozone pollution in eastern China during the non-winter season of 2015: observations and source attributions

NASA Astrophysics Data System (ADS)

Li, Guohui; Bei, Naifang; Cao, Junji; Wu, Jiarui; Long, Xin; Feng, Tian; Dai, Wenting; Liu, Suixin; Zhang, Qiang; Tie, Xuexi

2017-02-01

Rapid growth of industrialization, transportation, and urbanization has caused increasing emissions of ozone (O3) precursors recently, enhancing the O3 formation in eastern China. We show here that eastern China has experienced widespread and persistent O3 pollution from April to September 2015 based on the O3 observations in 223 cities. The observed maximum 1 h O3 concentrations exceed 200 µg m-3 in almost all the cities, 400 µg m-3 in more than 25 % of the cities, and even 800 µg m-3 in six cities in eastern China. The average daily maximum 1 h O3 concentrations are more than 160 µg m-3 in 45 % of the cities, and the 1 h O3 concentrations of 200 µg m-3 have been exceeded on over 10 % of days from April to September in 129 cities. Analyses of pollutant observations from 2013 to 2015 have shown that the concentrations of CO, SO2, NO2, and PM2.5 from April to September in eastern China have considerably decreased, but the O3 concentrations have increased by 9.9 %. A widespread and severe O3 pollution episode from 22 to 28 May 2015 in eastern China has been simulated using the Weather Research and Forecasting model coupled to chemistry (WRF-CHEM) to evaluate the O3 contribution of biogenic and various anthropogenic sources. The model generally performs reasonably well in simulating the temporal variations and spatial distributions of near-surface O3 concentrations. Using the factor separation approach, sensitivity studies have indicated that the industry source plays the most important role in the O3 formation and constitutes the culprit of the severe O3 pollution in eastern China. The transportation source contributes considerably to the O3 formation, and the O3 contribution of the residential source is not significant generally. The biogenic source provides a background O3 source, and also plays an important role in the south of eastern China. Further model studies are needed to comprehensively investigate O3 formation for supporting the design and implementation of O3 control strategies, considering rapid changes of emission inventories and photolysis caused by the Atmospheric Pollution Prevention and Control Action Plan released by the Chinese State Council in 2013.

Preparation of surface plasmon resonance biosensor based on magnetic core/shell Fe3O4/SiO2 and Fe3O4/Ag/SiO2 nanoparticles.

PubMed

Wang, Liying; Sun, Ying; Wang, Jing; Wang, Jian; Yu, Aimin; Zhang, Hanqi; Song, Daqian

2011-06-01

In this paper, surface plasmon resonance biosensors based on magnetic core/shell Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were developed for immunoassay. With Fe(3)O(4) and Fe(3)O(4)/Ag nanoparticles being used as seeding materials, Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were formed by hydrolysis of tetraethyl orthosilicate. The aldehyde group functionalized magnetic nanoparticles provide organic functionality for bioconjugation. The products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), FTIR and UV-vis absorption spectrometry. The magnetic nanoparticles possess the unique superparamagnetism property, exceptional optical properties and good compatibilities, and could be used as immobilization matrix for goat anti-rabbit IgG. The magnetic nanoparticles can be easily immobilized on the surface of SPR biosensor chip by a magnetic pillar. The effects of Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles on the sensitivity of SPR biosensors were also investigated. As a result, the SPR biosensors based on Fe(3)O(4)/SiO(2) nanoparticles and Fe(3)O(4)/Ag/SiO(2) nanoparticles exhibit a response for rabbit IgG in the concentration range of 1.25-20.00 μg ml(-1) and 0.30-20.00 μg ml(-1), respectively. Copyright © 2011 Elsevier B.V. All rights reserved.

Surface-catalyzed air oxidation of hydrazines: Environmental chamber studies

NASA Technical Reports Server (NTRS)

Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.

1988-01-01

The surface-catalyzed air oxidation reactions of fuel hydrazines were studied in a 6500-liter fluorocarbon-film chamber at 80 to 100 ppm concentrations. First-order rate constants for the reactions catalyzed by aluminum, water-damaged aluminum (Al/Al2O3), stainless steel 304L, galvanized steel and titanium plates with surface areas of 2 to 24 sq m were determined. With 23.8 sq m of Al/Al2O3 the surface-catalyzed air oxidation of hydrazine had a half-life of 2 hours, diimide (N2H2) was observed as an intermediate and traces of ammonia were present in the final product mixture. The Al/Al2O3 catalyzed oxidation of monomethylhydrazine yielded methyldiazine (HN = NCH3) as an intermediate and traces of methanol. Unsymmetrical dimethylhydrazine gave no detectable products. The relative reactivities of hydrazine, MMH and UDMH were 130 : 7.3 : 1.0, respectively. The rate constants for Al/Al2O3-catalyzed oxidation of hydrazine and MMH were proportional to the square of the surface area of the plates. Mechanisms for the surface-catalyzed oxidation of hydrazine and diimide and the formation of ammonia are proposed.

Thermal Mechanical Stability of Single-Crystal-Oxide Refractive Concentrators Evaluated for High-Temperature Solar-Thermal Propulsion

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Jacobson, Nathan S.; Miller, Robert A.

1999-01-01

Recently, refractive secondary solar concentrator systems were developed for solar thermal power and propulsion (ref. 1). Single-crystal oxides-such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium aluminum garnet (Y3Al5O12, or YAG), magnesium oxide (MgO), and sapphire (Al2O3)-are candidate refractive secondary concentrator materials. However, the refractive concentrator system will experience high-temperature thermal cycling in the solar thermal engine during the sun/shade transition of a space mission. The thermal mechanical reliability of these components in severe thermal environments is of great concern. Simulated mission tests are important for evaluating these candidate oxide materials under a variety of transient and steady-state heat flux conditions. In this research at the NASA Lewis Research Center, a controlled heat flux test approach was developed for investigating the thermal mechanical stability of the candidate oxide. This approach used a 3.0-kW continuous-wave (wavelength, 10.6 mm) carbon dioxide (CO2) laser (ref. 2). The CO2 laser is especially well-suited for single-crystal thermal shock tests because it can directly deliver well-characterized heat energy to the oxide surfaces. Since the oxides are opaque at the 10.6-mm wavelength of the laser beam, the light energy is absorbed at the surfaces rather than transmitting into the crystals, and thus generates the required temperature gradients within the specimens. The following figure is a schematic diagram of the test rig.

Accelerated effects of nano-ZnO on phosphorus removal by Chlorella vulgaris: Formation of zinc phosphate crystallites.

PubMed

Xiao, Huaixian; Liu, Na; Tian, Ke; Liu, Shixiang; Ge, Fei

2018-09-01

Nanoparticles have been reported to induce toxicity to aquatic organisms, however, their potential impacts on phosphorus removal from wastewater by algae are unclear. In this study, the effects of nanoparticle ZnO (nano-ZnO) on phosphate (PO 4 3- ) removal by a green alga Chlorella vulgaris were investigated. We found that PO 4 3- removal efficiency was accelerated with high concentrations of nano-ZnO (0.04-0.15mM) but reduced with low concentrations of nano-ZnO (0.005-0.04mM) compared to the control (without nano-ZnO), suggesting that PO 4 3- removal efficiency by C. vulgaris was related to nano-ZnO concentrations. Moreover, we observed changes of nano-ZnO morphology and detected element P on the surface of nano-ZnO by using transmission electronic microscopy (TEM) combined with energy dispersive X-ray spectroscopy (EDX), indicating that PO 4 3- was interacted with nano-ZnO or the dissolved Zn 2+ from nano-ZnO. Furthermore, we confirmed this interaction induced the formation of Zn 3 (PO 4 ) 2 crystallites sedimentation by employing X-ray diffraction analysis (XRD) and X-ray photoelectron spectroscopy (XPS), which finally accelerates the removal of PO 4 3- . Copyright © 2018 Elsevier B.V. All rights reserved.

Concentration of iodine-129 in surface seawater at subarctic and subtropical circulations in the Japan Sea

NASA Astrophysics Data System (ADS)

Suzuki, Takashi; Otosaka, Shigeyoshi; Togawa, Orihiko

2013-01-01

To investigate the migration of anthropogenic 129I in the environment, we measured 129I concentrations at both subarctic (above 40oN) and subtropical (below 40oN) circulations in the surface seawater of the Japan Sea. The averaged concentrations of stations 193, 194, 201, 206 and 210 above 200 m were (2.1 ± 0.3) × 1010 atoms/m3, (2.0 ± 0.2) × 1010 atoms/m3, (1.6 ± 0.3) × 1010 atoms/m3, (1.4 ± 0.3) × 1010 atoms/m3 and (1.7 ± 0.3) × 1010 atoms/m3, respectively. The averaged concentration at the subarctic circulation in the Japan Sea above 200 m (1.9 × 1010 atoms/m3) was higher than that in the subtropical circulation (1.5 × 1010 atoms/m3). This latitudinal distribution pattern of 129I is not consistent with those of bomb-derived radionuclides such as 14C, 90Sr and 137Cs. Taking into account latitudinal location and the total amount of releases from reprocessing plants, this discriminating latitudinal distribution of 129I in the Japan Sea would indicate that a significant amount of 129I originating from active reprocessing plants in Europe is supplied to the surface of the Japan Sea.

Soot Oxidation in Laminar Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure. Appendix D

NASA Technical Reports Server (NTRS)

Xu, F.; El-Leathy, A. M.; Faeth, G. M.

2000-01-01

Soot oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round jets burning in coflowing air considering acetylene, ethylene, proplyene and propane as fuels. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation mainly occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of stable major gas species (N2, H2O, H2, 02, CO, CO2, CH4, C2H2, C2H4, C2H6, C3H6, and C3H8) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by the deconvoluted Li/LiOH atomic absorption technique and flow velocities by laser velocimetry. It was found that soot surface oxidation rates are not particularly affected by fuel type for laminar diffusion flames and are described reasonably well by the OH surface oxidation mechanism with a collision efficiency of 0.10, (standard deviation of 0.07) with no significant effect of fuel type in this behavior; these findings are in good agreement with the classical laminar premixed flame measurements of Neoh et al. Finally, direct rates of surface oxidation by O2 were small compared to OH oxidation for present conditions, based on estimated O2 oxidation rates due to Nagle and Strickland-Constable, because soot oxidation was completed near the flame sheet where O2 concentrations were less than 1.2% by volume.

Prebiotic Polymerization: Oxidative Polymerization of 2,3 Dimercapto-1- Propanol on the Surface of Iron(III) Hydroxide Oxide

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1995-01-01

The oxidation of 2,3-dimercapto-1-propanol by ferric ions on the surface of iron(III) hydroxide oxide (Fe(OH)O) yielded polydisulfide oligomers. This polymerization occurred readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron(III) hydroxide oxide (20 mg, 160 micromole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the FE(OH)O phase. Reactions carried out at the same ratio of dithiol to FE(OH)O but at higher dithiol concentrations gave higher yields of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis is discussed.

Prebiotic polymerization: Oxidative polymerization of 2, 3-dimercapto-1-propanol on the surface of iron(III) hydroxide oxide

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1995-01-01

The oxidation of 2, 3-dimercapto-1-propanol by ferric ions on the surface of iron(III) hydroxide oxide (Fe(OH)O) yielded polydisulfide oligomers. This polymerization occurred readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron(III) hydroxide oxide (20 mg, 160 micromole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the Fe(OH)O phase. Reactions carried out at the same ratio of dithiol to Fe(OH)O but at higher dithiol concentrations gave higher yields of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis is discussed.

Impacts of different plant functional types on ambient ozone predictions in the Seoul Metropolitan Areas (SMA), Korea

NASA Astrophysics Data System (ADS)

Kim, H.-K.; Woo, J.-H.; Park, R. S.; Song, C. H.; Kim, J.-H.; Ban, S.-J.; Park, J.-H.

2013-09-01

Plant functional type (PFT) distributions affect the results of biogenic emission modeling as well as O3 and PM simulations using chemistry-transport models (CTMs). This paper analyzes the variations of both surface biogenic VOC emissions and O3 concentrations due to changes in the PFT distributions in the Seoul Metropolitan Areas, Korea. Also, this paper attempts to provide important implications for biogenic emissions modeling studies for CTM simulations. MM5-MEGAN-SMOKE-CMAQ model simulations were implemented over the Seoul Metropolitan Areas in Korea to predict surface O3 concentrations for the period of 1 May to 31 June 2008. Starting from MEGAN biogenic emissions analysis with three different sources of PFT input data, US EPA CMAQ O3 simulation results were evaluated by surface O3 monitoring datasets and further considered on the basis of geospatial and statistical analyses. The three PFT datasets considered were "(1)KORPFT", developed with a region specific vegetation database; (2) CDP, adopted from US NCAR; and (3) MODIS, reclassified from the NASA Terra and Aqua combined land cover products. Comparisons of MEGAN biogenic emission results with the three different PFT data showed that broadleaf trees (BT) are the most significant contributor, followed by needleleaf trees (NT), shrub (SB), and herbaceous plants (HB) to the total biogenic volatile organic compounds (BVOCs). In addition, isoprene from BT and terpene from NT were recognized as significant primary and secondary BVOC species in terms of BVOC emissions distributions and O3-forming potentials in the study domain. Multiple regression analyses with the different PFT data (δO3 vs. δPFTs) suggest that KORPFT can provide reasonable information to the framework of MEGAN biogenic emissions modeling and CTM O3 predictions. Analyses of the CMAQ performance statistics suggest that deviations of BT areas can significantly affect CMAQ isoprene and O3 predictions. From further evaluations of the isoprene and O3 prediction results, we explored the PFT area-loss artifact that occurs due to geographical disparity between the PFT and leaf area index distributions, and can cause increased bias in CMAQ O3. Thus, the PFT-loss artifact must be a source of limitation in the MEGAN biogenic emission modeling and the CTM O3 simulation results. Time changes of CMAQ O3 distributions with the different PFT scenarios suggest that hourly and local impacts from the different PFT distributions on occasional inter-deviations of O3 are quite noticeable, reaching up to 10 ppb. Exponentially diverging hourly BVOC emissions and O3 concentrations with increasing ambient temperature suggest that the use of representative PFT distributions becomes more critical for O3 air quality modeling (or forecasting) in support of air quality decision-making and human health studies.

Magnetic and plasmonic properties in noncompensated Fe-Sn codoped In2O3 nanodot arrays

NASA Astrophysics Data System (ADS)

Wang, Ya-Nan; Jiang, Feng-Xian; Yan, Li-Juan; Xu, Xiao-Hong

2018-05-01

The noncompensated Fe-Sn codoped In2O3 nanodot arrays with the Sn concentration of 0.02, 0.05, 0.1, 0.15 and 0.2 were deposited on Al2O3 (0 0 0 1) substrates using laser molecular beam epitaxy with the aid of anodic aluminium oxide templates. The structural and compositional results reveal that the nanodot arrays show the single phase cubic In2O3 structure and Sn and Fe dopant ions substitute In3+ sites of the In2O3 lattice with a tetravalence (Sn4+) and a mixed-valence (Fe2+/Fe3+), respectively. All the nanodot arrays exhibit the obvious room temperature ferromagnetic behavior and the localized surface plasmon resonance (LSPR) band. Moreover, the ferromagnetism and the LSPR absorption peak can be tuned by the Sn concentration or sizes of nanodot arrays.

Mutual effects of copper and phosphate on their interaction with γ-Al2O3: combined batch macroscopic experiments with DFT calculations.

PubMed

Ren, Xuemei; Yang, Shitong; Tan, Xiaoli; Chen, Changlun; Sheng, Guodong; Wang, Xiangke

2012-10-30

The mutual effects of Cu(II) and phosphate on their interaction with γ-Al(2)O(3) are investigated by using batch experiments combined with density functional theory (DFT) calculations. The results of batch experiments show that coexisting phosphate promotes the retention of Cu(II) on γ-Al(2)O(3), whereas phosphate retention is not affected by coexisting Cu(II) at low initial phosphate concentrations (≤ 3.6 mg P/L). Cu-phosphate aqueous complexes control Cu(II) retention through the formation of type B ternary surface complexes (where phosphate bridges γ-Al(2)O(3) and Cu(II)) at pH 5.5. This deduction is further supported by the results of DFT calculations. More specifically, the DFT calculation results indicate that the type B ternary surface complexes prefer to form outer-sphere or monodentate inner-sphere binding mode under our experimental conditions. The enhancement of phosphate retention on γ-Al(2)O(3) in the presence of Cu(II) at high initial phosphate concentrations (>3.6 mg P/L) may be attributed to the formation of 1:2 Cu(II)-phosphate species and/or surface precipitates. Understanding the mutual effects of phosphate and Cu(II) on their mobility and transport in mineral/water environments is more realistic to design effective remediation strategies for reducing their negative impacts on aquatic/terrestrial environments. Copyright © 2012 Elsevier B.V. All rights reserved.

Fabrication of silicon-on-diamond substrate with an ultrathin SiO2 bonding layer

NASA Astrophysics Data System (ADS)

Nagata, Masahiro; Shirahama, Ryouya; Duangchan, Sethavut; Baba, Akiyoshi

2018-06-01

We proposed and demonstrated a sputter etching method to prepare both a flat surface (root-mean-square surface roughness of approximately 0.2–0.3 nm) and an ultrathin SiO2 bonding layer at an accuracy of approximately 5 nm in thickness to fabricate a silicon-on-diamond substrate (SOD). We also investigated a plasma activation method on a SiO2 surface using various gases. We found that O2 plasma activation is more suitable for the bonding between SiO2 and Si than N2 or Ar plasma activation. We speculate that the concentration of hydroxyl groups on the SiO2 surface was increased by O2 plasma activation. We fabricated the SOD substrate with an ultrathin (15 nm in thickness) SiO2 bonding layer using the sputter etching and O2 plasma activation methods.

Leaf size and surface characteristics of Betula papyrifera exposed to elevated CO2 and O3.

PubMed

Riikonen, Johanna; Percy, Kevin E; Kivimäenpää, Minna; Kubiske, Mark E; Nelson, Neil D; Vapaavuori, Elina; Karnosky, David F

2010-04-01

Betula papyrifera trees were exposed to elevated concentrations of CO(2) (1.4 x ambient), O(3) (1.2 x ambient) or CO(2) + O(3) at the Aspen Free-air CO(2) Enrichment Experiment. The treatment effects on leaf surface characteristics were studied after nine years of tree exposure. CO(2) and O(3) increased epidermal cell size and reduced epidermal cell density but leaf size was not altered. Stomatal density remained unaffected, but stomatal index increased under elevated CO(2). Cuticular ridges and epicuticular wax crystallites were less evident under CO(2) and CO(2) + O(3). The increase in amorphous deposits, particularly under CO(2) + O(3,) was associated with the appearance of elongated plate crystallites in stomatal chambers. Increased proportions of alkyl esters resulted from increased esterification of fatty acids and alcohols under elevated CO(2) + O(3). The combination of elevated CO(2) and O(3) resulted in different responses than expected under exposure to CO(2) or O(3) alone. 2009 Elsevier Ltd. All rights reserved.

Mesoporous silica (MCM-41)-Fe2O3 as a novel magnetic nanosensor for determination of trace amounts of amino acids.

PubMed

Hasanzadeh, Mohammad; Shadjou, Nasrin; Omidinia, Eskandar

2013-08-01

Magnetic (Fe2O3) mobile crystalline material-41 (MCM-41) was prepared and characterized using transmission electron microscopy (TEM) and nitrogen adsorption-desorption techniques. Due to the large surface area (1213 m(2)g(-1)) and remarkable electrocatalytic properties of MCM-41-Fe2O3, the MCM-41-Fe2O3 modified glassy carbon electrode (MCM-41-Fe2O3/GCE) exhibits potent electrocatalytic activity toward the electro-oxidation of amino acids. MCM-41-Fe2O3/GCE brings new capabilities for electrochemical sensing by combining the advantages of Fe2O3 magnetic nanoparticles and MCM-41 with very large surface area. Cyclic voltammetry, hydrodynamic amperometry and flow injection analysis used to determination of amino acids at higher concentration range. Fast response time, excellent catalytic activity, and ease of preparation are the advantages of the proposed amino acid sensor. Copyright © 2013 Elsevier B.V. All rights reserved.

The response of Phanerozoic surface temperature to variations in atmospheric oxygen concentration

NASA Astrophysics Data System (ADS)

Payne, Rebecca C.; Britt, Amber V.; Chen, Howard; Kasting, James F.; Catling, David C.

2016-09-01

Recently, Poulsen et al. (2015) suggested that O2 has played a major role in climate forcing during the Phanerozoic. Specifically, they argued that decreased O2 levels during the Cenomanian stage of the middle Cretaceous (94-100 Ma) could help explain the extremely warm climate during that time. The postulated warming mechanism involves decreased Rayleigh scattering by a thinner atmosphere, which reduces the planetary albedo and allows greater surface warming. This warming effect is then amplified by cloud feedbacks within their 3-D climate model. This increase in shortwave surface forcing, in their calculations, exceeds any decrease in the greenhouse effect caused by decreased O2. Here we use a 1-D radiative-convective climate model (with no cloud feedback) to check their results. We also include a self-consistent calculation of the change in atmospheric ozone and its effect on climate. Our results are opposite to those of Poulsen et al.: we find that the climate warms by 1.4 K at 35% O2 concentrations as a result of increased pressure broadening of CO2 and H2O absorption lines and cools by 0.8 K at 10% O2 as a result of decreased pressure broadening. The surface temperature changes are only about 1 K either way, though, for reasonable variations in Phanerozoic O2 concentrations (10%-35% by volume). Hence, it seems unlikely that changes in atmospheric O2 account for the warm climate of the Cenomanian. Other factors, such as a higher-than-expected sensitivity of climate to increased CO2 concentrations, may be required to obtain agreement with the paleoclimate data.

Dry deposition of O3 and SO2 estimated from gradient measurements above a temperate mixed forest.

PubMed

Wu, Zhiyong; Staebler, Ralf; Vet, Robert; Zhang, Leiming

2016-03-01

Vertical profiles of O3 and SO2 concentrations were monitored at the Borden Forest site in southern Ontario, Canada from May 2008 to April 2013. A modified gradient method (MGM) was applied to estimate O3 and SO2 dry deposition fluxes using concentration gradients between a level above and a level below the canopy top. The calculated five-year mean (median) dry deposition velocity (Vd) were 0.35 (0.27) and 0.59 (0.54) cm s(-1), respectively, for O3 and SO2. Vd(O3) exhibited large seasonal variations with the highest monthly mean of 0.68 cm s(-1) in August and the lowest of 0.09 cm s(-1) in February. In contrast, seasonal variations of Vd(SO2) were smaller with monthly means ranging from 0.48 (May) to 0.81 cm s(-1) (December). The different seasonal variations between O3 and SO2 were caused by the enhanced SO2 uptake by snow surfaces in winter. Diurnal variations showed a peak value of Vd in early morning in summer months for both O3 and SO2. Canopy wetness increased the non-stomatal uptake of O3 while decreasing the stomatal uptake. This also applied to SO2, but additional factors such as surface acidity also played an important role on the overall uptake. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Tropospheric ozone pollution in India: effects on crop yield and product quality.

PubMed

Singh, Aditya Abha; Agrawal, S B

2017-02-01

Ozone (O 3 ) in troposphere is the most critical secondary air pollutant, and being phytotoxic causes substantial losses to agricultural productivity. Its increasing concentration in India particularly in Indo-Gangetic plains is an issue of major concern as it is posing a threat to agriculture. In view of the issue of rising surface level of O 3 in India, the aim of this compilation is to present the past and the prevailing concentrations of O 3 and its important precursor (oxides of nitrogen) over the Indian region. The resulting magnitude of reductions in crop productivity as well as alteration in the quality of the product attributable to tropospheric O 3 has also been taken up. Studies in relation to yield measurements have been conducted predominantly in open top chambers (OTCs) and also assessed by using antiozonant ethylene diurea (EDU). There is a substantial spatial difference in O 3 distribution at different places displaying variable O 3 concentrations due to seasonal and geographical variations. This review further recognizes the major information lacuna and also highlights future perspectives to get the grips with rising trend of ground level O 3 pollution and also to formulate the policies to check the emissions of O 3 precursors in India.

Tunable upconversion luminescence of monodisperse Y2O3: Er3+/Yb3+/Tm3+ nanoparticles

NASA Astrophysics Data System (ADS)

Wu, Qibai; Lin, Shaoteng; Xie, Zhongxiang; Zhang, Liqing; Qian, Yannan; Wang, Yaodong; Zhang, Haiyan

2017-12-01

Monodisperse Y2O3: Er3+/Yb3+/Tm3+ nanoparticles with various dopant concentrations have been synthesized successfully by a homogeneous precipitation method. Their phase structures and surface morphologies have been characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The diversities of upconversion luminescence spectra and CIE coordinates of prepared samples are investigated in detail at room temperature under 980 nm excitation. Through adjusting the concentrations of Yb3+, Tm3+ and Er3+ ions, three upconversion emission bands in red, green and blue region could be tunable to achieve the color of interest and near white light emission can be obtained in the tri-doped Y2O3 nanoparticles for a variety of application.

Oxidation of Gas-Phase SO2 on the Surfaces of Acidic Microdroplets: Implications for Sulfate and Sulfate Radical Anion Formation in the Atmospheric Liquid Phase.

PubMed

Hung, Hui-Ming; Hoffmann, Michael R

2015-12-01

The oxidation of SO2(g) on the interfacial layers of microdroplet surfaces was investigated using a spray-chamber reactor coupled to an electrospray ionization mass spectrometer. Four major ions, HSO3(-), SO3(•-), SO4(•-) and HSO4(-), were observed as the SO2(g)/N2(g) gas-mixture was passed through a suspended microdroplet flow, where the residence time in the dynamic reaction zone was limited to a few hundred microseconds. The relatively high signal intensities of SO3(•-), SO4(•-), and HSO4(-) compared to those of HSO3(-) as observed at pH < 3 without addition of oxidants other than oxygen suggests an efficient oxidation pathway via sulfite and sulfate radical anions on droplets possibly via the direct interfacial electron transfer from HSO3(-) to O2. The concentrations of HSO3(-) in the aqueous aerosol as a function of pH were controlled by the deprotonation of hydrated sulfur dioxide, SO2·H2O, which is also affected by the pH dependent uptake coefficient. When H2O2(g) was introduced into the spray chamber simultaneously with SO2(g), HSO3(-) is rapidly oxidized to form bisulfate in the pH range of 3 to 5. Conversion to sulfate was less at pH < 3 due to relatively low HSO3(-) concentration caused by the fast interfacial reactions. The rapid oxidation of SO2(g) on the acidic microdroplets was estimated as 1.5 × 10(6) [S(IV)] (M s(-1)) at pH ≤ 3. In the presence of acidic aerosols, this oxidation rate is approximately 2 orders of magnitude higher than the rate of oxidation with H2O2(g) at a typical atmospheric H2O2(g) concentration of 1 ppb. This finding highlights the relative importance of the acidic surfaces for SO2 oxidation in the atmosphere. Surface chemical reactions on aquated aerosol surfaces, as observed in this study, are overlooked in most atmospheric chemistry models. These reaction pathways may contribute to the rapid production of sulfate aerosols that is often observed in regions impacted by acidic haze aerosol such as Beijing and other megacities around the world.

Assessing the effects of oil sands related ozone precursor emissions on ambient ozone levels in the Alberta oil sands region, Canada

NASA Astrophysics Data System (ADS)

Cho, Sunny; Vijayaraghavan, Krish; Spink, David; Cosic, Biljana; Davies, Mervyn; Jung, Jaegun

2017-11-01

A study was undertaken to determine whether, and the extent to which, increased ground-level ozone (O3) precursor emissions from oil sands development have impacted ambient air quality in the north-eastern Alberta, Canada, over the period 1998 to 2012. Temporal trends in emissions of O3 precursors (NOx and VOC) and ambient air concentrations of O3 precursors, and O3 were examined using the Theil-Sen statistical analysis method. Statistically significant correlations between NOx emissions and ambient NOx concentrations were found mainly near surface (open-pit) mining areas where mine fleets are a large source of NOx emissions. No statistically significant trends in the 4th highest daily maximum 8-hr average O3 at any of the continuous and passive ambient air monitoring stations were found. A significant long-term decrease in monthly averaged O3 is observed at some ambient monitoring sites in summer. A visual examination of long-term variations in annual NOx and VOC emissions and annual 4th highest daily maximum 8-hr O3 concentrations does not reveal any indication of a correlation between O3 concentrations and O3 precursor emissions or ambient levels in the study area. Despite a significant increase in oil sands NOx emissions (8%/yr), there is no statistically significant increase in long-term O3 concentrations at any of monitoring stations considered. This suggests that there is surplus NOx available in the environment which results in a titration of ambient O3 in the areas that have ambient monitoring. The limited ambient O3 monitoring data distant from NOx emission sources makes it impossible to assess the impact of these increased O3 precursor levels on O3 levels on a regional scale. As a precautionary measure, the increasing oil sands development O3 precursor emissions would require that priority be given to the management of these emissions to prevent possible future O3 ambient air quality issues.

Factors Controlling Summertime Surface Ozone In The Western U.S

NASA Astrophysics Data System (ADS)

Gao, Mei

In this dissertation we investigate different factors controlling summertime surface ozone (O3) in the western U.S., including the impacts from increased wildfire emissions, the modulation by North American summer monsoon as well as long-range transport of O3 and its precursors from outside of North America. We first analyze the surface ozone observations from the Clean Air Status and Trend Network (CASTNet) using a global chemical transport model (GEOS-Chem) to investigate the impact of biomass burning on surface O3 in the western U.S. (WUS) mountain ranges during the June--October fire season of 2007, one of the stronger fire years in the WUS in the past decade. GEOS-Chem O3 captures the observed seasonal, synoptic and daily variations. Model daily afternoon average surface O3 concentrations at the CASTNet sites are within 2 ppb of the observations, with correlation coefficients of 0.51--0.83 and Taylor scores of 0.64--0.92. Observed maximum daily 8-hour (MAD8) surface O3 concentrations are 37--8 ppb at the sites, while the corresponding model results are higher by 6 ppb on average. Model results show July--September maximum surface O3 enhancement of ~9 ppb on average because of biomass burning. Peaks in fire-contributed surface O3 correspond broadly with high levels of potassium (K), reaffirming a strong fire influence. We find a policy relevant background (PRB) O3 of 45.6 ppb on average during July--September. Fire-contributed O3 accounts for up to 30% of the PRB O3, highest in the intense fire region (Montana, Idaho, and Wyoming) with maxima in August and September. We also examine an unexpected summertime surface O3 minimum (~30--5 ppb) in July--August 2007 observed throughout the Southwestern U.S. (SWUS) by interpreting observations of O3 and rainfall from the Clean Air Status and Trends Network (CASTNet) with a global chemical transport model. The O3 minimum reflects competing chemical and dynamic factors as well as anthropogenic and natural influences. Its reoccurrence annually in 2000--11 corresponds to the seasonal rainfall maximum during the North American summer monsoon (NASM) (negative O3 and positive rainfall anomalies at the CASTNet sites, (r = -0.5 to -0.7, p < 0.05). Relative to June 15--July 15, 2007 (pre-onset of the NASM), increased cloudiness in July 15--August 15 (post-onset) weakens photochemistry, reduces O3 production from anthropogenic emissions, thereby depresses O3 throughout the lower troposphere and at the surface (-5 ppb at Chiricahua, AZ and -3 ppb on average across the SWUS). The resulting changes are largest at rainfall maxima, particularly in the core of the Great Plains low-level jet. Enhanced lightning NOx emissions post-onset augments O3 production in the middle troposphere followed by downward mixing in convective downdrafts, thereby increases O3 significantly throughout the tropospheric column and non-negligibly at the surface (+2 ppb at Chiricahua and +1 ppb averaged over the SWUS). The resulting DeltaO 3 changes is largest (+8 ppb) in the middle troposphere in the anti-cyclonic circulation associated with the reoccurring summertime high over the Southern U.S. Weaker photochemistry post-onset dominates the overall DeltaO 3 change near the surface, while enhanced lightning dominates in much of the free troposphere. Additionally, we find that transport leads to a net export of O3 throughout the tropospheric column and the influence from stratospheric intrusion is vanishingly small. These competing effects suppress O3 in the lower troposphere (DeltaO3 change up to -5 ppb) while enhance O3 at higher altitudes (DeltaO 3 change up to +7 ppb) across the SWUS during the monsoon. Better understanding of these effects is critical to estimate present and predict future background O3 in the U.S. Southwest as the NASM changes under a changing climate. Lastly we use the GEOS-Chem 3-D global tropospheric chemical transport model and its adjoint to quantify the source contributions to O3 pollution observed at Mt. Bachelor Observatory (MBO) during the summer of 2008. We found that MBO experienced distinct O3 pollution episodes from Siberia wildfire emissions. We also used the adjoint of GEOS-Chem to show the model O3 at MBO is largely sensitive to NOx emissions from biomass burning sources in Siberia and northern California, lightning sources over southwestern U.S. and Mexico, and anthropogenic sources in western U.S. and eastern Asia. For the CO emissions, the largest O 3 sensitivity is to the biomass burning sources in northern California and Siberia. The peak sensitivity to biomass burning CO emissions is comparable to the peak O3 sensitivity to anthropogenic NOx emissions. (Abstract shortened by UMI.).

Pulmonary risk of intraoral surface conditioning using crystalline silica.

PubMed

Mayer, Beate; Raithel, Hans; Weltle, Dieter; Niedermeier, Wilhelm

2003-01-01

This study evaluated the pulmonary risk caused by possible respirable dust of Al2O3 and SiO(x) resulting from chairside tribochemical sandblasting procedures in a dental office. Dust was collected using a trap near the working field, and quantitative morphologic determination and identification were performed with SEM and EDAX. Forty blasting processes (total time 20 minutes) were aimed at a dummy to obtain maximum pollution of the workplace. Respirable dust fraction was measured using personal air samplers with an 8-microm cellulose-nitrate filter and a volume flow rate of 2 L/min. Mass of the respirable dust fraction was determined, and respirable free crystalline silica was identified with the help of infrared spectroscopy. Blasting of metal or ceramic surfaces with tribochemical agents produces respirable and potentially harmful SiO(x) and Al2O3 particles with a diameter of less than 5 microm, showing a total concentration in the air of less than 0.3 mg/m3. With and without dental suction, the concentration of the respirable free crystalline silica was smaller than 0.02 mg/m3. Concern regarding the risk of chairside tribochemical methods and possible impairment of health of patients and dental staff is unfounded, even under extreme conditions or without protective measures, since the concentrations of SiO(x) found in the air of the workplace were far below the current threshold value of 0.15 mg/m3.

Effect of H2O2 and nonionic surfactant in alkaline copper slurry

NASA Astrophysics Data System (ADS)

Haobo, Yuan; Yuling, Liu; Mengting, Jiang; Guodong, Chen; Weijuan, Liu; Shengli, Wang

2015-01-01

For improving the polishing performance, in this article, the roles of a nonionic surfactant (Fatty alcohol polyoxyethylene ether) and H2O2 were investigated in the chemical mechanical planarization process, respectively. Firstly, the effects of the nonionic surfactant on the within-wafer non-uniformity (WIWNU) and the surface roughness were mainly analyzed. In addition, the passivation ability of the slurry, which had no addition of BTA, was also discussed from the viewpoint of the static etch rate, electrochemical curve and residual step height under different concentrations of H2O2. The experimental results distinctly revealed that the nonionic surfactant introduced in the slurry improved the WIWNU and surface roughness, and that a 2 vol% was considered as an appropriate concentration relatively. When the concentration of H2O2 surpasses 3 vol%, the slurry will possess a relatively preferable passivation ability, which can effectively decrease the step height and contribute to acquiring a flat and smooth surface. Hence, based on the result of these experiments, the influences of the nonionic surfactant and H2O2 are further understood, which means the properties of slurry can be improved.

Interacting effects of ozone and CO2 on growth and physiological processes in northern forest trees

Treesearch

J. G. Isebrands; D. F. Karnosky

1996-01-01

Globally, surface-level concentrations of both CO2 and ozone (O3) are increasing annually. Because many studies have shown beneficial effects of increasing CO2, predictions have been made that elevated levels of CO2 would compensate for growth decreases caused by O3...

Synthesis and photocatalytic activity of p–n junction CeO2/Co3O4 photocatalyst for the removal of various dyes from wastewater

NASA Astrophysics Data System (ADS)

Tang, Yuanzheng; Zhang, Meng; Wu, Zhengying; Chen, Zhigang; Liu, Chengbao; Lin, Yun; Chen, Feng

2018-04-01

CeO2, Co3O4, and Co3O4/CeO2 composites are successfully synthesized by a simple coprecipitation method. X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) results indicate that the CeO2, Co3O4, and Co3O4/CeO2 precursors sintered at 500 °C has good crystallization. The cerium nitrate introduced into cobalt nitrate precursor solution improved the surface morphology and photocatalytic activity of Co3O4 significantly. The photo-degradation of methylene blue (MB), xylenol orange (XO), methyl orange (MO), and methyl red (MR) catalyzed by prepared nanocomposites were studied under visible light irradiation. Photocatalytic experiment results indicate that the photocatalytic activity of Co3O4/CeO2 composites for degradation of various dyes highly depend on pH value. The optimum conditions for the photocatalytic experiments of Co3O4/CeO2 composites were determined to be as follows: dye concentration, 50 mg L‑1, and catalyst concentration, 50 mg L‑1. The excellent photocatalytic activity of the p–n junction Co3O4/CeO2 composites can be ascribed to the ·O2‑ radicals and h+.

The Impact of Iodide-Mediated Ozone Deposition and ...

EPA Pesticide Factsheets

The air quality of many large coastal areas in the United States is affected by the confluence of polluted urban and relatively clean marine airmasses, each with distinct atmospheric chemistry. In this context, the role of iodide-mediated ozone (O3) deposition over seawater and marine halogen chemistry accounted for in both the lateral boundary conditions and coastal waters surrounding the continental U.S. is examined using the Community Multiscale Air Quality (CMAQ) model. Several nested simulations are conducted in which these halogen processes are implemented separately in the continental U.S. and hemispheric CMAQ domains, the latter providing lateral boundary conditions for the former. Overall, it is the combination of these processes within both the continental U.S. domain and from lateral boundary conditions that lead to the largest reductions in modeled surface O3 concentrations. Predicted reductions in surface O3 concentrations occur mainly along the coast where CMAQ typically has large overpredictions. These results suggest that a realistic representation of halogen processes in marine regions can improve model prediction of O3 concentrations near the coast. The National Exposure Research Laboratory (NERL) Computational Exposure Division (CED) develops and evaluates data, decision-support tools, and models to be applied to media-specific or receptor-specific problem areas. CED uses modeling-based approaches to characterize exposures, evaluate fate and

Inactivation of feline calicivirus, a norovirus surrogate, by chlorine dioxide gas.

PubMed

Morino, Hirofumi; Fukuda, Toshiaki; Miura, Takanori; Lee, Cheolsung; Shibata, Takashi; Sanekata, Takeshi

2009-12-01

The efficacy of gaseous chlorine dioxide (ClO2) against feline calicivirus (FCV), a norovirus surrogate, in the dry and the wet states on a hard surface was evaluated. We demonstrated that low-concentration ClO2 gas (mean 0.08 ppm, 0.22 microg/I) could inactivate FCV in the wet state with 0.5% fetal bovine serum (FBS) within 6 h in 45 to 55% relative humidity (RH) (> 3 log10 reductions) and FCV in the dry state with 2% FBS (percentage of FBS in the viral suspension) within 10 h in 75 to 85% RH (> 3 log10 reductions) at 20 degrees C, respectively. Furthermore, a < 0.3 ppm concentration of ClO2 gas (mean 0.26 ppm, 0.73 microg/l) could inactivate (below the detection limit) FCV in the dry state with 5% FBS within 24 h in 75 to 85% RH at 20 degrees C. In contrast, in 45 to 55% RH at 20 degrees C, ClO2 gas had little effect even when the FCV in the dry state was exposed to high-concentration ClO2 (mean 8 ppm, 22.4 microg/l) for 24 h. These results suggest that humidity plays an important role in the inactivation by ClO2 gas of FCV in the dry state. According to the International Chemical Safety Card, threshold limit values for ClO2 gas are 0.1 ppm as an 8-h time-weighted average and 0.3 ppm as a 15 min short-term exposure limit. From these data, we propose that the treatment of wet areas of human activity such as kitchens, toilets, etc., with low-concentration ClO2 gas would be useful for reducing the risk of infection by noroviruses (NV) without adverse effects. In addition, we believe that the application of a combination of a < 0.3 ppm concentration of ClO2 gas and a humidifier in places without human activity may make it possible to inactivate NV in the dry state on any surface within a contaminated room without serious adverse effects.

Optimizing Low-Concentration Mercury Removal from Aqueous Solutions by Reduced Graphene Oxide-Supported Fe3O4 Composites with the Aid of an Artificial Neural Network and Genetic Algorithm

PubMed Central

Cao, Rensheng; Hu, Jiwei; Ruan, Wenqian; Xiong, Kangning; Wei, Xionghui

2017-01-01

Reduced graphene oxide-supported Fe3O4 (Fe3O4/rGO) composites were applied in this study to remove low-concentration mercury from aqueous solutions with the aid of an artificial neural network (ANN) modeling and genetic algorithm (GA) optimization. The Fe3O4/rGO composites were prepared by the solvothermal method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy (AFM), N2-sorption, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and superconduction quantum interference device (SQUID). Response surface methodology (RSM) and ANN were employed to model the effects of different operating conditions (temperature, initial pH, initial Hg ion concentration and contact time) on the removal of the low-concentration mercury from aqueous solutions by the Fe3O4/rGO composites. The ANN-GA model results (with a prediction error below 5%) show better agreement with the experimental data than the RSM model results (with a prediction error below 10%). The removal process of the low-concentration mercury obeyed the Freudlich isotherm and the pseudo-second-order kinetic model. In addition, a regeneration experiment of the Fe3O4/rGO composites demonstrated that these composites can be reused for the removal of low-concentration mercury from aqueous solutions. PMID:29112141

Defect-mediated magnetism of transition metal doped zinc oxide thin films

NASA Astrophysics Data System (ADS)

Roberts, Bradley Kirk

Magnetism in transition metal doped wide band-gap materials is of interest to further the fundamental science of materials and future spintronics applications. Large inter-dopant separations require mediation of ferromagnetism by some method; carrier-mediated mechanisms are typically applicable to dilute magnetic semiconductors with low Curie temperatures. Dilute magnetic oxides, commonly with poor conductivity and TC above room temperature, cannot be described within this theory. Recent experiment and theory developments suggest that ferromagnetic exchange in these materials can be mediated by defects. This research includes experimental results justifying and developing this approach. Thin films of Cr doped ZnO (band gap ˜3.3 eV) were deposited with several processing variations to enhance the effects of either 0-dimensional (vacancy, hydrogen-related defect) or two-dimensional defects (surface/interface) and thereby affect magnetism and conductivity. We observe surface magnetism in dielectric thin films of oxygen-saturated ZnO:Cr with spontaneous magnetic moment and conductance dropping approximately exponentially with increasing thickness. Uniform defect concentrations would not result in such magnetic ordering behavior indicating that magnetism is mediated either by surface defects or differing concentrations of point defects near the surface. Polarized neutron reflectivity profiling confirms a magnetically active region of ˜8 nm at the film surface. Hydrogen is notoriously present as a defect and carrier dopant in ZnO, and artificial introduction of hydrogen in dielectric ZnO:Cr films results in varying electronic and magnetic behavior. Free carriers introduced with hydrogen doping are not spin-polarized requiring an alternative explanation for ferromagnetism. We find from positron annihilation spectroscopy measurements that hydrogen doping increases the concentration of an altered VZn-related defect (a preliminary interpretation) throughout the film, which is may be magnetically active as mediator. Measurements suggest that this defect contribution is strongest (or concentration higher) near the surface too. This study concerns the wide-gap oxide ZnO when doped with the transition metal Cr, below the percolation threshold, and subject to defects that mediate ferromagnetism independent of polarized free carriers. Ultimately, by adjusting the volumetric concentration of certain defects, ferromagnetic ordering in ZnO:Cr can be controlled. The potential applicability of novel theories of defect-mediated magnetism to this system is discussed.

Optimization of preparation of NDV F Gene encapsulated in N-2-HACC-CMC nanoparticles

NASA Astrophysics Data System (ADS)

Li, S. S.; Zhang, Y.; Zhao, K.; Wang, X. H.

2018-01-01

In this study, the biodegradable materials N-2-hydroxypropyl trimethyl ammonium chloride chitosan (N-2-HACC) and N, O-carboxymethyl chitosan (CMC) are used as delivery carrier for the pVAX I -F(o)-C3d6. The optimal preparation condition is as follows: concentration of N-2-HACC is 1.0 mg/ml, concentration of CMC is 0.85 mg/ml, concentration of pVAX I -F(o)-C3d6 is 100 μg ml. The results show that the prepared N-2-HACC-CMC/pFDNA NPs have regular round shape, smooth surface and good dispersion, the particle size is 310 nm, Zeta potential is 50 mV, the entrapment efficiency is 92 %, the loading capacity is 51 % (n=3).

Surface interactions affect the toxicity of engineered metal oxide nanoparticles toward Paramecium.

PubMed

Li, Kungang; Chen, Ying; Zhang, Wen; Pu, Zhichao; Jiang, Lin; Chen, Yongsheng

2012-08-20

To better understand the potential impacts of engineered metal oxide nanoparticles (NPs) in the ecosystem, we investigated the acute toxicity of seven different types of engineered metal oxide NPs against Paramecium multimicronucleatum, a ciliated protozoan, using the 48 h LC(50) (lethal concentration, 50%) test. Our results showed that the 48 h LC(50) values of these NPs to Paramecium ranged from 0.81 (Fe(2)O(3) NPs) to 9269 mg/L (Al(2)O(3) NPs); their toxicity to Paramecium increased as follows: Al(2)O(3) < TiO(2) < CeO(2) < ZnO < SiO(2) < CuO < Fe(2)O(3) NPs. On the basis of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, interfacial interactions between NPs and cell membrane were evaluated, and the magnitude of interaction energy barrier correlated well with the 48 h LC(50) data of NPs to Paramecium; this implies that metal oxide NPs with strong association with the cell surface might induce more severe cytotoxicity in unicellular organisms.

A novel approach to enhancement of surface properties of CdO films by using surfactant: dextrin

NASA Astrophysics Data System (ADS)

Sahin, Bünyamin; Bayansal, Fatih; Yüksel, Mustafa

2015-12-01

We studied the effect of an organic surfactant, dextrin, concentration on structural, morphological and optical properties of nanostructured CdO films deposited on glass substrates by using an easy and low-cost SILAR method. Microstructures of the nanostructured CdO films were optimized by adjusting dextrin concentration. XRD, SEM and UV-Vis Spectroscopy were used to study phase structure, surface morphology and optical properties of CdO films. Furthermore, effects of dextrin concentration on the surface roughness characteristics of CdO samples were reported. The results showed that the presence of organic surfactant highly affected the physical properties of CdO nanomaterials.

Climate change impacts on human health over Europe through its effect on air quality.

PubMed

Doherty, Ruth M; Heal, Mathew R; O'Connor, Fiona M

2017-12-05

This review examines the current literature on the effects of future emissions and climate change on particulate matter (PM) and O 3 air quality and on the consequent health impacts, with a focus on Europe. There is considerable literature on the effects of climate change on O 3 but fewer studies on the effects of climate change on PM concentrations. Under the latest Intergovernmental Panel on Climate Change (IPCC) 5th assessment report (AR5) Representative Concentration Pathways (RCPs), background O 3 entering Europe is expected to decrease under most scenarios due to higher water vapour concentrations in a warmer climate. However, under the extreme pathway RCP8.5 higher (more than double) methane (CH 4 ) abundances lead to increases in background O 3 that offset the O 3 decrease due to climate change especially for the 2100 period. Regionally, in polluted areas with high levels of nitrogen oxides (NO x ), elevated surface temperatures and humidities yield increases in surface O 3 - termed the O 3 climate penalty - especially in southern Europe. The O 3 response is larger for metrics that represent the higher end of the O 3 distribution, such as daily maximum O 3 . Future changes in PM concentrations due to climate change are much less certain, although several recent studies also suggest a PM climate penalty due to high temperatures and humidity and reduced precipitation in northern mid-latitude land regions in 2100.A larger number of studies have examined both future climate and emissions changes under the RCP scenarios. Under these pathways the impact of emission changes on air quality out to the 2050s will be larger than that due to climate change, because of large reductions in emissions of O 3 and PM pollutant precursor emissions and the more limited climate change response itself. Climate change will also affect climate extreme events such as heatwaves. Air pollution episodes are associated with stagnation events and sometimes heat waves. Air quality during the 2003 heatwave over Europe has been examined in numerous studies and mechanisms for enhancing O 3 have been identified.There are few studies on health effects associated with climate change impacts alone on air quality, but these report higher O 3 -related health burdens in polluted populated regions and greater PM 2.5 health burdens in these emission regions. Studies that examine the combined impacts of climate change and anthropogenic emissions change under the RCP scenarios report reductions in global and European premature O 3 -respiratory related and PM mortalities arising from the large decreases in precursor emissions. Under RCP 8.5 the large increase in CH 4 leads to global and European excess O 3 -respiratory related mortalities in 2100. For future health effects, besides uncertainty in future O 3 and particularly PM concentrations, there is also uncertainty in risk estimates such as effect modification by temperature on pollutant-response relationships and potential future adaptation that would alter exposure risk.

Simulation and experiment on the catalytic degradation of high-concentration SF6 on TiO2 surface under UV light

NASA Astrophysics Data System (ADS)

Zhang, Ying; Li, Yalong; Cui, Zhaolun; Chen, Dachang; Zhang, Xiaoxing

2018-05-01

The high-temperature effect gas SF6 is used in the power industry, and its emissions are increasing daily. Therefore, the degradation of SF6 is particularly important. In this work, SF6 with a high concentration of 2% was degraded using the catalytic principle of TiO2 under UV light at normal temperature and pressure. Experimental results proved that this method can effectively degrade SF6. Moreover, the addition of TiO2 can effectively increase the degradation rate of SF6. The degradation of eight pieces of TiO2 with a unit area of 3 cm2 was 8.98% after 3 h of catalysis. FTIR spectral analysis showed that the main degradation products were SO2F2, SiF4, SF4, and SO2. Adding H2O can further increase the degradation rate, which can reach 27.22% in 3 h. The main degradation products were SO2F2, SiF4, SF4, SiH4, HF, and SO2. Finally, simulations verified the catalytic decomposition of SF6 on the surface of TiO2.

Three-dimensional ordered macroporous bismuth vanadates: PMMA-templating fabrication and excellent visible light-driven photocatalytic performance for phenol degradation

NASA Astrophysics Data System (ADS)

Liu, Yuxi; Dai, Hongxing; Deng, Jiguang; Zhang, Lei; Au, Chak Tong

2012-03-01

Three-dimension ordered macroporous (3D-OM) bismuth vanadates with a monoclinic crystal structure and high surface area (18-24 m2 g-1) have been prepared using ascorbic acid (AA)- or citric acid (CA)-assisted poly(methyl methacrylate) (PMMA)-templating strategy with bismuth nitrate and ammonium metavanadate as the metal sources, HNO3 as the pH adjuster and ethylene glycol and methanol as the solvent. The materials were characterized by a number of analytical techniques. The photocatalytic performance of the porous BiVO4 samples was evaluated for the degradation of phenol in the presence of a small amount of H2O2 under visible light illumination. The effects of the initial phenol concentration and the H2O2 amount on the photocatalytic activity of the photocatalyst were examined. It is shown that the chelating agent, AA or CA, and the amount in which it is added had a significant impact on the quality of the 3D-OM structure, with a ``(Bi + V) : chelating agent'' molar ratio of 2 : 1 being the most appropriate. Among the as-prepared BiVO4 samples, the one with a surface area of ca. 24 m2 g-1 showed the best visible light-driven photocatalytic performance for phenol degradation (phenol conversion = ca. 94% at phenol concentration = 0.1 mmol L-1 and in the presence of 0.6 mL H2O2). A higher phenol conversion could be achieved within the same reaction time if the phenol concentration in the aqueous solution was lowered, but an excess amount of H2O2 was not a favorable factor for the enhancement of the catalytic activity. It is concluded that the excellent photocatalytic activity of 3D-OM BiVO4 is due to the high quality 3D-OM structured BiVO4 that has a high surface area and surface oxygen vacancy density. We are sure that the 3D-OM material is a promising photocatalyst for the removal of organics from wastewater under visible light illumination.Three-dimension ordered macroporous (3D-OM) bismuth vanadates with a monoclinic crystal structure and high surface area (18-24 m2 g-1) have been prepared using ascorbic acid (AA)- or citric acid (CA)-assisted poly(methyl methacrylate) (PMMA)-templating strategy with bismuth nitrate and ammonium metavanadate as the metal sources, HNO3 as the pH adjuster and ethylene glycol and methanol as the solvent. The materials were characterized by a number of analytical techniques. The photocatalytic performance of the porous BiVO4 samples was evaluated for the degradation of phenol in the presence of a small amount of H2O2 under visible light illumination. The effects of the initial phenol concentration and the H2O2 amount on the photocatalytic activity of the photocatalyst were examined. It is shown that the chelating agent, AA or CA, and the amount in which it is added had a significant impact on the quality of the 3D-OM structure, with a ``(Bi + V) : chelating agent'' molar ratio of 2 : 1 being the most appropriate. Among the as-prepared BiVO4 samples, the one with a surface area of ca. 24 m2 g-1 showed the best visible light-driven photocatalytic performance for phenol degradation (phenol conversion = ca. 94% at phenol concentration = 0.1 mmol L-1 and in the presence of 0.6 mL H2O2). A higher phenol conversion could be achieved within the same reaction time if the phenol concentration in the aqueous solution was lowered, but an excess amount of H2O2 was not a favorable factor for the enhancement of the catalytic activity. It is concluded that the excellent photocatalytic activity of 3D-OM BiVO4 is due to the high quality 3D-OM structured BiVO4 that has a high surface area and surface oxygen vacancy density. We are sure that the 3D-OM material is a promising photocatalyst for the removal of organics from wastewater under visible light illumination. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr12046a

2D SnO2 Nanosheets: Synthesis, Characterization, Structures, and Excellent Sensing Performance to Ethylene Glycol

PubMed Central

Wan, Wenjin; Li, Yuehua; Ren, Xingping; Zhao, Yinping; Gao, Fan; Zhao, Heyun

2018-01-01

Two dimensional (2D)SnO2 nanosheets were synthesized by a substrate-free hydrothermal route using sodium stannate and sodium hydroxide in a mixed solvent of absolute ethanol and deionized water at a lower temperature of 130 °C. The characterization results of the morphology, microstructure, and surface properties of the as-prepared products demonstrated that SnO2 nanosheets with a tetragonal rutile structure, were composed of oriented SnO2 nanoparticles with a diameter of 6–12 nm. The X-ray diffraction (XRD) and high-resolution transmission electron microscope (FETEM) results demonstrated that the dominant exposed surface of the SnO2 nanoparticles was (101), but not (110). The growth and formation was supposed to follow the oriented attachment mechanism. The SnO2 nanosheets exhibited an excellent sensing response toward ethylene glycol at a lower optimal operating voltage of 3.4 V. The response to 400 ppm ethylene glycol reaches 395 at 3.4 V. Even under the low concentration of 5, 10, and 20 ppm, the sensor exhibited a high response of 6.9, 7.8, and 12.0 to ethylene glycol, respectively. The response of the SnO2 nanosheets exhibited a linear dependence on the ethylene glycol concentration from 5 to 1000 ppm. The excellent sensing performance was attributed to the present SnO2 nanoparticles with small size close to the Debye length, the larger specific surface, the high-energy exposed facets of the (101) surface, and the synergistic effects of the SnO2 nanoparticles of the nanosheets. PMID:29462938

High surface O3 episodes in Seoul under different meteorological regimes during KORUS-AQ campaign.

NASA Astrophysics Data System (ADS)

Kim, H.; Lee, M.; Jung, J.; Cho, S.; Shin, H.; Lee, G.; Park, M.; Hong, J.

2017-12-01

To examine chemical characteristics of ozone (O3) formation in Seoul Metropolitan Area (SMA), H2O2, PAN, and HONO were measured in conjunction with O3 and its precursors. The experiment was conducted at Olympic Park in Seoul during May 12 June 15, 2016. For the entire experiment period, the high O3 episodes of hourly mean concentration over 100 ppbv occurred on May 20, 23, 25, 29, and 30 and June 10 and 14. These episodes were different in meteorological conditions, precursor strengths, and chemical characteristics. The local influence was dominant under stagnant condition on May 20, 23 and June 10. When stagnant conditions developed over the Korean peninsula, the PBL (Planetary Boundary Layer) height often changed rapidly, leading to abrupt change in O3 and NOx. Particularly the nighttime concentrations of reactive gases such as O3 and NOx were sensitive to the change in PBL height. It is thought to be driven by land-sea breeze circulation. During May 25 28 when air was coming from the Eastern China, O3 was enhanced with aerosols and high SO2 and CO but low NOx concentration. Odd-Oxygen (O3+NO2, OX) ratio indicates the different chemical regimes, particularly at night(8PM - 7AM). O3/OX ratio was close to zero when local influence was dominant due to O3-titration by NOx. In contrast, this ratio was high over 0.6 in Chinese outflow plumes.

Air pollution and associated human mortality: the role of air pollutant emissions, climate change and methane concentration increases from the preindustrial period to present

NASA Astrophysics Data System (ADS)

Fang, Y.; Naik, V.; Horowitz, L. W.; Mauzerall, D. L.

2013-02-01

Increases in surface ozone (O3) and fine particulate matter (≤2.5 μm aerodynamic diameter, PM2.5) are associated with excess premature human mortalities. We estimate changes in surface O3 and PM2.5 from pre-industrial (1860) to present (2000) and the global present-day (2000) premature human mortalities associated with these changes. We extend previous work to differentiate the contribution of changes in three factors: emissions of short-lived air pollutants, climate change, and increased methane (CH4) concentrations, to air pollution levels and associated premature mortalities. We use a coupled chemistry-climate model in conjunction with global population distributions in 2000 to estimate exposure attributable to concentration changes since 1860 from each factor. Attributable mortalities are estimated using health impact functions of long-term relative risk estimates for O3 and PM2.5 from the epidemiology literature. We find global mean surface PM2.5 and health-relevant O3 (defined as the maximum 6-month mean of 1-h daily maximum O3 in a year) have increased by 8 ± 0.16 μg m-3 and 30 ± 0.16 ppbv (results reported as annual average ±standard deviation of 10-yr model simulations), respectively, over this industrial period as a result of combined changes in emissions of air pollutants (EMIS), climate (CLIM) and CH4 concentrations (TCH4). EMIS, CLIM and TCH4 cause global population-weighted average PM2.5 (O35) to change by +7.5 ± 0.19 μg m-3 (+25 ± 0.30 ppbv), +0.4 ± 0.17 μg m-3 (+0.5 ± 0.28 ppbv), and 0.04 ± 0.24 μg m-3 (+4.3 ± 0.33 ppbv), respectively. Total global changes in PM2.5 are associated with 1.5 (95% confidence interval, CI, 1.2-1.8) million cardiopulmonary mortalities and 95 (95% CI, 44-144) thousand lung cancer mortalities annually and changes in O3 are associated with 375 (95% CI, 129-592) thousand respiratory mortalities annually. Most air pollution mortality is driven by changes in emissions of short-lived air pollutants and their precursors (95% and 85% of mortalities from PM2.5 and O3 respectively). However, changing climate and increasing CH4 concentrations also contribute to premature mortality associated with air pollution globally (by up to 5% and 15%, respectively). In some regions, the contribution of climate change and increased CH4 together are responsible for more than 20% of the respiratory mortality associated with O3 exposure. We find the interaction between climate change and atmospheric chemistry has influenced atmospheric composition and human mortality associated with industrial air pollution. Our study highlights the benefits to air quality and human health of CH4 mitigation as a component of future air pollution control policy.

Removal of BrO₃⁻ from drinking water samples using newly developed agricultural waste-based activated carbon and its determination by ultra-performance liquid chromatography-mass spectrometry.

PubMed

Naushad, Mu; Khan, Mohammad R; ALOthman, Zeid A; AlSohaimi, Ibrahim; Rodriguez-Reinoso, Francisco; Turki, Turki M; Ali, Rahmat

2015-10-01

Activated carbon was prepared from date pits via chemical activation with H3PO4. The effects of activating agent concentration and activation temperature on the yield and surface area were studied. The optimal activated carbon was prepared at 450 °C using 55 % H3PO4. The prepared activated carbon was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric-differential thermal analysis, and Brunauer, Emmett, and Teller (BET) surface area. The prepared date pit-based activated carbon (DAC) was used for the removal of bromate (BrO3 (-)). The concentration of BrO3 (-) was determined by ultra-performance liquid chromatography-mass tandem spectrometry (UPLC-MS/MS). The experimental equilibrium data for BrO3 (-) adsorption onto DAC was well fitted to the Langmuir isotherm model and showed maximum monolayer adsorption capacity of 25.64 mg g(-1). The adsorption kinetics of BrO3 (-) adsorption was very well represented by the pseudo-first-order equation. The analytical application of DAC for the analysis of real water samples was studied with very promising results.

Characterizing distributions of surface ozone and its impact on grain production in China, Japan and South Korea: 1990 and 2020

NASA Astrophysics Data System (ADS)

Wang, Xiaoping; Mauzerall, Denise L.

Using an integrated assessment approach, we evaluate the impact that surface O 3 in East Asia had on agricultural production in 1990 and is projected to have in 2020. We also examine the effect that emission controls and the enforcement of environmental standards could have in increasing grain production in China. We find that given projected increases in O 3 concentrations in the region, East Asian countries are presently on the cusp of substantial reductions in grain production. Our conservative estimates, based on 7- and 12-h mean (M7 or M12) exposure indices, show that due to O 3 concentrations in 1990 China, Japan and South Korea lost 1-9% of their yield of wheat, rice and corn and 23-27% of their yield of soybeans, with an associated value of 1990US 3.5, 1.2 and 0.24 billion, respectively. In 2020, assuming no change in agricultural production practices and again using M7 and M12 exposure indices, grain loss due to increased levels of O 3 pollution is projected to increase to 2-16% for wheat, rice and corn and 28-35% for soybeans; the associated economic costs are expected to increase by 82%, 33%, and 67% in 2020 over 1990 for China, Japan and South Korea, respectively. For most crops, the yield losses in 1990 based on SUM06 or W126 exposure indices are lower than yield losses estimated using M7 or M12 exposure indices in China and Japan but higher in South Korea; in 2020, the yield losses based on SUM06 or W126 exposure indices are substantially higher for all crops in all three countries. This is primarily due to the nature of the cumulative indices which weight elevated values of O 3 more heavily than lower values. Chinese compliance with its ambient O 3 standard in 1990 would have had a limited effect in reducing the grain yield loss caused by O 3 exposure, resulting in only US 0.2 billion of additional grain revenues, but in 2020 compliance could reduce the yield loss by one third and lead to an increase of US$ 2.6 (M7 or M12) -27 (SUM06) billion in grain revenues. We conclude that East Asian countries may have tremendous losses of crop yields in the near future due to projected increases in O 3 concentrations. They likely could achieve substantial increases in future agricultural production through reduction of surface O 3 concentrations and/or use of O 3 resistant crop cultivars.

The distribution of antibiotics in water of a river basin in South China

NASA Astrophysics Data System (ADS)

Meng, T.; Cheng, W.; Wang, M.; Wan, T.; Cheng, M.; Zhang, C. C.; Jia, Z. Y.

2017-08-01

In water environment field, one of the most attractive research topics is the determination of contamination characteristics of antibiotics in water. In order to investigate the distribution of antibiotics in surface water and drinking water of a certain river basin in southern China, we determined the types and concentrations of antibiotics that contaminated the river by performing HPLC-ESI-MS/MS method. Thus, we detected 17 antibiotics in four surface water samples (B1, B2, B3, and B4). In sampling points B3 and B4, we detected 16 antibiotics separately. The detection rates of norfloxacin, ofloxacin, and erythromycin-H2O were 100%, and the antibiotic erythromycin-H2O had the maximum concentration. In six drinking water samples (A1, A2, A3, A4, A5, and A6), we detected 13 antibiotics. In A5 water samples, we detected all the 13 antibiotics. The detection rate of ofloxacin and erythromycin-H2O was 100%, and erythromycin-H2O was the antibiotic with the highest concentration. We also found that from the upstream to the downstream of the river basin, the types of antibiotics in river increased gradually. In the upstream water samples (B1), we detected three antibiotics. Erythromycin-H2O was the antibiotic with the highest concentration of 6.61 ng/L, and sulfapyridine had the lowest concentration of 2.82 ng/L. In the downstream water samples (B4), we detected 16 antibiotics. Erythromycin-H2O was the antibiotic with the highest concentration of 277.58 ng/L, and the Sulfamonomethoxine was the antibiotic with the second-highest concentration of 242.1 ng/L. In addition, different membrane treatment processes could remove different amounts of antibiotics from the water samples. The study is an important reference for providing environmental protection to river water basin.

Observations and impacts of transported Canadian wildfire smoke on ozone and aerosol air quality in the Maryland region on June 9-12, 2015.

PubMed

Dreessen, Joel; Sullivan, John; Delgado, Ruben

2016-09-01

Canadian wildfire smoke impacted air quality across the northern Mid-Atlantic (MA) of the United States during June 9-12, 2015. A multiday exceedance of the new 2015 70-ppb National Ambient Air Quality Standard (NAAQS) for ozone (O3) followed, resulting in Maryland being incompliant with the Environmental Protection Agency's (EPA) revised 2015 O3 NAAQS. Surface in situ, balloon-borne, and remote sensing observations monitored the impact of the wildfire smoke at Maryland air quality monitoring sites. At peak smoke concentrations in Maryland, wildfire-attributable volatile organic compounds (VOCs) more than doubled, while non-NOx oxides of nitrogen (NOz) tripled, suggesting long range transport of NOx within the smoke plume. Peak daily average PM2.5 was 32.5 µg m(-3) with large fractions coming from black carbon (BC) and organic carbon (OC), with a synonymous increase in carbon monoxide (CO) concentrations. Measurements indicate that smoke tracers at the surface were spatially and temporally correlated with maximum 8-hr O3 concentrations in the MA, all which peaked on June 11. Despite initial smoke arrival late on June 9, 2015, O3 production was inhibited due to ultraviolet (UV) light attenuation, lower temperatures, and nonoptimal surface layer composition. Comparison of Community Multiscale Air Quality (CMAQ) model surface O3 forecasts to observations suggests 14 ppb additional O3 due to smoke influences in northern Maryland. Despite polluted conditions, observations of a nocturnal low-level jet (NLLJ) and Chesapeake Bay Breeze (BB) were associated with decreases in O3 in this case. While infrequent in the MA, wildfire smoke may be an increasing fractional contribution to high-O3 days, particularly in light of increased wildfire frequency in a changing climate, lower regional emissions, and tighter air quality standards. The presented event demonstrates how a single wildfire event associated with an ozone exceedance of the NAAQS can prevent the Baltimore region from complying with lower ozone standards. This relatively new problem in Maryland is due to regional reductions in NOx emissions that led to record low numbers of ozone NAAQS violations in the last 3 years. This case demonstrates the need for adequate means to quantify and justify ozone impacts from wildfires, which can only be done through the use of observationally based models. The data presented may also improve future air quality forecast models.

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

Zhang, Hailin; Li, Ping; Wang, Zheming

Boehmite (γ-AlOOH) was synthesized to selectively adsorb V(V) from K 2CrO 4-KVO 3-H 2O solutions with highly concentrated Cr(VI) and low concentration V(V). The synthesized γ-AlOOH has a BET surface area of 433.2 m 2/g and an average pore size of 3.5 nm. It possesses a maximum adsorption capacity of V(V) of 1.53 mmol/g from K 2CrO 4-KVO 3-H 2O solutions. The adsorption of V(V) onto γ-AlOOH follows the Langmuir isotherm model and pseudo-second-order kinetics equation by forming innersphere complexes while the Cr(VI) adsorption forms both inner-sphere and outer-sphere chromate complexes depending on solution pH. The γ-AlOOH was further synthesizedmore » in situ by adding HNO 3 into the K 2CrO 4-KAlO 2- KVO 3-H 2O solutions and then used for synchronous adsorption of V(V) and Cr(VI), resulting in increased adsorption capacity of V(V) of 2.88 mmol/g and decreased adsorption capacity of Cr(VI) to 0.073 mmol/g, respectively. In the latter process, adsorption pH values were adjustable, and adsorption reached equilibrium instantaneously, supporting a novel in situ synthesis and adsorption integration strategy with adjustable surface charge of adsorbent and disappearance of diffusion effect.« less

Interaction between isoprene and ozone fluxes in a poplar plantation and its impact on air quality at the European level

NASA Astrophysics Data System (ADS)

Zenone, Terenzio; Hendriks, Carlijn; Brilli, Federico; Fransen, Erik; Gioli, Beniamio; Portillo-Estrada, Miguel; Schaap, Martijn; Ceulemans, Reinhart

2016-09-01

The emission of isoprene and other biogenic volatile organic compounds from vegetation plays an important role in tropospheric ozone (O3) formation. The potentially large expansion of isoprene emitting species (e.g., poplars) for bioenergy production might, therefore, impact tropospheric O3 formation. Using the eddy covariance technique we have simultaneously measured fluxes isoprene, O3 and of CO2 from a poplar (Populus) plantation grown for bioenergy production. We used the chemistry transport model LOTOS-EUROS to scale-up the isoprene emissions associated with the existing poplar plantations in Europe, and we assessed the impact of isoprene fluxes on ground level O3 concentrations. Our findings suggest that isoprene emissions from existing poplar-for-bioenergy plantations do not significantly affect the ground level of O3 concentration. Indeed the overall land in Europe covered with poplar plantations has not significantly changed over the last two decades despite policy incentives to produce bioenergy crops. The current surface area of isoprene emitting poplars-for-bioenergy remains too limited to significantly enhance O3 concentrations and thus to be considered a potential threat for air quality and human health.

Interaction between isoprene and ozone fluxes in a poplar plantation and its impact on air quality at the European level.

PubMed

Zenone, Terenzio; Hendriks, Carlijn; Brilli, Federico; Fransen, Erik; Gioli, Beniamio; Portillo-Estrada, Miguel; Schaap, Martijn; Ceulemans, Reinhart

2016-09-12

The emission of isoprene and other biogenic volatile organic compounds from vegetation plays an important role in tropospheric ozone (O3) formation. The potentially large expansion of isoprene emitting species (e.g., poplars) for bioenergy production might, therefore, impact tropospheric O3 formation. Using the eddy covariance technique we have simultaneously measured fluxes isoprene, O3 and of CO2 from a poplar (Populus) plantation grown for bioenergy production. We used the chemistry transport model LOTOS-EUROS to scale-up the isoprene emissions associated with the existing poplar plantations in Europe, and we assessed the impact of isoprene fluxes on ground level O3 concentrations. Our findings suggest that isoprene emissions from existing poplar-for-bioenergy plantations do not significantly affect the ground level of O3 concentration. Indeed the overall land in Europe covered with poplar plantations has not significantly changed over the last two decades despite policy incentives to produce bioenergy crops. The current surface area of isoprene emitting poplars-for-bioenergy remains too limited to significantly enhance O3 concentrations and thus to be considered a potential threat for air quality and human health.

Wettability of MnxSiyOz by Liquid Zn-Al Alloys

NASA Astrophysics Data System (ADS)

Kim, Yunkyum; Shin, Minsoo; Tang, Chengying; Lee, Joonho

2010-08-01

The wettability of MnxSiyOz by liquid Zn-Al alloys was investigated to obtain basic information on the coating properties of high-strength steels with surface oxides in the hot-dip galvanizing process. In this study, the contact angles of liquid Zn-Al alloys (Al concentrations were 0.12 and 0.23 wt pct) on four different MnxSiyOz oxides, namely MnO, MnSiO3, Mn2SiO4, and SiO2, were measured with the dispensed drop method. The contact angle did not change across time. With an increasing Al concentration, the contact angle was slightly decreased for MnO and Mn2SiO4, but there was no change for MnSiO3 and SiO2. With an increasing SiO2 content, the contact angle gradually increased by 54 wt pct to form MnSiO3, and for pure SiO2 substrate, the contact angle decreased again. Consequently, the MnSiO3 substrate showed the worst wettability among the four tested oxide substrates.

H2O Paradox and its Implications on H2O in Moon

NASA Astrophysics Data System (ADS)

Zhang, Youxue

2017-04-01

The concentration of H2O in the mantle of a planetary body plays a significant role in the viscosity and partial melting and hence the convection and evolution of the planetary body. Even though the composition of the primitive terrestrial mantle (PTM) is thought to be well known [1-2], the concentration of H2O in PTM remains paradoxial because different methods of estimation give different results [3]: Using H2O/Ce ratio in MORB and OIB and Ce concentration in PTM, the H2O concentration in PTM would be (300÷×1.5) ppm; using mass balance by adding surface water to the mantle [3-4], H2O concentration in PTM would be (900÷×1.3) ppm [2-3]. The inconsistency based on these two seemingly reliable methods is referred to as the H2O paradox [3]. For Moon, H2O contents in the primitive lunar mantle (PLM) estimated from H2O in plagioclase in lunar anorthosite and that from H2O/Ce ratio in melt inclusions are roughly consistent at ˜110 ppm [5-6] even though there is still debate about the volatile depletion trend [7]. One possible solution to the H2O paradox in PTM is to assume that early Earth experienced whole mantle degassing, which lowered the H2O/Ce ratio in the whole mantle but without depleting Ce in the mantle. The second possible solution is that some deep Earth reservoirs with high H2O/Ce ratios have not been sampled by MORB and OIB. Candidates include the transition zone [8] and the D" layer. The third possible solution is that ocean water only partially originated from mantle degassing, but partially from extraterrestrial sources such as comets [9-10]. At present, there is not enough information to determine which scenario is the answer to the H2O paradox. On the other hand, each scenario would have its own implications to H2O in PLM. If the first scenario applies to Moon, because degassed H2O or H2 would have escaped from the lunar surface, the very early lunar mantle could have much higher H2O [11] than that obtained using the H2O/Ce ratio method. The second scenario is unlikely on Moon because there was unlikely plate tectonics, and because there is no similar H2O-rich transition zone or D" layer due to the much lower maximum pressure in Moon. In the third scenario, volatiles from an extralunar source would likely be lost from the high vacuum environment of the lunar surface, meaning that it would not impact on the H2O content estimation. [1] McDonough & Sun (1995) Chem. Geol. 120, 223. [2] Palme & O'Neill (2014) Treatise on Geochemistry 3, 1. [3] Zhang (2014) Treatise on Geochemistry 6, 37. [4] Zhang & Zindler (1989) JGR 94, 13719. [5] Hui et al. (2013) Nature Geosci. 6, 177. [6] Chen et al. (2015) EPSL 427, 37. [7] Albarede et al. (2015) MPS 50, 568. [8] Sobolev et al. (2016) Nature 531, 628. [9] Chyba (1987) Nature 330, 632. [10] Hartogh et al. (2011) Nature 478, 218. [11] Hui et al. (2016) Goldschmidt Conf. Abstr.

Ti4+ to Ti3+ conversion of TiO2 uppermost layer by low-temperature vacuum annealing: interest for titanium biomedical applications.

PubMed

Guillemot, F; Porté, M C; Labrugère, C; Baquey, Ch

2002-11-01

Because of the Ti(3+) defects responsibility for dissociative adsorption of water onto TiO(2) surfaces and due to the hydroxyls influence on the biological behavior of titanium, controlling the Ti(3+) surface defects density by means of low-temperature vacuum annealing is proposed to improve the bone/implant interactions. Experiments have been carried out on Ti-6Al-4V alloys exhibiting a porous surface generated primarily by chemical treatment. XPS investigations have shown that low-temperature vacuum annealing can create a controlled number of Ti(3+) defects (up to 21% Ti(3+)/Ti(4+) at 573 K). High Ti(3+) defect concentration is linked to surface porosity. Such surfaces, exhibiting high hydrophilicity and microporosity, would confer to titanium biomaterials a great ability to interact with surrounding proteins and cells and hence would favor the bone anchorage of as-treated implants.

Speciation and pulmonary effects of acidic SO x formed on the surface of ultrafine zinc oxide aerosols

NASA Astrophysics Data System (ADS)

Amdur, Mary O.; Chen, Lung Chi; Guty, John; Lam, Hua Fuan; Miller, Patricia D.

Ultrafine metal oxides and SO 2 react during coal combustion or smelting operations to form primary emissions coated with an acidic SO x layer. A ZnO-SO 2-H 2O (mixed 500°C) system generates such particles to provide greatly needed information on both quantitative composition of the surface layer and its effects on the lung. Total S on the particles is related to ZnO concentration and is predominantly S VI. As a surface layer, 20 μg m -3 H 2SO 4 decreases pulmonary diffusing capacity in guinea pigs after four daily 3-h exposures and produces bronchial hypersensitivity following a single 1-h exposure. That 200 μg m -3 H 2SO 4 aerosols of equivalent particle size are needed to produce the same degree of bronchial hypersensitivity emphasizes the importance of the surface layer.

The Improvement of Electrical Characteristics of Pt/Ti Ohmic Contacts to Ga-Doped ZnO by Homogenized KrF Pulsed Excimer Laser Treatment

NASA Astrophysics Data System (ADS)

Oh, Min-Suk

2018-04-01

We investigated the effect of KrF excimer laser surface treatment on Pt/Ti ohmic contacts to Ga-doped n-ZnO ( N d = 4.3 × 1017 cm-3). The treatment of the n-ZnO surfaces by laser irradiation greatly improved the electrical characteristics of the metal contacts. The Pt/Ti ohmic layer on the laser-irradiated n-ZnO showed specific contact resistances of 2.5 × 10-4 ˜ 4.8 × 10-4 Ω cm2 depending on the laser energy density and gas ambient, which were about two orders of magnitude lower than that of the as-grown sample, 8.4 × 10-2 Ω cm2. X-ray photoelectron spectroscopy and photoluminescence measurements showed that the KrF excimer laser treatments increased the electron concentration near the surface region of the Ga-doped n-ZnO due to the preferential evaporation of oxygen atoms from the ZnO surface by the laser-induced dissociation of Zn-O bonds.

A Comparative Study of Polymer and Biomolecule Surface Modifications by an Atmospheric Pressure Plasma Jet and Surface Microdischarge in Controlled Environments

NASA Astrophysics Data System (ADS)

Bartis, Elliot; Knoll, Andrew; Luan, Pingshan; Hart, Connor; Seog, Joonil; Oehrlein, Gottlieb; Graves, David; Lempert, Walter

2014-10-01

In this work, polymer- and lipopolysaccharide-coated Si substrates were exposed to a surface microdischarge (SMD) and an atmospheric pressure plasma jet (APPJ) in controlled ambients. We seek to understand how plasma-ambient interactions impact biodeactivation and surface modifications by regulating the ambient gas chemistry and the proximity of the plasma to the ambient. A key difference between the SMD and APPJ is that the APPJ needs an Ar feed gas and the SMD does not. By adding small N2/O2 admixtures to Ar, we find that the O2 admixture in the APPJ is a key factor for both deactivation and surface modification. After plasma treatments, we detected a new chemical species on a variety of surfaces that was identified as NO3. We find that NO3 forms even with no N2 in the feed gas, demonstrating that this species forms due to interactions with ambient N2. Despite a very different discharge mechanism, the SMD modifies surfaces similarly to the APPJ, including NO3 formation. The SMD generates large O3 concentrations, which do not correlate with NO3, suggesting that O3 alone is not involved in the NO3 formation mechanism. The authors gratefully acknowledge financial support by the US Department of Energy (DE-SC0005105 and DE-SC0001939) and National Science Foundation (PHY-1004256).

An insight into the origin of room-temperature ferromagnetism in SnO2 and Mn-doped SnO2 quantum dots: an experimental and DFT approach.

PubMed

Manikandan, Dhamodaran; Boukhvalov, D W; Amirthapandian, S; Zhidkov, I S; Kukharenko, A I; Cholakh, S O; Kurmaev, E Z; Murugan, Ramaswamy

2018-02-28

SnO 2 and Mn-doped SnO 2 single-phase tetragonal crystal structure quantum dots (QDs) of uniform size with control over dopant composition and microstructure were synthesized using the high pressure microwave synthesis technique. On a broader vision, we systematically investigated the influence of dilute Mn ions in SnO 2 under the strong quantum confinement regime through various experimental techniques and density functional theoretical (DFT) calculations to disclose the physical mechanism governing the observed ferromagnetism. DFT calculations revealed that the formation of the stable (001) surface was much more energetically favorable than that of the (100) surface, and the formation energy of the oxygen vacancies in the stable (001) surface was comparatively higher in the undoped SnO 2 QDs. X-ray photoelectron spectroscopy (XPS) and first-principles modeling of doped QDs revealed that the lower doping concentration of Mn favored the formation of MnO-like (Mn 2+ ) structures in defect-rich areas and the higher doping concentration of Mn led to the formation of multiple configurations of Mn (Mn 2+ and Mn 3+ ) in the stable surfaces of SnO 2 QDs. Electronic absorption spectra indicated the characteristic spin allowed ligand field transitions of Mn 2+ and Mn 3+ and the red shift in the band gap. DFT calculations clearly indicated that only the substitutional dopant antiferromagnetic configurations were more energetically favorable. The gradual increase of magnetization at a low level of Mn-doping could be explained by the prevalence of antiferromagnetic manganese-vacancy pairs. Higher concentrations of Mn led to the appearance of ferromagnetic interactions between manganese and oxygen vacancies. The increase in the concentration of metallic dopants caused not just an increase in the total magnetic moment of the system but also changed the magnetic interactions between the magnetic moments on the metal ions and oxygen. The present study provides new insight into the fundamental understanding of the origin of ferromagnetism in transition metal-doped QDs.

SU-E-T-178: Optically Stimulated Luminescence (OSL) Dosimetry: A Study of A-Al2O3:C Assessed by PENELOPE Monte Carlo Simulation.

PubMed

Nicolucci, P; Schuch, F

2012-06-01

To use the Monte Carlo code PENELOPE to study attenuation and tissue equivalence properties of a-Al2O3:C for OSL dosimetry. Mass attenuation coefficients of α-Al2O3 and α-Al2O3:C with carbon percent weight concentrations from 1% to 150% were simulated with PENELOPE Monte Carlo code and compared to mass attenuation coefficients from soft tissue for photon beams ranging from 50kV to 10MV. Also, the attenuation of primary photon beams of 6MV and 10MV and the generation of secondary electrons by α-Al2O3 :C dosimeters positioned on the entrance surface of a water phantom were studied. A difference of up to 90% was found in the mass attenuation coefficient between the pure \\agr;-A12O3 and the material with 150% weight concentration of dopant at 1.5 keV, corresponding to the K-edge photoelectric absorption of aluminum. However for energies above 80 keV the concentration of carbon does not affect the mass attenuation coefficient and the material presents tissue equivalence for the beams studied. The ratio between the mass attenuation coefficients for \\agr-A12O3:C and for soft tissue are less than unit due to the higher density of the \\agr-A12O3 (2.12 g/cm s ) and its tissue equivalence diminishes to lower concentrations of carbon and for lower energies due to the relation of the radiation interaction effects with atomic number. The larger attenuation of the primary photon beams by the dosimeter was 16% at 250 keV and the maximum increase in secondary electrons fluence to the entrance surface of the phantom was found as 91% at 2MeV. The use of the OSL dosimeters in radiation therapy can be optimized by use of PENELOPE Monte Carlo simulation to provide a study of the attenuation and response characteristics of the material. © 2012 American Association of Physicists in Medicine.

Surface modification of mixed-phase hydrogenated TiO2 and corresponding photocatalytic response

NASA Astrophysics Data System (ADS)

Samsudin, Emy Marlina; Hamid, Sharifah Bee Abd; Juan, Joon Ching; Basirun, Wan Jefrey; Kandjani, Ahmad Esmaielzadeh

2015-12-01

Preparation of highly photo-activated TiO2 is achievable by hydrogenation at constant temperature and pressure, with controlled hydrogenation duration. The formation of surface disorders and Ti3+ is responsible for the color change from white unhydrogenated TiO2 to bluish-gray hydrogenated TiO2. This color change, together with increased oxygen vacancies and Ti3+ enhanced the solar light absorption from UV to infra-red region. Interestingly, no band gap narrowing is observed. The photocatalytic activity in the UV and visible region is controlled by Ti3+ and oxygen vacancies respectively. Both Ti3+ and oxygen vacancies increases the electron density on the catalyst surface thus facilitates rad OH radicals formation. The lifespan of surface photo-excited electrons and holes are also sustained thus prevents charge carrier recombination. However, excessive amount of oxygen vacancies deteriorates the photocatalytic activity as it serves as charge traps. Hydrogenation of TiO2 also promotes the growth of active {0 0 1} facets and facilitates the photocatalytic activity by higher concentration of surface OH radicals. However, the growth of {0 0 1} facets is small and insignificant toward the overall photo-kinetics. This work also shows that larger role is played by Ti3+ and oxygen vacancies rather than the surface disorders created during the hydrogenation process. It also demonstrates the ability of hydrogenated TiO2 to absorb wider range of photons even though at a similar band gap as unhydrogenated TiO2. In addition, the photocatalytic activity is shown to be decreased for extended hydrogenation duration due to excessive catalyst growth and loss in the total surface area. Thus, a balance in the physico-chemical properties of hydrogenated TiO2 is crucial to enhance the photocatalytic activity by simply controlling the hydrogenation duration.

Dispersed synthesis of uniform Fe3O4 magnetic nanoparticles via in situ decomposition of iron precursor along cotton fibre for Sudan dyes analysis in food samples.

PubMed

Bentahir, Yassine; Elmarhoum, Said; Salghi, Rachid; Algarra, Manuel; Ríos, Angel; Zougagh, Mohammed

2017-11-01

Fe 3 O 4 magnetic nanoparticles, with a negative charge surface, are known to have efficient adsorbent properties, but they tend to be agglomerated into larger aggregates or flocs, which can cause loss of specific area. The addition of cotton fibre, as a stabiliser in preparation of the Fe 3 O 4 nanoparticles, is able to efficiently reduce particle aggregation, and thus, effective particle size, resulting in much greater specific surface area and adsorption sites. Fe 3 O 4 nanoparticles synthesis was accomplished by in situ high-temperature decomposition of the precursor ferric ion in the presence of cotton fibre and ethylene glycol solvent. The morphology of Fe 3 O 4 nanoparticles was characterised by field emission scanning electron microscopy and X-ray diffraction, which confirmed that the magnetic nanoparticles are highly dispersed. These Fe 3 O 4 nanoparticles were used for clean-up and pre-concentration of Sudan dyes in chilli and hot red sauces, prior to their determination by capillary liquid chromatography diode array detection. A comparative study of analyte pre-concentration was conducted with magnetic nanoparticles prepared with and without cotton fibre showing that both solid phases adsorb the analytes, but higher recoveries were obtained when using cotton fibre which therefore was selected for extraction of Sudan dyes.

Excess titanium dioxide nanoparticles on the cell surface induce cytotoxicity by hindering ion exchange and disrupting exocytosis processes.

PubMed

Wang, Yanli; Yao, Chenjie; Li, Chenchen; Ding, Lin; Liu, Jian; Dong, Peng; Fang, Haiping; Lei, Zhendong; Shi, Guosheng; Wu, Minghong

2015-08-14

To date, considerable effort has been devoted to determine the potential toxicity of nanoparticles to cells and organisms. However, determining the mechanism of cytotoxicity induced by different types of nanoparticles remains challenging. Herein, typically low toxicity nanomaterials were used as a model to investigate the mechanism of cytotoxicity induced by low toxicity nanomaterials. We studied the effect of nano-TiO2, nano-Al2O3 and nano-SiO2 deposition films on the ion concentration on a cell-free system simulating the cell membrane. The results showed that the ion concentration of K(+), Ca(2+), Na(+), Mg(2+) and SO4(2-) decreased significantly following filtration of the prepared deposition films. More specifically, at a high nano-TiO2 concentration (200 mg L(-1)) and a long nano-TiO2 deposition time (48 h), the concentration of Na(+) decreased from 2958.01 to 2775.72, 2749.86, 2757.36, and 2719.82 mg L(-1), respectively, for the four types of nano-TiO2 studied. Likewise, the concentration of SO4(2-) decreased from 38.83 to 35.00, 35.80, 35.40, and 35.27 mg L(-1), respectively. The other two kinds of typical low toxicity nanomaterials (nano-Al2O3 and nano-SiO2) have a similar impact on the ion concentration change trend. Adsorption of ions on nanoparticles and the hydrated shell around the ions strongly hindered the ions through the nanoparticle films. The endocytosed nanoparticles could be released from the cells without inducing cytotoxicity. Hindering the ion exchange and disrupting the exocytosis process are the main factors that induce cytotoxicity in the presence of excess nano-TiO2 on the cell surface. The current findings may offer a universal principle for understanding the mechanism of cytotoxicity induced by low toxicity nanomaterials.

Electrically conductive nanostructured silver doped zinc oxide (Ag:ZnO) prepared by solution-immersion technique

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

Afaah, A. N., E-mail: afaahabdullah@yahoo.com; Asib, N. A. M., E-mail: amierahasib@yahoo.com; Aadila, A., E-mail: aadilaazizali@gmail.com

2016-07-06

p-type ZnO films have been fabricated on ZnO-seeded glass substrate, using AgNO{sub 3} as a source of silver dopant by facile solution-immersion. Cleaned glass substrate were seeded with ZnO by mist-atomisation, and next the seeded substrates were immersed in Ag:ZnO solution. The effects of Ag doping concentration on the Ag-doped ZnO have been investigated. The substrates were immersed in different concentrations of Ag dopant with variation of 0, 1, 3, 5 and 7 at. %. The surface morphology of the films was characterized by field emission scanning electron microscope (FESEM). In order to investigate the electrical properties, the films weremore » characterized by Current-Voltage (I-V) measurement. FESEM micrographs showed uniform distribution of nanostructured ZnO and Ag:ZnO. Besides, the electrical properties of Ag-doped ZnO were also dependent on the doping concentration. The I-V measurement result indicated the electrical properties of 1 at. % Ag:ZnO thin film owned highest electrical conductivity.« less

Pool boiling of water-Al2O3 and water-Cu nanofluids on horizontal smooth tubes

PubMed Central

2011-01-01

Experimental investigation of heat transfer during pool boiling of two nanofluids, i.e., water-Al2O3 and water-Cu has been carried out. Nanoparticles were tested at the concentration of 0.01%, 0.1%, and 1% by weight. The horizontal smooth copper and stainless steel tubes having 10 mm OD and 0.6 mm wall thickness formed test heater. The experiments have been performed to establish the influence of nanofluids concentration as well as tube surface material on heat transfer characteristics at atmospheric pressure. The results indicate that independent of concentration nanoparticle material (Al2O3 and Cu) has almost no influence on heat transfer coefficient while boiling of water-Al2O3 or water-Cu nanofluids on smooth copper tube. It seems that heater material did not affect the boiling heat transfer in 0.1 wt.% water-Cu nanofluid, nevertheless independent of concentration, distinctly higher heat transfer coefficient was recorded for stainless steel tube than for copper tube for the same heat flux density. PMID:21711741

Role of the heterojunctions in In2O3-composite SnO2 nanorod sensors and their remarkable gas-sensing performance for NOx at room temperature

NASA Astrophysics Data System (ADS)

Xu, Shuang; Gao, Jun; Wang, Linlin; Kan, Kan; Xie, Yu; Shen, Peikang; Li, Li; Shi, Keying

2015-08-01

Establishing heterostructures, as a good strategy to improve gas sensing performance, has been studied extensively. In this research, In2O3-composite SnO2 nanorod (ICTOs) heterostructures have been prepared via electrospinning, followed by calcination. It is found that In2O3 can improve the carrier density and oxygen deficiency of SnO2. In particular, the 3ICTO (Sn : In atom ratio of 25 : 0.3) nanorods with special particle distributions show an excellent sensing response towards different concentrations of NOx at room temperature. The highest sensing response is up to 8.98 for 100 ppm NOx with a fast response time of 4.67 s, which is over 11 times higher than that of pristine SnO2 nanorods at room temperature and the lowest detection limit is down to 0.1 ppm. More significantly, it presents good stability after 30 days for NOx of low concentration (0.1 ppm and 0.5 ppm). In addition, the rational band structure model combined with the surface depletion model which describe the NOx gas sensing mechanism of 3ICTO are presented. The 3ICTO nanorods may be promising in the application of gas sensors.Establishing heterostructures, as a good strategy to improve gas sensing performance, has been studied extensively. In this research, In2O3-composite SnO2 nanorod (ICTOs) heterostructures have been prepared via electrospinning, followed by calcination. It is found that In2O3 can improve the carrier density and oxygen deficiency of SnO2. In particular, the 3ICTO (Sn : In atom ratio of 25 : 0.3) nanorods with special particle distributions show an excellent sensing response towards different concentrations of NOx at room temperature. The highest sensing response is up to 8.98 for 100 ppm NOx with a fast response time of 4.67 s, which is over 11 times higher than that of pristine SnO2 nanorods at room temperature and the lowest detection limit is down to 0.1 ppm. More significantly, it presents good stability after 30 days for NOx of low concentration (0.1 ppm and 0.5 ppm). In addition, the rational band structure model combined with the surface depletion model which describe the NOx gas sensing mechanism of 3ICTO are presented. The 3ICTO nanorods may be promising in the application of gas sensors. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03796d

Influence of tropospheric ozone control on exposure to ultraviolet radiation at the surface.

PubMed

Madronich, Sasha; Wagner, Mark; Groth, Philip

2011-08-15

Improving air quality by reducing ambient ozone (O(3)) will likely lower O(3) concentrations throughout the troposphere and increase the transmission of solar ultraviolet (UV) radiation to the surface. The changes in surface UV radiation between two control scenarios (nominally 84 and 70 ppb O(3) for summer 2020) in the Eastern two-thirds of the contiguous U.S. are estimated, using tropospheric O(3) profiles calculated with a chemistry-transport model (Community Multi-Scale Air Quality, CMAQ) as inputs to a detailed model of the transfer of solar radiation through the atmosphere (tropospheric ultraviolet-visible, TUV) for clear skies, weighed for the wavelengths known to induce sunburn and skin cancer. Because the incremental emission controls differ according to region, strong spatial variability in O(3) reductions and in corresponding UV radiation increments is seen. The geographically averaged UV increase is 0.11 ± 0.03%, whereas the population-weighted increase is larger, 0.19 ± 0.06%, because O(3) reductions are greater in more densely populated regions. These relative increments in exposure are non-negligible given the already high incidence of UV-related health effects, but are lower by an order of magnitude or more than previous estimates.

Photocatalytic Active Bismuth Fluoride/Oxyfluoride Surface Crystallized 2Bi2O3-B2O3 Glass-Ceramics

NASA Astrophysics Data System (ADS)

Sharma, Sumeet Kumar; Singh, V. P.; Chauhan, Vishal S.; Kushwaha, H. S.; Vaish, Rahul

2018-03-01

The present article deals with 2Bi2O3-B2O3 (BBO) glass whose photocatalytic activity has been enhanced by the method of wet etching using an aqueous solution of hydrofluoric acid (HF). X-ray diffraction of the samples reveals that etching with an aqueous solution of HF leads to the formation of BiF3 and BiO0.1F2.8 phases. Surface morphology obtained from scanning electron microscopy show granular and plate-like morphology on the etched glass samples. Rhodamine 6G (Rh 6G) has been used to investigate the photocatalytic activity of the as-quenched and etched glasses. Enhanced visible light-driven photocatalytic activity was observed in HF etched glass-ceramics compared to the as-quenched BBO glass. Contact angle of the as-quenched glass was 90.2°, which decreases up to 20.02° with an increase in concentration of HF in the etching solution. Enhanced photocatalytic activity and increase in the hydrophilic nature suggests the efficient treatment of water pollutants by using the prepared surface crystallized glass-ceramics.

Artifacts in measuring aerosol uptake kinetics: the roles of time, concentration and adsorption

NASA Astrophysics Data System (ADS)

Renbaum, L. H.; Smith, G. D.

2011-07-01

In laboratory studies of organic aerosol particles reacting with gas-phase oxidants, high concentrations of radicals are often used to study on the timescale of seconds reactions which may be occurring over days or weeks in the troposphere. Implicit in this approach is the assumption that radical concentration and time are interchangeable parameters, though this has not been established. Here, the kinetics of OH- and Cl-initiated oxidation reactions of model single-component liquid (squalane) and supercooled (brassidic acid and 2-octyldodecanoic acid) organic aerosols are studied by varying separately the radical concentration and the reaction time. Two separate flow tubes with residence times of 2 and 66 s are used, and [OH] and [Cl] are varied by adjusting either the laser photolysis fluence or the radical precursor concentration ([O3] or [Cl2], respectively) used to generate the radicals. It is found that the rates measured by varying the radical concentration and the reaction time are equal only if the precursor concentrations are the same in the two approaches. Further, the rates depend on the concentrations of the precursor species with a Langmuir-type functional form suggesting that O3 and Cl2 saturate the surface of the liquid particles. It is believed that the presence of O3 inhibits the rate of OH reaction, perhaps by reacting with OH radicals or by O3 or intermediate species blocking surface sites, while Cl2 enhances the rate of Cl reaction by participating in a radical chain mechanism. These results have important implications for laboratory experiments in which high concentrations of gas-phase oxidants are used to study atmospheric reactions over short timescales and may explain the variability in recent measurements of the reactive uptake of OH on squalane particles in reactor systems used in this and other laboratories.

Chemical Controls of Ozone Dry Deposition to the Sea Surface Microlayer

NASA Astrophysics Data System (ADS)

Carpenter, L.; Chance, R.; Tinel, L.; Saint, A.; Sherwen, T.; Loades, D.; Evans, M. J.; Boxhall, P.; Hamilton, J.; Stolle, C.; Wurl, O.; Ribas-Ribas, M.; Pereira, R.

2017-12-01

Oceanic dry deposition of atmospheric ozone (O3) is both the largest and most uncertain O3 depositional sink, and is widely acknowledged to be controlled largely by chemical reactions in the sea surface microlayer (SML) involving iodide (I-) and dissolved organic material (DOM). These reactions not only determine how quickly O3 can be removed from the atmosphere, but also result in emissions of trace gases including volatile organic compounds and may constitute a source of secondary organic aerosols to the marine atmosphere. Iodide concentrations at the sea surface vary by approximately an order of magnitude spatially, leading to more than fivefold variation in ozone deposition velocities (and volatile iodine fluxes). Sea-surface temperature is a reasonable predictor of [I-], however two recent parameterisations for surface I- differ by a factor of two at low latitudes. The nature and reactivity of marine DOM to O3 is almost completely unknown, although studies have suggested approximately equivalent chemical control of I- and DOM on ozone deposition. Here we present substantial new measurements of oceanic I- in both bulk seawater and the overlying SML, and show improved estimates of the global sea surface iodide distribution. We also present analyses of water-soluble DOM isolated from the SML and bulk seawater, and corresponding laboratory studies of ozone uptake to bulk and SML seawater, with the aim of characterizing the reactivity of O3 towards marine DOM.

Atomic layer deposition of indium oxide thin film from a liquid indium complex containing 1-dimethylamino-2-methyl-2-propoxy ligands

NASA Astrophysics Data System (ADS)

Han, Jeong Hwan; Jung, Eun Ae; Kim, Hyo Yeon; Kim, Da Hye; Park, Bo Keun; Park, Jin-Seong; Son, Seung Uk; Chung, Taek-Mo

2016-10-01

In2O3 thin films were grown from a newly developed, liquid, homoleptic, In-based complex, tris(1-dimethylamino-2-methyl-2-propoxy)indium [In(dmamp)3], and O3 by atomic layer deposition (ALD) at growth temperatures of 150-200 °C. In(dmamp)3 exhibited single-step evaporation with negligible residue and excellent thermal stability between 30 and 250 °C. The self-limiting surface reaction of In2O3 during ALD was demonstrated by varying the In(dmamp)3 and O3 pulse lengths, with a growth rate of 0.027 nm/cycle achieved at 200 °C. The In2O3 films grown at temperatures over 175 °C exhibited negligible concentrations of impurities, whereas that grown below 175 °C had concentrations of residual C of 6-8 at.%. Glancing angle X-ray diffraction revealed that the In2O3 films were polycrystalline in nature when the deposition temperature was greater than 200 °C. The In2O3 films grown at 150-200 °C exhibited carrier concentrations of 1.5 × 1018-6.6 × 1019 cm-3, resistivities of 15.1-2 × 10-3 Ω cm, and Hall mobilities of 0.8-42 cm2/(V s).

Observational Studies and a Statistical Early Warning of Surface Ozone Pollution in Tangshan, the Largest Heavy Industry City of North China

PubMed Central

Li, Pei; Xin, Jinyuan; Bai, Xiaoping; Wang, Yuesi; Wang, Shigong; Liu, Shixi; Feng, Xiaoxin

2013-01-01

Continuous measurements of surface ozone (O3) and nitrogen oxides (NOX) at an urban site (39°37′N, 118°09′E) in Tangshan, the largest heavy industry city of North China during summertime from 2008 to 2011 are presented. The pollution of O3 was serious in the city. The daily maximum 1 h means (O3_1-hr max) reached 157 ± 55, 161 ± 54, 120 ± 50, and 178 ± 75 μg/m3 corresponding to an excess over the standard rates of 21%, 27%, 10%, and 40% in 2008–2011, respectively. The total oxidant level (OX = O3 + NO2) was high, with seasonal average concentrations up to 100 μg/m3 in summer. The level of OX at a given location was made up of NOX-independent and NOX-dependent contributions. The independent part can be considered as a regional contribution and was about 100 μg/m3 in Tangshan. Statistical early warning analysis revealed that the O3 levels would exceed the standard rate by 50% on the day following a day when the daily average ozone concentration (O3_mean) exceeded 87 μg/m3 and the daily maximum temperature (T_max) exceeded 29 °C. The exceed-standard rate would reach 80% when O3_mean and T_max exceeded 113 μg/m3 and 31 °C. Similarly, the exceed-standard rate would reach 100% when O3_mean and T_max exceeded 127 μg/m3 and 33 °C, respectively. PMID:23485953

Photochemical modeling of the Antarctic stratosphere: Observational constraints from the airborne Antarctic ozone experiment and implications for ozone behavior

NASA Technical Reports Server (NTRS)

Rodriguez, Jose M.; Sze, Nien-Dak; Ko, Malcolm K. W.

1988-01-01

The rapid decrease in O3 column densities observed during Antarctic spring has been attributed to several chemical mechanisms involving nitrogen, bromine, or chlorine species, to dynamical mechanisms, or to a combination of the above. Chlorine-related theories, in particular, predict greatly elevated concentrations of ClO and OClO and suppressed abundances of NO2 below 22 km. The heterogeneous reactions and phase transitions proposed by these theories could also impact the concentrations of HCl, ClNO3 and HNO3 in this region. Observations of the above species have been carried out from the ground by the National Ozone Expedition (NOZE-I, 1986, and NOZE-II, 1987), and from aircrafts by the Airborne Antarctic Ozone Experiment (AAOE) during the austral spring of 1987. Observations of aerosol concentrations, size distribution and backscattering ratio from AAOE, and of aerosol extinction coefficients from the SAM-II satellite can also be used to deduce the altitude and temporal behavior of surfaces which catalyze heterogeneous mechanisms. All these observations provide important constraints on the photochemical processes suggested for the spring Antarctic stratosphere. Results are presented for the concentrations and time development of key trace gases in the Antarctic stratosphere, utilizing the AER photochemical model. This model includes complete gas-phase photochemistry, as well as heterogeneous reactions. Heterogeneous chemistry is parameterized in terms of surface concentrations of aerosols, collision frequencies between gas molecules and aerosol surfaces, concentrations of HCl/H2O in the frozen particles, and probability of reaction per collision (gamma). Values of gamma are taken from the latest laboratory measurements. The heterogeneous chemistry and phase transitions are assumed to occur between 12 and 22 km. The behavior of trace species at higher altitudes is calculated by the AER 2-D model without heterogeneous chemistry. Calculations are performed for solar illumination conditions typical of 60, 70, and 80 S, from July 15 to October 31.

Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO2 in the decomposition of high concentration ozone

NASA Astrophysics Data System (ADS)

Ding, Yanhua; Zhang, Xiaolei; Chen, Li; Wang, Xiaorui; Zhang, Na; Liu, Yufeng; Fang, Yongzheng

2017-06-01

The catalytic decomposition of gaseous ozone (O3) is investigated using anatase TiO2 (A-TiO2) and Aluminum-reduced A-TiO2 (ARA-TiO2) at high concentration and high relative humidity (RH) without light illumination. Compared with the pristine A-TiO2, the ARA-TiO2 sample possesses a unique crystalline core-amorphous shell structure. It is proved to be an excellent solar energy ;capture; for solar thermal collectors due to lots of oxygen vacancies. The results indicate that the overall decomposition efficiency of O3 without any light irradiation has been greatly improved from 4.8% on A-TiO2 to 100% on ARA-TiO2 under the RH=100% condition. The ozone conversion over T500/ARA-TiO2 catalyst is still maintained at 95% after a 72 h test under the reaction condition of 18.5 g/m3 ozone initial concentration, and RH=90%. The results can be explained that T500/ARA-TiO2 possesses the largest amorphous contour, the lowest crystallinity, the most surface-active Ti3+/Ti4+couples, and the most oxygen vacancies. This result opens a new door to widen the application of TiO2 in the thermal-catalytic field.

Aerosols from fires: an examination of the effects on ozone photochemistry in the Western United States.

PubMed

Jiang, Xiaoyan; Wiedinmyer, Christine; Carlton, Annmarie G

2012-11-06

This study presents a first attempt to investigate the roles of fire aerosols in ozone (O(3)) photochemistry using an online coupled meteorology-chemistry model, the Weather Research and Foresting model with Chemistry (WRF-Chem). Four 1-month WRF-Chem simulations for August 2007, with and without fire emissions, were carried out to assess the sensitivity of O(3) predictions to the emissions and subsequent radiative feedbacks associated with large-scale fires in the Western United States (U.S.). Results show that decreases in planetary boundary layer height (PBLH) resulting from the radiative effects of fire aerosols and increases in emissions of nitrogen oxides (NO(x)) and volatile organic compounds (VOCs) from the fires tend to increase modeled O(3) concentrations near the source. Reductions in downward shortwave radiation reaching the surface and surface temperature due to fire aerosols cause decreases in biogenic isoprene emissions and J(NO(2)) photolysis rates, resulting in reductions in O(3) concentrations by as much as 15%. Thus, the results presented in this study imply that considering the radiative effects of fire aerosols may reduce O(3) overestimation by traditional photochemical models that do not consider fire-induced changes in meteorology; implementation of coupled meteorology-chemistry models are required to simulate the atmospheric chemistry impacted by large-scale fires.

Mechanisms of devitrification of grain boundary glassy phases in Si3N4 materials

NASA Technical Reports Server (NTRS)

Hench, L. L.

1982-01-01

Changes in the grain boundary (g.b.) phases of Si3N4 are analyzed, the effects of composition and thermal history on devitrification of the g.b. phases are determined, devitrification of the g.b. phases of Si3N are related to mechanical behavior and oxidation sensitivity of the material. The phase relationships that occur within the grain boundaries of Si3N4 containing various densification aids are reviewed. Comparisons of the effects of MgO, Y2O3, CeO2, and Y2O3 + AL2O3 are made in terms of the phase equilibria of the Si3N4 + SiO2 + additive compositional system. Two new equilibrium phase diagrams for the Si3N4-SiO2 and Y2O3 and Si3N4-SiO2-Ce2O3 systems are preented. The effects of Y2O3 vs CeO2 densification aids on the fracture surfaces of Si3N4 are compared. Auger electron spectroscopy shows that both oxides are concentrated within the fracture surface. Scanning electron microscopy shows evidence that Si3N4 with CeO2 formed an intergranular structure of fine grained oxynitride reaction products, as predicted by phase quilibria, whereas the Y2O3 containing sample shows evidence of an intergranular glassy phase.

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

Gallegos, N.G.; Alvarez, A.M.; Cagnoli, M.V.

SiO{sub 2} covered with MgO has been used as support of iron catalysts in the Fischer-Tropsch reaction. Catalysts of 5% (w/w) iron concentration and 2, 4, and 8% (w/w) of MgO on SiO{sub 2} were prepared. Selective chemisorption of CO, volumetric oxidation, and Moessbauer spectroscopy were used to characterize the type of iron species and the metallic crystal sizes. MgO covers the SiO{sub 2} surface and modifies the metallic crystal size. The activity to total hydrocarbons increases with the amount of MgO added. An optimal concentration of about 4% (w/w) was found to have the highest selectivity to olefins. 45more » refs., 13 figs., 3 tabs.« less

Spatial resolution in thin film deposition on silicon surfaces by combining silylation and UV/ozonolysis

NASA Astrophysics Data System (ADS)

Guo, Lei; Zaera, Francisco

2014-12-01

A simple procedure has been developed for the processing of silicon wafers in order to facilitate the spatially resolved growth of thin solid films on their surfaces. Specifically, a combination of silylation and UV/ozonolysis was tested as a way to control the concentration of the surface hydroxo groups required for subsequent atomic layer deposition (ALD) of metals or oxides. Water contact angle measurements were used to evaluate the hydrophilicity/hydrophobicity of the surface, a proxy for OH surface coverage, and to optimize the UV/ozonolysis treatment. Silylation with hexamethyldisilazane, trichloro(octadecyl)silane, or trimethylchlorosilane was found to be an efficient way to block the hydroxo sites and to passivate the underlying surface, and UV/O3 treatments were shown to effectively remove the silylation layer and to regain the surface reactivity. Both O3 and 185 nm UV radiation were determined necessary for the removal of the silylation layer, and additional 254 nm radiation was found to enhance the process. Attenuated total reflection-infrared absorption spectroscopy was employed to assess the success of the silylation and UV/O3 removal steps, and atomic force microscopy data provided evidence for the retention of the original smoothness of the surface. Selective growth of HfO2 films via TDMAHf + H2O ALD was seen only on the UV/O3 treated surfaces; total inhibition of the deposition was observed on the untreated silylated surfaces (as determined by x-ray photoelectron spectroscopy and ellipsometry). Residual film growth was still detected on the latter if the ALD was carried out at high temperatures (250 °C), because the silylation layer deteriorates under such harsh conditions and forms surface defects that act as nucleation sites for the growth of oxide grains (as identified by electron microscopy and scanning electron microscopy). We believe that the silylation-UV/O3 procedure advanced here could be easily implemented for the patterning of surfaces in many microelectronic applications.

Single-Gap Superconductivity and Dome of Superfluid Density in Nb-Doped SrTiO 3

NASA Astrophysics Data System (ADS)

Thiemann, Markus; Beutel, Manfred H.; Dressel, Martin; Lee-Hone, Nicholas R.; Broun, David M.; Fillis-Tsirakis, Evangelos; Boschker, Hans; Mannhart, Jochen; Scheffler, Marc

2018-06-01

SrTiO3 exhibits a superconducting dome upon doping with Nb, with a maximum critical temperature Tc≈0.4 K . Using microwave stripline resonators at frequencies from 2 to 23 GHz and temperatures down to 0.02 K, we probe the low-energy optical response of superconducting SrTiO3 with a charge carrier concentration from 0.3 to 2.2 ×1020 cm-3 , covering the majority of the superconducting dome. We find single-gap electrodynamics even though several electronic bands are superconducting. This is explained by a single energy gap 2 Δ due to gap homogenization over the Fermi surface consistent with the low level of defect scattering in Nb-doped SrTiO3 . Furthermore, we determine Tc, 2 Δ , and the superfluid density as a function of charge carrier concentration, and all three quantities exhibit the characteristic dome shape.

Effects of nano-SiO{sub 2} particles on surface tracking characteristics of silicone rubber composites

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

Liu, Yong, E-mail: tjuliuyong@tju.edu.cn; Li, Zhonglei; Du, Boxue

Compared with neat silicone rubber composites (SiRCs), SiRCs filled with nano-sized SiO{sub 2} particles at weight ratios from 0.1 to 1.0 wt. % exhibit a higher surface flashover voltage and a greater resistance to surface tracking. Scanning electron microscopy images of tracking morphologies indicate that the SiO{sub 2} particles are situated in close proximity to the polymeric chains and act as bridges to stabilize the chains and maintain the structure of the composite. Higher concentrations of nano-sized SiO{sub 2} particles, however, (above 0.3 wt. %) produce defects in the molecular network which lead to reductions in both the surface flashover voltage and the resistancemore » to surface tracking, although these reduced values are still superior to those of neat SiRCs. Therefore, SiRCs filled with nano-sized SiO{sub 2} particles, especially at an optimal weight ratio (0.1 to 0.3 wt. %), may have significant potential applications as outdoor insulators for power systems.« less

Effect of soil parameters on the kinetics of the displacement of Fe from FeEDDHA chelates by Cu.

PubMed

Schenkeveld, Walter D C; Reichwein, Arjen M; Temminghoff, Erwin J M; van Riemsdijk, Willem H

2012-06-28

In soil application, o,o-FeEDDHA (iron (3+) ethylene diamine-N,N'-bis(2-hydroxy phenyl acetic acid) complex) is the active ingredient of FeEDDHA chelate-based Fe fertilizers. The effectiveness of o,o-FeEDDHA is potentially compromised by the displacement of Fe from FeEDDHA by Cu. The actual impact of Cu competition is codetermined by the kinetics of the displacement reaction. In this study, the influence of soil parameters on the displacement kinetics has been examined in goethite suspensions. The displacement reaction predominantly takes place on the reactive surface rather than in solution. The rate at which the o,o-FeEDDHA concentration declined depended on the available reactive surface area, the Cu loading, and the FeEDDHA loading. Soil factors reducing FeEDDHA adsorption (high ionic strength, humic acid adsorption onto the goethite surface, and monovalent instead of divalent cations in the electrolyte) decreased the displacement rate. For meso o,o-FeEDDHA, the displacement rate equation was derived, which is first order in FeEDDHA loading and half order in Cu loading. For soil conditions, the equation can be simplified to an exponential decay function in meso o,o-FeEDDHA solution concentration.

Measuring near-field nanoparticle concentration profiles by correlating surface plasmon resonance reflectance with effective refractive index of nanofluids.

PubMed

Kim, Iltai; Kihm, Kenneth D

2010-02-01

Time-dependent and near-field nanoparticle concentrations are determined by correlating the surface plasmon resonance (SPR) reflectance intensities with the effective refractive index (ERI) of the nanofluid under evaporation. A critical angle measurement for total internal reflection identifies the ERI of the nanofluid at different nanoparticle concentrations. The corresponding SPR reflectance intensities correlate the nanofluidic ERI with the nanoparticle concentrations. Example applications for evaporating nanofluidic droplets containing 47 nmAl(2)O(3) particles demonstrate the feasibility of this new imaging tool for measuring time-resolved and full-field nanoparticle concentration profiles.

Pathway and Surface Mechanism Studies of 1,3-butadiene Selective Oxidation Over Vanadium-Molybdenum-Oxygen Catalysts

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

Schroeder, William David

2001-01-01

The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m 2/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO 3/(MoO 3 + V 2O 5). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V +4 and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of watermore » to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from 12% to over 25%. The catalytic effects of water addition were related to competitive adsorption with various V 2O 5-based surface sites, including the vanadyl V=O, corner sharing V-O-V and edge sharing V-O oxygen. Higher levels of water addition were proposed to impose acidic character by dissociative adsorption. In addition, a novel combinatorial synthesis technique for VMoO was used to investigate the phase transitions of V 2O 5, solid solutions of Mo in V 2O 5, V 9Mo 6O 40, and other reduced VMoO compounds, characterized by laser Raman spectroscopy. The natural composition gradient imposed by the sputter deposition apparatus was used to create VMoO arrays containing 225 samples ranging from 7.0-42 mol% MoO 3/(V 2O 5 + MoO 3), determined by EDS analysis.« less

TiO2 nanofibers resembling 'yellow bristle grass' in morphology by a soft chemical transformation.

PubMed

Nandan, Sandeep; Deepak, T G; Nair, Shantikumar V; Nair, A Sreekumaran

2015-05-28

We synthesized a uniquely shaped one-dimensional (1-D) TiO2 nanostructure having the morphology of yellow bristle grass with high surface area by the titanate route under mild reaction conditions. The electrospun TiO2-SiO2 composite nanofibers upon treatment with concentrated NaOH at 80 °C under ambient pressure for 24 h resulted in sodium titanate (Na2Ti3O7) nanostructures. The Na2Ti3O7 nanostructures have an overall 1-D fibrous morphology but the highly porous fiber surfaces were decorated with layered thorn-like features (a morphology resembling that of yellow bristle grass) resulting in high surface area (113 m(2) g(-1)) and porosity. The Na2Ti3O7 nanostructures were converted into TiO2 nanostructures of the same morphology by acidification (0.1 N HCl) followed by low temperature sintering (110 °C) processes. Dye-sensitized solar cells (DSCs) constructed out of the material (cells of area 0.20 cm(2) and thickness 12 μm) showed a power conversion efficiency (η) of 8.02% in comparison with commercial P-25 TiO2 (η = 6.1%).

Secondary organic aerosols from ozone-initiated reactions with emissions from wood-based materials and a "green" paint

NASA Astrophysics Data System (ADS)

Toftum, J.; Freund, S.; Salthammer, T.; Weschler, C. J.

This study examined the formation and growth of secondary organic aerosols (SOA) generated when ozone was added to a 1 m 3 glass chamber that contained either pine shelving, oriented strand board (OSB), beech boards, or beach boards painted with an "eco" paint. The experiments were conducted at close to real-world conditions; the chamber was ventilated at ˜0.5 air changes/h; the loadings (exposed surface of building materials to chamber volume) were in the range of 1-2.5 m 2 m -3; and the initial O 3 concentrations were between 15 and 40 ppb. Throughout each experiment particles were measured with both a condensation nuclei counter and an optical counter, while terpenes were measured before and after the ozone exposure period using sorbent tubes. The pine boards emitted primarily α-pinene and 3-carene and lesser amounts of 5 other terpenes; when O 3 was introduced, the particle counts increased dramatically; the mass concentration reached ˜15 μg m -3 at ˜20 ppb O 3, and ˜95 μg m -3 at ˜40 ppb O 3. The OSB emitted primarily limonene and α-pinene. Although the particle counts increased when O 3 was introduced, the increase was not as large as anticipated based on the terpene concentrations. The beech boards emitted negligible quantities of terpenes, and the introduction of O 3 resulted in almost no increase in the particle concentration. Beech boards painted with an "eco" paint emitted large amounts of limonene and lesser amounts of carvone; upon introduction of O 3 the particle counts increased sharply with the mass concentration reaching ˜20 μg m -3 at ˜15 ppb O 3 and ˜160 μg m -3 at ˜35 ppb O 3. These experiments demonstrate that the emission of terpenes and potential generation of SOA varies greatly among different types of wood and pressed wood materials. In the case of the pine boards and painted beech boards, the SOA concentrations generated at modest O 3 concentrations approach or exceed current guideline levels for PM 2.5 established by the US EPA and the World Health Organization.

FAS grafted superhydrophobic ceramic membrane

NASA Astrophysics Data System (ADS)

Lu, Jun; Yu, Yun; Zhou, Jianer; Song, Lixin; Hu, Xingfang; Larbot, Andre

2009-08-01

The hydrophobic properties of γ-Al 2O 3 membrane have been obtained by grafting fluoroalkylsilane (FAS) on the surface of the membrane. The following grafting parameters were studied: the eroding time of the original membrane, the grafting time, the concentration of FAS solution and the multiplicity of grafting. Hydrophobicity of the membranes was characterized by contact angle (CA) measurement. The thermogravimetric analysis (TGA) was used to investigate the weight loss process (25-800 °C) of the fluoroalkylsilane grafted on Al 2O 3 powders under different grafting conditions. The morphologies of the membranes modified under different parameters were examined by field emission scanning electron microscopy (FE-SEM) and the surface roughness (Ra) was measured using white light interferometers. A needle-like structure was observed on the membrane surface after modification, which causes the change of Ra. On the results above, we speculated a model to describe the reaction between FAS and γ-Al 2O 3 membrane surface as well as the formed surface morphology.

Rapid Adsorption of Heavy Metals by Fe3O4/Talc Nanocomposite and Optimization Study Using Response Surface Methodology

PubMed Central

Kalantari, Katayoon; Ahmad, Mansor B.; Masoumi, Hamid Reza Fard; Shameli, Kamyar; Basri, Mahiran; Khandanlou, Roshanak

2014-01-01

Fe3O4/talc nanocomposite was used for removal of Cu(II), Ni(II), and Pb(II) ions from aqueous solutions. Experiments were designed by response surface methodology (RSM) and a quadratic model was used to predict the variables. The adsorption parameters such as adsorbent dosage, removal time, and initial ion concentration were used as the independent variables and their effects on heavy metal ion removal were investigated. Analysis of variance was incorporated to judge the adequacy of the models. Optimal conditions with initial heavy metal ion concentration of 100, 92 and 270 mg/L, 120 s of removal time and 0.12 g of adsorbent amount resulted in 72.15%, 50.23%, and 91.35% removal efficiency for Cu(II), Ni(II), and Pb(II), respectively. The predictions of the model were in good agreement with experimental results and the Fe3O4/talc nanocomposite was successfully used to remove heavy metals from aqueous solutions. PMID:25050784

Degradation of 4-Chloro-3,5-Dimethylphenol by a Heterogeneous Fenton-Like Reaction Using Nanoscale Zero-Valent Iron Catalysts

PubMed Central

Xu, Lejin; Wang, Jianlong

2013-01-01

Abstract Degradation of 4-chloro-3,5-dimethylphenol (PCMX) by a heterogeneous Fenton-like process using nanoparticulate zero-valent iron (nZVI) and hydrogen peroxide (H2O2) at pH 6.3 was investigated. Interactive effects of three factors—initial PCMX concentration, nZVI dosage, and H2O2 concentration—were investigated using the response surface method based on the Box–Behnken design. Experimental results showed that complete decomposition of PCMX and 65% of total organic carbon removal were observed after 30 min of reaction at neutral pH under recommended reaction conditions: nZVI, 1.0 g/L; H2O2, 18 mM; and initial PCMX concentration, 0.15 g/L. Based on the effects of scavengers n-butanol and KI, removal of PCMX was mainly attributed to the attack of •OH, especially the surface-bonded •OH. A possible degradation pathway of PCMX was proposed. PMID:23781127

Rapid adsorption of heavy metals by Fe3O4/talc nanocomposite and optimization study using response surface methodology.

PubMed

Kalantari, Katayoon; Ahmad, Mansor B; Masoumi, Hamid Reza Fard; Shameli, Kamyar; Basri, Mahiran; Khandanlou, Roshanak

2014-07-21

Fe3O4/talc nanocomposite was used for removal of Cu(II), Ni(II), and Pb(II) ions from aqueous solutions. Experiments were designed by response surface methodology (RSM) and a quadratic model was used to predict the variables. The adsorption parameters such as adsorbent dosage, removal time, and initial ion concentration were used as the independent variables and their effects on heavy metal ion removal were investigated. Analysis of variance was incorporated to judge the adequacy of the models. Optimal conditions with initial heavy metal ion concentration of 100, 92 and 270 mg/L, 120 s of removal time and 0.12 g of adsorbent amount resulted in 72.15%, 50.23%, and 91.35% removal efficiency for Cu(II), Ni(II), and Pb(II), respectively. The predictions of the model were in good agreement with experimental results and the Fe3O4/talc nanocomposite was successfully used to remove heavy metals from aqueous solutions.

Quantitative measurements of ground state atomic oxygen in atmospheric pressure surface micro-discharge array

NASA Astrophysics Data System (ADS)

Li, D.; Kong, M. G.; Britun, N.; Snyders, R.; Leys, C.; Nikiforov, A.

2017-06-01

The generation of atomic oxygen in an array of surface micro-discharge, working in atmospheric pressure He/O2 or Ar/O2 mixtures, is investigated. The absolute atomic oxygen density and its temporal and spatial dynamics are studied by means of two-photon absorption laser-induced fluorescence. A high density of atomic oxygen is detected in the He/O2 mixture with up to 10% O2 content in the feed gas, whereas the atomic oxygen concentration in the Ar/O2 mixture stays below the detection limit of 1013 cm-3. The measured O density near the electrode under the optimal conditions in He/1.75% O2 gas is 4.26  ×  1015 cm-3. The existence of the ground state O (2p 4 3 P) species has been proven in the discharge at a distance up to 12 mm away from the electrodes. Dissociative reactions of the singlet O2 with O3 and deep vacuum ultraviolet radiation, including the radiation of excimer \\text{He}2\\ast , are proposed to be responsible for O (2p 4 3 P) production in the far afterglow. A capability of the surface micro-discharge array delivering atomic oxygen to long distances over a large area is considered very interesting for various biomedical applications.

Vertical Profiles as Observational Constraints on Nitrous Oxide (N2O) Emissions in an Agricultural Region

NASA Astrophysics Data System (ADS)

Pusede, S.; Diskin, G. S.

2015-12-01

We use diurnal variability in near-surface N2O vertical profiles to derive N2O emission rates. Our emissions estimates are ~3 times greater than are accounted for by inventories, a discrepancy in line with results from previous studies using different approaches. We quantify the surface N2O concentration's memory of local surface emissions on previous days to be 50-90%. We compare measured profiles both over and away from a dense N2O source region in the San Joaquin Valley, finding that profile shapes, diurnal variability, and changes in integrated near-surface column abundances are distinct according to proximity to source areas. To do this work, we use aircraft observations from the wintertime DISCOVER-AQ project in California's San Joaquin Valley, a region of intense agricultural activity.

Oxidation of pyrite in an anoxic atmosphere

USGS Publications Warehouse

Thorpe, A.N.; Senftle, F.E.; Alexander, Corrine; Dulong, F.T.; LaCount, R.B.; Friedman, S.

1987-01-01

Pyrite (FeS2) inclusions in coal, when heated in an oxygen deficient atmosphere (approximately 1% oxygen), become coated with magnetic Fe3O4 due to oxidation. Most of the FeS2 can thus be removed from the coal by magnetic separation to reduce the sulphur concentration. The oxidation products have been studied in greater detail by measuring the SO2 and O2 in the effluent gas during the heating process and by performing further magnetic measurements. At 582 K, the pyrite surface was oxidized to FeSO4. Significant oxidation of FeSO4 and FeS2 to Fe3O4 was observed starting at 677 K. At about 681 K, the Fe3O4 is further oxidized to ??-Fe2O3. At 681 K, under isothermal conditions, the oxidation is impeded by the ??-Fe2O3 formed on the surfaces of the grains. If the temperature is rapidly increased, the oxygen penetrates the ??-Fe2O3 veneer to the FeS2 core of the pyrite grains and oxidizes essentially the whole pyrite mass to Fe3O4 before ??-Fe2O3 can be formed. ?? 1987.

Structure-Based Design, Synthesis and Testing of Non-Peptide, Cell-Permeable, Potent Small Molecule Smac Mimetics as a New Therapy for Prostate Cancer. Revision

DTIC Science & Technology

2007-02-01

from pyroglutamic acid 7 in eight steps according to a reported method.32 Hydrogenation of the double bond in 8 catalyzed by 10% Pd-C, followed by...with 70% perchloric acid and concentrated hydrochloric acid . RCH2PPh3Br + O O OMe OMe a,b O O OMe OMe R c,d O O OH OH R CHO 21a-1h 3a-3h 4a-4h Scheme...Smac to XIAP BIR3 is mediated by AVPI four amino acid residues in Smac and a well-defined surface binding groove in XIAP BIR3. While the alanine residue

Device Performance and Reliability Improvements of AlGaN/GaN/Si MOSFET Using Defect-Free Gate Recess and Laser Annealing

DTIC Science & Technology

2012-07-18

For AlGaN, it is found that Al2O3, Ga2O3 and N-O states were detected on native oxide and HF-treated surfaces. During the course of the ALD process...the N-O bonds are seen to decrease to a level near XPS detection limits, as well as a small decrease in the Ga2O3 concentration, consistent with a...and the other at 1118.2 eV, indicative of a Ga 3+ oxidation state, likely due to Ga2O3 , consistent with previous reports.22,23 There is no evidence

Seasonal lake surface water temperature trends reflected by heterocyst glycolipid-based molecular thermometers

NASA Astrophysics Data System (ADS)

Bauersachs, T.; Rochelmeier, J.; Schwark, L.

2015-06-01

It has been demonstrated that the relative distribution of heterocyst glycolipids (HGs) in cultures of N2-fixing heterocystous cyanobacteria is largely controlled by growth temperature, suggesting a potential use of these components in paleoenvironmental studies. Here, we investigated the effect of environmental parameters (e.g., surface water temperatures, oxygen concentrations and pH) on the distribution of HGs in a natural system using water column filtrates collected from Lake Schreventeich (Kiel, Germany) from late July to the end of October 2013. HPLC-ESI/MS (high-performance liquid chromatography coupled to electrospray ionization-mass spectrometry) analysis revealed a dominance of 1-(O-hexose)-3,25-hexacosanediols (HG26 diols) and 1-(O-hexose)-3-keto-25-hexacosanol (HG26 keto-ol) in the solvent-extracted water column filtrates, which were accompanied by minor abundances of 1-(O-hexose)-3,27-octacosanediol (HG28 diol) and 1-(O-hexose)-3-keto-27-octacosanol (HG28 keto-ol) as well as 1-(O-hexose)-3,25,27-octacosanetriol (HG28 triol) and 1-(O-hexose)-3-keto-25,27-octacosanediol (HG28 keto-diol). Fractional abundances of alcoholic and ketonic HGs generally showed strong linear correlations with surface water temperatures and no or only weak linear correlations with both oxygen concentrations and pH. Changes in the distribution of the most abundant diol and keto-ol (e.g., HG26 diol and HG26 keto-ol) were quantitatively expressed as the HDI26 (heterocyst diol index of 26 carbon atoms) with values of this index ranging from 0.89 in mid-August to 0.66 in mid-October. An average HDI26 value of 0.79, which translates into a calculated surface water temperature of 15.8 ± 0.3 °C, was obtained from surface sediments collected from Lake Schreventeich. This temperature - and temperatures obtained from other HG indices (e.g., HDI28 and HTI28) - is similar to the one measured during maximum cyanobacterial productivity in early to mid-September and suggests that HGs preserved in the sediment record of Lake Schreventeich reflect summer surface water temperatures. As N2-fixing heterocystous cyanobacteria are widespread in present-day freshwater and brackish environments, we conclude that the distribution of HGs in sediments may allow for the reconstruction of surface water temperatures of modern and potentially ancient lacustrine settings.

Impact of Future Emissions and Climate Change on Surface Ozone over China

NASA Astrophysics Data System (ADS)

Ma, C. T.; Westervelt, D. M.; Fiore, A. M.; Rieder, H. E.; Kinney, P.; Wang, S.; Correa, G. J. P.

2017-12-01

China's immense ambient air pollution problem and world-leading greenhouse gas emissions place it at the forefront of global efforts to address these related environmental concerns. Here, we analyze the impact of ECLIPSE (Evaluating the Climate and Air Quality Impacts of Short-Lived Pollutants) future emissions scenarios representative of current legislation (CLE) and maximum technically feasible emissions reductions (MFR) on surface ozone (O3) concentrations over China in the 2030s and 2050s, in the context of a changing climate. We use a suite of simulations performed with the NOAA Geophysical Fluid Dynamics Laboratory's AM3 global chemistry-climate model. To estimate the impact of climate change in isolation on Chinese air quality, we hold emissions of air pollutants including O3 precursors fixed at 2015 levels but allow climate (global sea surface temperatures and sea ice cover) to change according to decadal averages for the years 2026-2035 and 2046-2055 from a three-member ensemble of GFDL-CM3 simulations under the RCP8.5 high warming scenario. Evaluation of the present-day simulation (2015 CLE) with observations from 1497 chiefly urban air quality monitoring stations shows that simulated surface O3 is positively biased by 26 ppb on average over the domain of China. Previous studies, however, have shown that the modeled ozone response to changes in NOx emissions over the Eastern United States mirrors the magnitude and structure of observed changes in maximum daily average 8-hour (MDA8) O3 distributions. Therefore, we use the model's simulated changes for the 2030s and 2050s to project changes in policy-relevant MDA8 O3 concentrations. We find an overall increase in MDA8 O3 for CLE scenarios in which emissions of NOx precursors are projected to increase, and under MFR scenarios, an overall decrease, with the highest changes occurring in summertime for both 2030 and 2050 MFR. Under climate change alone, the model simulates a mean summertime decrease of 1.3 ppb and wintertime increase of 3.3 ppb by 2050. Adjustment of the observed site-level MDA8 O3 distribution to reflect regionally interpolated projected changes from AM3 allows us to examine changes in the number of days in exceedance of MDA8 O3 Level I (50 ppb) and Level II (80 ppb) Chinese national ambient air quality standards.

Electrostatic powder spraying process for the fabrication of stable superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Gu, Guotuan; Tian, Yuping; Li, Zhantie; Lu, Dongfang

2011-03-01

Nano-sized Al2O3 particles were modified by heptadecafluorodecyl trimethoxysilane and 2,3-epoxy propoxy propyl trimethoxysilicane to make it both hydrophobic and reactive. The reactive nano-particles were mixed with polyester resin containing curing agents and electrostatic sprayed on stainless steel substrates to obtain stable superhydrophobic coatings after curing. The water contact angle (WCA) on the hybrid coating is influenced by the content of Al2O3 particles in the coating. As the Al2O3 concentration in the coating was increased from 0% to 8%, WCA increased from 68° to 165°. Surface topography of the coatings was examined using scanning electron microscopy (SEM). Nano-particles covered on the coating surface formed continuous film with greatly enhanced roughness, which was found to be responsible for the superhydrophobicity. The method is simple and cost effective and can be used for preparing self-cleaning superhydrophobic coating on large areas.

Low Ozone in the Marine Boundary Layer of the Tropical Pacific Ocean

NASA Technical Reports Server (NTRS)

Singh, Hanwant B.; Gregory, G. L.; Andesrson, B.; Browell, E.; Sachse, G. W.; Davis, D. D.; Crawford, J.; Bradshaw, J. D.; Talbot, R.; Blake, D. R.;

Nonmethane hydrocarbons and ozone in three rural southeast United States national parks: A model sensitivity analysis and comparison to measurements

NASA Astrophysics Data System (ADS)

Kang, Daiwen; Aneja, Viney P.; Mathur, Rohit; Ray, John D.

2003-10-01

A detailed modeling analysis is conducted focusing on nonmethane hydrocarbons and ozone in three southeast United States national parks for a 15-day time period (14-29 July 1995) characterized by high O3 surface concentrations. The three national parks are Smoky Mountains National Park (GRSM), Mammoth Cave National Park (MACA), and Shenandoah National Park (SHEN), Big Meadows. A base emission scenario and eight variant predictions are analyzed, and predictions are compared with data observed at the three locations for the same time period. Model-predicted concentrations are higher than observed values for O3 (with a cutoff of 40 ppbv) by 3.0% at GRSM, 19.1% at MACA, and 9.0% at SHEN (mean normalized bias error). They are very similar to observations for overall mean ozone concentrations at GRSM and SHEN. They generally agree (the same order of magnitude) with observed values for lumped paraffin compounds but are an order of magnitude lower for other species (isoprene, ethene, surrogate olefin, surrogate toluene, and surrogate xylene). Model sensitivity analyses here indicate that each location differs in terms of volatile organic compound (VOC) capacity to produce O3, but a maximum VOC capacity point (MVCP) exists at all locations that changes the influence of VOCs on O3 from net production to production suppression. Analysis of individual model processes shows that more than 50% of daytime O3 concentrations at the high-elevation rural locations (GRSM and SHEN) are transported from other areas; local chemistry is the second largest O3 contributor. At the low-elevation location (MACA), about 80% of daytime O3 is produced by local chemistry and 20% is transported from other areas. Local emissions (67-95%) are predominantly responsible for VOCs at all locations, the rest coming from transport. Chemistry processes are responsible for about 50% removal of VOCs for all locations; less than 10% are lost to surface deposition and the rest are exported to other areas. Metrics, such as VOC potential for O3 production (VPOP), which links the chemistry processes of both O3 and VOCs and MVCP, are devised to measure the different characteristics of O3 production and VOCs. The values of the defined metrics are mapped for the entire modeling domain. Implications of this model exercise in understanding O3 production are analyzed and discussed. Even though this study was focused on three United States national parks, the research results and conclusions may be applicable to other or to similar rural environments in the southeast United States.

Impact of future land-cover changes on HNO3 and O3 surface dry deposition

NASA Astrophysics Data System (ADS)

Verbeke, T.; Lathière, J.; Szopa, S.; de Noblet-Ducoudré, N.

2015-12-01

Dry deposition is a key component of surface-atmosphere exchange of compounds, acting as a sink for several chemical species. Meteorological factors, chemical properties of the trace gas considered and land surface properties are strong drivers of dry deposition efficiency and variability. Under both climatic and anthropogenic pressure, the vegetation distribution over the Earth has been changing a lot over the past centuries and could be significantly altered in the future. In this study, we perform a modeling investigation of the potential impact of land-cover changes between the present day (2006) and the future (2050) on dry deposition velocities at the surface, with special interest for ozone (O3) and nitric acid (HNO3), two compounds which are characterized by very different physicochemical properties. The 3-D chemistry-transport model LMDz-INCA is used, considering changes in vegetation distribution based on the three future projections, RCPs 2.6, 4.5 and 8.5, and present-day (2007) meteorology. The 2050 RCP 8.5 vegetation distribution leads to a rise of up to 7 % (+0.02 cm s-1) in the surface deposition velocity calculated for ozone (Vd,O3) and a decrease of -0.06 cm s-1 in the surface deposition velocity calculated for nitric acid (Vd,HNO3) relative to the present-day values in tropical Africa and up to +18 and -15 %, respectively, in Australia. When taking into account the RCP 4.5 scenario, which shows dramatic land-cover change in Eurasia, Vd,HNO3 increases by up to 20 % (annual-mean value) and reduces Vd,O3 by the same magnitude in this region. When analyzing the impact of surface dry deposition change on atmospheric chemical composition, our model calculates that the effect is lower than 1 ppb on annual-mean surface ozone concentration for both the RCP 8.5 and RCP 2.6 scenarios. The impact on HNO3 surface concentrations is more disparate between the two scenarios regarding the spatial repartition of effects. In the case of the RCP 4.5 scenario, a significant increase of the surface O3 concentration reaching locally by up to 5 ppb (+5 %) is calculated on average during the June-August period. This scenario also induces an increase of HNO3 deposited flux exceeding locally 10 % for monthly values. Comparing the impact of land-cover change to the impact of climate change, considering a 0.93 °C increase of global temperature, on dry deposition velocities, we estimate that the strongest increase over lands occurs in the Northern Hemisphere during winter, especially in Eurasia, by +50 % (+0.07 cm s-1) for Vd,O3 and +100 % (+0.9 cm s-1) for Vd,HNO3. However, different regions are affected by both changes, with climate change impact on deposition characterized by a latitudinal gradient, while the land-cover change impact is much more heterogeneous depending on vegetation distribution modification described in the future RCP scenarios. The impact of long-term land-cover changes on dry deposition is shown to be significant and to differ strongly from one scenario to another. It should therefore be considered in biosphere-atmospheric chemistry interaction studies in order to have a fully consistent picture.

Manganese-cerium oxide catalysts prepared by non-thermal plasma for NO oxidation: Effect of O2 in discharge atmosphere

NASA Astrophysics Data System (ADS)

Liu, Lu; Zheng, Chenghang; Wu, Shenghao; Gao, Xiang; Ni, Mingjiang; Cen, Kefa

2017-09-01

Non-thermal plasma with different O2 concentration in discharge atmosphere was applied to synthesize manganese and cerium mixed-oxides catalysts, which were compared in NO oxidation activity. Discharge atmosphere displayed a crucial influence on the performance of the catalysts prepared by plasma. Relatively low O2 concentration in discharge atmosphere allows synthesizing manganese-cerium oxides catalysts in a moderate environment and therefore is favorable for better physicochemical properties which lead to superior catalytic behavior. The best catalyst was obtained by treatment with 10% O2/N2 plasma and presented over 80% NO conversion in the temperature range of 275-325 °C, whereas catalyst prepared in pure O2 discharge atmosphere had the same activity with a catalyst prepared by calcinations. A correlation between the surface properties of the plasma prepared catalysts and its catalytic activity in NO oxidation is proposed. The amount of the surface adsorbed oxygen has an obvious linear correlation with the amount of Ce3+, the H2 consumption at low temperatures and the catalytic performance. The superior catalytic performance is mainly attributed to the stronger interaction between manganese oxides and ceria, and the formation of poorly crystallized Mn-O-Ce phase in the catalyst which resulted from the slow decomposition of nitrates and organics during plasma treatment. Catalysts prepared in relatively low O2 concentration have large specific surface area and is abundant in Ce3+ species and active oxygen species. The study suggests that plasma treatment with proper discharge gas components is a promising method to prepare effective manganese- cerium oxides catalyst for NO oxidation.

Concentration specific and tunable photoresponse of bismuth vanadate functionalized hexagonal ZnO nanocrystals based photoanodes for photoelectrochemical application

NASA Astrophysics Data System (ADS)

Singh, Sonal; Ruhela, Aakansha; Rani, Sanju; Khanuja, Manika; Sharma, Rishabh

2018-02-01

In the present work, dual layer BiVO4/ZnO photoanode is instigated for photo-electrochemical (PEC) water splitting applications. Two different photocatalytic layers ZnO and BiVO4, reduces charge carrier recombination and charge transfer resistance at photoanode/electrolyte junction. The concentration-specific, tunable and without 'spike and overshoot' features, photocurrent density response is originated by varying BiVO4 concentration in the BiVO4/ZnO photoanode. The crystal structure of ZnO (hexagonal wurtzite structure) and BiVO4 (monoclinic scheelite structure) is confirmed by X-ray diffraction studies. The band gap of BiVO4/ZnO was estimated to be ca. 2.42 eV through Kubler-Munk function F(R∞) using diffuse reflectance spectroscopy. Electrochemical behavior of samples was analyzed with photocurrent measurements, electrochemical impedance, Mott-Schottky plots, bulk separation efficiency and surface transfer efficiency. The maximum photocurrent density of BiVO4/ZnO photoanode was found to be 2.3 times higher than pristine ZnO sample.0.038 M BiVO4/ZnO exhibited the highest separation efficiency of 72% and surface transfer efficiency of 64.7% at +1.23 V vs. RHE. Mott-Schottky study revealed the maximum charge carrier density in the same sample.

Rapid fabrication of superhydrophobic Al/Fe2O3 nanothermite film with excellent energy-release characteristics and long-term storage stability

NASA Astrophysics Data System (ADS)

Ke, Xiang; Zhou, Xiang; Hao, Gaozi; Xiao, Lei; Liu, Jie; Jiang, Wei

2017-06-01

One of the challenges for the application of energetic materials is their energy-retaining capabilities after long-term storage. In this study, we report a facile method to fabricate superhydrophobic Al/Fe2O3 nanothermite film by combining electrophoretic deposition and surface modification technologies. Different concentrations of dispersion solvents and additives are investigated to optimize the deposition parameters. Meanwhile, the dependence of deposition rates on nanoparticle concentrations is also studied. The surface morphology and chemical composition are characterized by field-emission scanning electron microscopy, X-ray diffraction, X-ray energy-dispersive spectroscopy, and X-ray photoelectron spectroscopy. A static contact angles as high as 156° shows the superhydrophobicity of the nanothermite film. Natural and accelerated aging tests are performed and the thermal behavior is analyzed. Thermal analysis shows that the surface modification contributes to significantly improved energy-release characteristics for both fresh and aged samples, which is supposed to be attributed to the preignition reaction between Al2O3 shell and FAS-17. Superhydrophobic Al/Fe2O3 nanothermite film exhibits excellent long-time storage stability with 83.4% of energy left in natural aging test and 60.5% in accelerated aging test. This study is instructive to the practical applications of nanothermites, especially in highly humid environment.

Structural, morphological and Raman studies on hybridized PVDF/BaTiO3 nanocomposites

NASA Astrophysics Data System (ADS)

Rajamanickam, N.; Jayakumar, K.; Ramachandran, K.

2017-05-01

Hybridized nanocomposites of polyvinylidene fluoride (PVDF) and nano - barium titanate (BaTiO3) were prepared using the solution casting method for different concentrations of nano-BaTiO3 and were characterized by X-ray diffraction and scanning electron microscopy. The flower like structure for morphology was observed in SEM. Raman analysis showed that the modified BaTiO3 particles, due to higher specific surfaces, induce, predominantly, the crystallization of the electrically active β-phase of PVDF, while the initial micron size particles induce the formation of the most common but non-polar α-crystal form.

Electrochemically deposited gallium oxide nanostructures on silicon substrates

PubMed Central

2014-01-01

We report a synthesis of β-Ga2O3 nanostructures on Si substrate by electrochemical deposition using a mixture of Ga2O3, HCl, NH4OH, and H2O. The presence of Ga3+ ions contributed to the deposition of Ga2O3 nanostructures on the Si surface with the assistance of applied potentials. The morphologies of the grown structures strongly depended on the molarity of Ga2O3 and pH level of electrolyte. β-Ga2O3 nanodot-like structures were grown on Si substrate at a condition with low molarity of Ga2O3. However, Ga2O3 nanodot structures covered with nanorods on top of their surfaces were obtained at higher molarity, and the densities of nanorods seem to increase with the decrease of pH level. High concentration of Ga3+ and OH- ions may promote the reaction of each other to produce Ga2O3 nanorods in the electrolyte. Such similar nature of Ga2O3 nanorods was also obtained by using hydrothermal process. The grown structures seem to be interesting for application in electronic and optoelectronic devices as well as to be used as a seed structure for subsequent chemical synthesis of GaN by thermal transformation method. PMID:24629107

Preparation of a Superhydrophobic and Peroxidase-like Activity Array Chip for H2O2 Sensing by Surface-Enhanced Raman Scattering.

PubMed

Yu, Zhi; Park, Yeonju; Chen, Lei; Zhao, Bing; Jung, Young Mee; Cong, Qian

2015-10-28

In this paper, we propose a novel and simple method for preparing a dual-biomimetic functional array possessing both superhydrophobic and peroxidase-like activity that can be used for hydrogen peroxide (H2O2) sensing. The proposed method is an integration innovation that combines the above two properties and surface-enhanced Raman scattering (SERS). We integrated a series of well-ordered arrays of Au points (d = 1 mm) onto a superhydrophobic copper (Cu)/silver (Ag) surface by replicating an arrayed molybdenum template. Instead of using photoresists and the traditional lithography method, we utilized a chemical etching method (a substitution reaction between Cu and HAuCl4) with a Cu/Ag superhydrophobic surface as the barrier layer, which has the benefit of water repellency. The as-prepared Au points were observed to possess peroxidase-like activity, allowing for catalytic oxidation of the chromogenic molecule o-phenylenediamine dihydrochloride (OPD). Oxidation was evidenced by a color change in the presence of H2O2, which allows the array chip to act as an H2O2 sensor. In this study, the water repellency of the superhydrophobic surface was used to fabricate the array chip and increase the local reactant concentration during the catalytic reaction. As a result, the catalytic reaction occurred when only 2 μL of an aqueous sample (OPD/H2O2) was placed onto the Au point, and the enzymatic product, 2,3-diaminophenazine, showed a SERS signal distinguishable from that of OPD after mixing with 2 μL of colloidal Au. Using the dual-biomimetic functional array chip, quantitative analysis of H2O2 was performed by observing the change in the SERS spectra, which showed a concentration-dependent behavior for H2O2. This method allows for the detection of H2O2 at concentrations as low as 3 pmol per 2 μL of sample, which is a considerable advantage in H2O2 analysis. The as-prepared substrate was convenient for H2O2 detection because only a small amount of sample was required in each analysis. Highly sensitive detection was realized using SERS. Therefore, this chip was shown to exhibit significant potential for applications in bioanalysis.

The effect of O2 content on the corrosion behaviour of X65 and 5Cr in water-containing supercritical CO2 environments

NASA Astrophysics Data System (ADS)

Hua, Yong; Barker, Richard; Neville, Anne

2015-11-01

The general and localized corrosion behaviour of X65 carbon steel and 5Cr low alloy steel were evaluated in a water-saturated supercritical CO2 environment in the presence of varying concentrations of O2. Experiments were performed at a temperature of 35 °C and a pressure of 80 bar to simulate the conditions encountered during CO2 transport and injection. Results indicated that increasing O2 concentration from 0 to 1000 ppm caused a progressive reduction in the general corrosion rate, but served to increase the extent of localized corrosion observed on both materials. Pitting (or localized attack) rates for X65 ranged between 0.9 and 1.7 mm/year, while for 5Cr rose from 0.3 to 1.4 mm/year as O2 concentration was increased from 0 to 1000 ppm. General corrosion rates were over an order of magnitude lower than the pitting rates measured. Increasing O2 content in the presence of X65 and 5Cr suppressed the growth of iron carbonate (FeCO3) on the steel surface and resulted in the formation of a corrosion product consisting mainly of iron oxide (Fe2O3). 5Cr was shown to offer more resistance to pitting corrosion in comparison to X65 steel over the conditions tested. At concentrations of O2 above 500 ppm 5Cr produced general corrosion rates less than 0.04 mm/year, which were half that recorded for X65. The improved corrosion resistance of 5Cr was believed to be at least partially attributed to the formation of a Cr-rich film on the steel surface which was shown using X-ray photoelectron spectroscopy to contain chromium oxide (Cr2O3) and chromium hydroxide (Cr(OH)3). A final series of tests conducted with the addition of 1000 ppm O2 in under-saturated conditions (water content below solubility limit) revealed that no corrosion was observed when the water content was below 1200 ppm for both materials.

Heterogeneous Interactions of ClONO2 and HCl with Sulfuric Acid Tetrahydrate: Implications for the Stratosphere

NASA Technical Reports Server (NTRS)

Zhang, Renyi; Jayne, John T.; Molina, Mario J.

1994-01-01

The reaction probabilities for ClONO2+H2O- HOCl + HNO3 and ClONO2+ HCl Cl2 +HNO3 have been investigated on sulfuric acid tetrahydrate (SAT, H2SO4-4H2O)surfaces at temperatures between 190 and 230 K and at reactant concentrations that are typical in the lower stratosphere, using a fast-flow reactor coupled to a quadrupole mass spectrometer. The results indicate that the reaction probabilities as well as HCl uptake depend strongly on the thermodynamic state of SAT surface: they decrease significantly with decreasing H2O partial pressure at a given temperature, and decrease with increasing temperature at a given H2O partial pressure, as the SAT changes from the H2O-rich form to the H2SO4-rich form. For H2O-rich SAT at 195 K gamma(sub 1) approx. = -0.01 and gamma(sub 2) greater or equal to 0.1, whereas the values for H2SO4-rich SAT decrease by more than 2 orders of magnitude. At low concentrations of HCl, close to those found in the stratosphere, the amount of HCl taken up by H2O-rich SAT films corresponds to a coverage of the order of a tenth of a monolayer (approx. = 10(exp 14) molecules/sq cm); H2SO4-rich SAT films take up 2 orders of magnitude less HCl (les than 10(exp 12) molecules/sq cm). Substantial HCl uptake at high HCl concentrations is also observed, as a result of surface melting. The data reveal that frozen stratospheric sulfate aerosols may play an important role in chlorine activation in the winter polar stratosphere via processes similar to those occurring on the surfaces of polar stratospheric cloud particles.

Sodium Aluminate Concentration Effects on Microstructure and Corrosion Behavior of the Plasma Electrolytic Oxidation Coatings on Pure Titanium

NASA Astrophysics Data System (ADS)

Molaei, Maryam; Fattah-Alhosseini, Arash; Gashti, Seyed Omid

2018-01-01

Sodium aluminate (NaAlO2) concentration was varied in order to understand the influence of the chemical composition of electrolyte on the spark characteristics, microstructure, and corrosion behavior of plasma electrolytic oxidation (PEO) coatings. For this purpose, PEO coatings were formed on the pure titanium substrate surface using solutions of four diverse sodium aluminate concentrations (6, 8, 10, and 12 g/L). The PEO process was carried out at constant time and voltage (180 seconds and 420 V). Studying the microstructures of samples by scanning electron microscope (SEM) and their corrosion behavior in 3.5 wt pct NaCl solutions indicated that the increase in NaAlO2 concentration (up to 10 g/L) led to an increase in uniformity and compactness, thus decreasing the size of micro-pores and increment of corrosion resistance. However, at a certain level of NaAlO2 concentration (12 g/L), large and severe sparks were created on the surface of the sample during the process, worsening the corrosion resistance and microstructure of coating.

Excess titanium dioxide nanoparticles on the cell surface induce cytotoxicity by hindering ion exchange and disrupting exocytosis processes

NASA Astrophysics Data System (ADS)

Wang, Yanli; Yao, Chenjie; Li, Chenchen; Ding, Lin; Liu, Jian; Dong, Peng; Fang, Haiping; Lei, Zhendong; Shi, Guosheng; Wu, Minghong

2015-07-01

To date, considerable effort has been devoted to determine the potential toxicity of nanoparticles to cells and organisms. However, determining the mechanism of cytotoxicity induced by different types of nanoparticles remains challenging. Herein, typically low toxicity nanomaterials were used as a model to investigate the mechanism of cytotoxicity induced by low toxicity nanomaterials. We studied the effect of nano-TiO2, nano-Al2O3 and nano-SiO2 deposition films on the ion concentration on a cell-free system simulating the cell membrane. The results showed that the ion concentration of K+, Ca2+, Na+, Mg2+ and SO42- decreased significantly following filtration of the prepared deposition films. More specifically, at a high nano-TiO2 concentration (200 mg L-1) and a long nano-TiO2 deposition time (48 h), the concentration of Na+ decreased from 2958.01 to 2775.72, 2749.86, 2757.36, and 2719.82 mg L-1, respectively, for the four types of nano-TiO2 studied. Likewise, the concentration of SO42- decreased from 38.83 to 35.00, 35.80, 35.40, and 35.27 mg L-1, respectively. The other two kinds of typical low toxicity nanomaterials (nano-Al2O3 and nano-SiO2) have a similar impact on the ion concentration change trend. Adsorption of ions on nanoparticles and the hydrated shell around the ions strongly hindered the ions through the nanoparticle films. The endocytosed nanoparticles could be released from the cells without inducing cytotoxicity. Hindering the ion exchange and disrupting the exocytosis process are the main factors that induce cytotoxicity in the presence of excess nano-TiO2 on the cell surface. The current findings may offer a universal principle for understanding the mechanism of cytotoxicity induced by low toxicity nanomaterials.To date, considerable effort has been devoted to determine the potential toxicity of nanoparticles to cells and organisms. However, determining the mechanism of cytotoxicity induced by different types of nanoparticles remains challenging. Herein, typically low toxicity nanomaterials were used as a model to investigate the mechanism of cytotoxicity induced by low toxicity nanomaterials. We studied the effect of nano-TiO2, nano-Al2O3 and nano-SiO2 deposition films on the ion concentration on a cell-free system simulating the cell membrane. The results showed that the ion concentration of K+, Ca2+, Na+, Mg2+ and SO42- decreased significantly following filtration of the prepared deposition films. More specifically, at a high nano-TiO2 concentration (200 mg L-1) and a long nano-TiO2 deposition time (48 h), the concentration of Na+ decreased from 2958.01 to 2775.72, 2749.86, 2757.36, and 2719.82 mg L-1, respectively, for the four types of nano-TiO2 studied. Likewise, the concentration of SO42- decreased from 38.83 to 35.00, 35.80, 35.40, and 35.27 mg L-1, respectively. The other two kinds of typical low toxicity nanomaterials (nano-Al2O3 and nano-SiO2) have a similar impact on the ion concentration change trend. Adsorption of ions on nanoparticles and the hydrated shell around the ions strongly hindered the ions through the nanoparticle films. The endocytosed nanoparticles could be released from the cells without inducing cytotoxicity. Hindering the ion exchange and disrupting the exocytosis process are the main factors that induce cytotoxicity in the presence of excess nano-TiO2 on the cell surface. The current findings may offer a universal principle for understanding the mechanism of cytotoxicity induced by low toxicity nanomaterials. Electronic supplementary information (ESI) available: Nano-TiO2 characterization; changes in nucleus morphology; apoptosis assay; variations in Ca2+; schematic of the experiment to simulate ion exchange; TEM images; ion concentration change after being filtered through the nano-deposition films; theoretical simulation methods; ROS generation; intercellular communication; the movie shows the process of Na+ in the films. See DOI: 10.1039/c5nr03269e

Air quality models and unusually large ozone increases: Identifying model failures, understanding environmental causes, and improving modeled chemistry

NASA Astrophysics Data System (ADS)

Couzo, Evan A.

Several factors combine to make ozone (O3) pollution in Houston, Texas, unique when compared to other metropolitan areas. These include complex meteorology, intense clustering of industrial activity, and significant precursor emissions from the heavily urbanized eight-county area. Decades of air pollution research have borne out two different causes, or conceptual models, of O 3 formation. One conceptual model describes a gradual region-wide increase in O3 concentrations "typical" of many large U.S. cities. The other conceptual model links episodic emissions of volatile organic compounds to spatially limited plumes of high O3, which lead to large hourly increases that have exceeded 100 parts per billion (ppb) per hour. These large hourly increases are known to lead to violations of the federal O 3 standard and impact Houston's status as a non-attainment area. There is a need to further understand and characterize the causes of peak O 3 levels in Houston and simulate them correctly so that environmental regulators can find the most cost-effective pollution controls. This work provides a detailed understanding of unusually large O 3 increases in the natural and modeled environments. First, we probe regulatory model simulations and assess their ability to reproduce the observed phenomenon. As configured for the purpose of demonstrating future attainment of the O3 standard, the model fails to predict the spatially limited O3 plumes observed in Houston. Second, we combine ambient meteorological and pollutant measurement data to identify the most likely geographic origins and preconditions of the concentrated O3 plumes. We find evidence that the O3 plumes are the result of photochemical activity accelerated by industrial emissions. And, third, we implement changes to the modeled chemistry to add missing formation mechanisms of nitrous acid, which is an important radical precursor. Radicals control the chemical reactivity of atmospheric systems, and perturbations to radical budgets can shift chemical pathways. The mechanism additions increase the concentrations of nitrous acid, especially right after sunrise. The overall effect on O3 is small (up to three ppb), but we demonstrate the successful implementation of a surface sub-model that chemically processes adsorbed compounds. To our knowledge, this is the first time that chemical processing on surfaces has been used in a three-dimensional regulatory air quality model.

Effect of operational and water quality parameters on conventional ozonation and the advanced oxidation process O3/H2O2: Kinetics of micropollutant abatement, transformation product and bromate formation in a surface water.

PubMed

Bourgin, Marc; Borowska, Ewa; Helbing, Jakob; Hollender, Juliane; Kaiser, Hans-Peter; Kienle, Cornelia; McArdell, Christa S; Simon, Eszter; von Gunten, Urs

2017-10-01

The efficiency of ozone-based processes under various conditions was studied for the treatment of a surface water (Lake Zürich water, Switzerland) spiked with 19 micropollutants (pharmaceuticals, pesticides, industrial chemical, X-ray contrast medium, sweetener) each at 1 μg L -1 . Two pilot-scale ozonation reactors (4-5 m 3  h -1 ), a 4-chamber reactor and a tubular reactor, were investigated by either conventional ozonation and/or the advanced oxidation process (AOP) O 3 /H 2 O 2 . The effects of selected operational parameters, such as ozone dose (0.5-3 mg L -1 ) and H 2 O 2 dose (O 3 :H 2 O 2  = 1:3-3:1 (mass ratio)), and selected water quality parameters, such as pH (6.5-8.5) and initial bromide concentration (15-200 μg L -1 ), on micropollutant abatement and bromate formation were investigated. Under the studied conditions, compounds with high second-order rate constants k O3 >10 4  M -1  s -1 for their reaction with ozone were well abated (>90%) even for the lowest ozone dose of 0.5 mg L -1 . Conversely, the abatement efficiency of sucralose, which only reacts with hydroxyl radicals (OH), varied between 19 and 90%. Generally, the abatement efficiency increased with higher ozone doses and higher pH and lower bromide concentrations. H 2 O 2 addition accelerated the ozone conversion to OH, which enables a faster abatement of ozone-resistant micropollutants. Interestingly, the abatement of micropollutants decreased with higher bromide concentrations during conventional ozonation due to competitive ozone-consuming reactions, except for lamotrigine, due to the suspected reaction of HOBr/OBr - with the primary amine moieties. In addition to the abatement of micropollutants, the evolution of the two main transformation products (TPs) of hydrochlorothiazide (HCTZ) and tramadol (TRA), chlorothiazide (CTZ) and tramadol N-oxide (TRA-NOX), respectively, was assessed by chemical analysis and kinetic modeling. Both selected TPs were quickly formed initially to reach a maximum concentration followed by a decrease of their concentrations for longer contact times. For the studied conditions, the TP's concentrations at the outlet of the reactors ranged from 0 to 61% of the initial parent compound concentration, CTZ being a more persistent TP against further oxidation than TRA-NOX. Finally, it was demonstrated in both reactors that the formation of bromate (BrO 3 - ), a potentially carcinogenic oxidation by-product, could be controlled by H 2 O 2 addition with a general improvement on micropollutant abatement. Post-treatment by granular activated carbon (GAC) filtration enabled the reduction of micropollutants and TPs concentrations but no changes in bromate were observed. The combined algae assay showed that water quality was significantly improved after oxidation and GAC post-treatment, driven by the abatement of the spiked pesticides (diuron and atrazine). Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis and characterization of SiO2/(PMMA/Fe3O4) magnetic nanocomposites.

PubMed

Wang, Zhifei; Guo, Yafei; Li, Song; Sun, Yueming; He, Nongyue

2008-04-01

Magnetic silica nanocomposites (magnetic nanoparticles core coated by silica shell) have the wide promising applications in the biomedical field and usually been prepared based on the famous Stöber process. However, the flocculation of Fe3O4 nanoparticles easily occurs during the silica coating, which limits the amount of magnetic silica particles produced in the Stöber process. In this paper, PMMA/Fe3O4 nanoparticles were used in the Stöber process instead of the "nude" Fe3O4 nanoparticles. And coating Fe3O4 with PMMA polymer beforehand can prevent magnetic nanoparticles from the aggregation that usually comes from the increasing of ionic strength during the hydrolyzation of tetraethoxysilane (TEOS) by the steric hindrance. The results show that the critical concentration of magnetic nanoparticles can increase from 12 mg/L for "nude" Fe3O4 nanoparticles to 3 g/L for PMMA/Fe3O4 nanoparticles during the Stöber process. And before the deposition of silica shell, the surface of PMMA/FeO4 nanoparticles had to be further modified by hydrolyzing them in CH3OH/NH3 x H2O mixture solution, which provides the carboxyl groups on their surface to react further with the silanol groups of silicic acid.

Surface modification of Polycaprolactone (PCL) microcarrier for performance improvement of human skin fibroblast cell culture

NASA Astrophysics Data System (ADS)

Samsudin, N.; Hashim, Y. Z. H.; Arifin, M. A.; Mel, M.; Salleh, H. Mohd; Sopyan, I.; Hamid, M. Abdul

2018-01-01

Polycaprolactone (PCL) has many advantages for use in biomedical engineering field. In the present work PCL microcarriers of 150-200 μm were fabricated using oil-in-water (o/w) emulsification coupled with solvent evaporation method. The surface charge of PCL microcarrier was then been improved by using ultraviolet/ozone treatment to introduce oxygen functional group. Immobilisation of gelatin onto PCL microspheres using zero-length crosslinker provides a stable protein-support complex, with no diffusional barrier which is ideal for mass processing. The optimum concentration of carboxyl group (COOH) absorbed on the surface was 1495.9 nmol/g and the amount of gelatin immobilized was 1797.3 μg/g on UV/O3 treated microcarriers as compared to the untreated (320 μg/g) microcarriers. The absorption of functional oxygen groups on the surface and the immobilized gelatin was confirmed with Fourier Transformed Infrared spectroscopy and the enhancement of hydrophilicity of the surface was confirmed using water contact angle measurement which decreased (86.93° - 49.34°) after UV/O3 treatment and subsequently after immobilisation of gelatin. The attachment and growth kinetics for human skin fibroblast cell (HSFC) showed that adhesion occurred much more rapidly for gelatin immobilised surface as compared to untreated PCL and UV/O3 PCL microcarrier.

Microstructure evolution and electrical characterization of Lanthanum doped Barium Titanate (BaTiO{sub 3}) ceramics

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

Billah, Masum, E-mail: masum.buet09@gmail.com; Ahmed, A., E-mail: jhinukbuetmme@gmail.com; Rahman, Md. Miftaur, E-mail: miftaurrahman@mme.buet.ac.bd

2016-07-12

In the current work, we investigated the structural and dielectric properties of Lanthanum oxide (La{sub 2}O{sub 3}) doped Barium Titanate (BaTiO{sub 3}) ceramics and established a correlation between them. Solid state sintering method was used to dope BaTiO{sub 3} with 0.3, 0.5 and 0.7 mole% La{sub 2}O{sub 3} under different sintering parameters. The raw materials used were La{sub 2}O{sub 3} nano powder of ~80 nm grain size and 99.995% purity and BaTiO{sub 3} nano powder of 100 nm grain size and 99.99% purity. Grain size distribution and morphology of fracture surface of sintered pellets were examined by Field Emission Scanningmore » Electron Microscope and X-Ray Diffraction analysis was conducted to confirm the formation of desired crystal structure. The research result reveal that grain size and electrical properties of BaTiO{sub 3} ceramic significantly enhanced for small amount of doping (up to 0.5 mole% La{sub 2}O{sub 3}) and then decreased with increasing doping concentration. Desired grain growth (0.80-1.3 µm) and high densification (<90% theoretical density) were found by proper combination of temperature, sintering parameters and doping concentration. We found the resultant stable value of dielectric constant was 10000-12000 at 100-300 Hz in the temperature range of 30°-50° C for 0.5 mole% La{sub 2}O{sub 3} with corresponding shift of curie temperature around 30° C. So overall this research showed that proper La{sup 3+} concentration can control the grain size, increase density, lower curie temperature and hence significantly improve the electrical properties of BaTiO{sub 3} ceramics.« less

Synthesis and characterization of Co3O4 prepared from atmospheric pressure acid leach liquors of nickel laterite ores

NASA Astrophysics Data System (ADS)

Meng, Long; Guo, Zhan-cheng; Qu, Jing-kui; Qi, Tao; Guo, Qiang; Hou, Gui-hua; Dong, Peng-yu; Xi, Xin-guo

2018-01-01

A chemical precipitation-thermal decomposition method was developed to synthesize Co3O4 nanoparticles using cobalt liquor obtained from the atmospheric pressure acid leaching process of nickel laterite ores. The effects of the precursor reaction temperature, the concentration of Co2+, and the calcination temperature on the specific surface area, morphology, and the electrochemical behavior of the obtained Co3O4 particles were investigated. The precursor basic cobaltous carbonate and cobaltosic oxide products were characterized and analyzed by Fourier transform infrared spectroscopy, thermogravimetric differential thermal analysis, X-ray diffraction, field-emission scanning electron microscopy, specific surface area analysis, and electrochemical analysis. The results indicate that the specific surface area of the Co3O4 particles with a diameter of 30 nm, which were obtained under the optimum conditions of a precursor reaction temperature of 30°C, 0.25 mol/L Co2+, and a calcination temperature of 350°C, was 48.89 m2/g. Electrodes fabricated using Co3O4 nanoparticles exhibited good electrochemical properties, with a specific capacitance of 216.3 F/g at a scan rate of 100 mV/s.

Synergy of iron and copper oxides in the catalytic formation of PCDD/Fs from 2-monochlorophenol.

PubMed

Potter, Phillip M; Guan, Xia; Lomnicki, Slawomir M

2018-07-01

Transition metal oxides present in waste incineration systems have the ability to catalyze the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) through surface reactions involving organic dioxin precursors. However, studies have concentrated on the catalytic effects of individual transition metal oxides, while the complex elemental composition of fly ash introduces the possibility of synergistic or inhibiting effects between multiple, catalytically active components. In this study, we have tested fly ash surrogates containing different ratios (by weight) of iron (III) oxide and copper (II) oxide. Such Fe 2 O 3 /CuO mixed-oxide surrogates (in the Fe:Cu ratio of 3.5, 0.9 and 0.2 ) were used to study the cooperative effects between two transition metals that are present in high concentrations in most combustion systems and are known to individually catalyze the formation of PCDD/Fs. The presence of both iron and copper oxides increased the oxidative power of the fly ash surrogates in oxygen rich conditions and led to extremely high PCDD/F yields under pyrolytic conditions (up to >5% yield) from 2-monochlorophenol precursor. PCDD/F congener profiles from the mixed oxide samples are similar to results obtained from only CuO, however the total PCDD/F yield increases with increasing Fe 2 O 3 content. Careful analysis of the reaction products and changes to the oxidation states of active metals indicate the CuO surface sites are centers for reaction while the Fe 2 O 3 is affecting the bonds in CuO and increasing the ability of copper centers to form surface-bound radicals that are precursors to PCDD/Fs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Springtime high surface ozone events over the western United States: Quantifying the role of stratospheric intrusions

NASA Astrophysics Data System (ADS)

Fiore, A. M.; Lin, M.; Cooper, O. R.; Horowitz, L. W.; Naik, V.; Levy, H.; Langford, A. O.; Johnson, B. J.; Oltmans, S. J.; Senff, C. J.

2011-12-01

As the National Ambient Air Quality (NAAQS) standard for ozone (O_{3}) is lowered, it pushes closer to policy-relevant background levels (O_{3} concentrations that would exist in the absence of North American anthropogenic emissions), making attainment more difficult with local controls. We quantify the Asian and stratospheric components of this North American background, with a primary focus on the western United States. Prior work has identified this region as a hotspot for deep stratospheric intrusions in spring. We conduct global simulations at 200 km and 50 km horizontal resolution with the GFDL AM3 model, including a stratospheric O_{3} tracer and two sensitivity simulations with anthropogenic emissions from Asia and North America turned off. The model is evaluated with a suite of in situ and satellite measurements during the NOAA CalNex campaign (May-June 2010). The model reproduces the principle features in the observed surface to near tropopause distribution of O_{3} along the California coast, including its latitudinal variation and the development of regional high-O_{3} episodes. Four deep tropopause folds are diagnosed and we find that the remnants of these stratospheric intrusions are transported to the surface of Southern California and Western U.S. Rocky Mountains, contributing 10-30 ppbv positive anomalies relative to the simulated campaign mean stratospheric component in the model surface layer. We further examine the contribution of North American background, including its stratospheric and Asian components, to the entire distribution of observed MDA8 O_{3} at 12 high-elevation CASTNet sites in the Mountain West. We find that the stratospheric O_{3} tracer constitutes 50% of the North American background, and can enhance surface maximum daily 8-hour average (MDA8) O_{3} by 20 ppb when observed surface O_{3} is in the range of 60-80 ppbv. Our analysis highlights the potential for natural sources such as deep stratospheric intrusions to contribute to high surface O_{3} episodes in the western U.S., representing a major challenge if the NAAQS were to be tightened. We further demonstrate the potential for using satellite (AIRS and OMI) measurements of total column O_{3} to develop space-based criteria to define these exceptional events in support of regional air quality management.

Experimental and Computational Evidence of Highly Active Fe Impurity Sites on the Surface of Oxidized Au for the Electrocatalytic Oxidation of Water in Basic Media

DOE PAGES

Klaus, Shannon; Trotochaud, Lena; Cheng, Mu-Jeng; ...

2015-10-22

Addition of Fe to Ni- and Co-based (oxy)hydroxides has been shown to enhance the activity of these materials for electrochemical oxygen evolution. Here we show that Fe cations bound to the surface of oxidized Au exhibit enhanced oxygen evolution reaction (OER) activity. We find that the OER activity increases with increasing surface concentration of Fe. Density functional theory analysis of the OER energetics reveals that oxygen evolution over Fe cations bound to a hydroxyl-terminated oxidized Au (Fe-Au 2O 3) occurs at an overpotential ~0.3V lower than over hydroxylated Au 2O 3 (0.82V). This finding agrees well with experimental observations andmore » is a consequence of the more optimal binding energetics of OER reaction intermediates at Fe cations bound to the surface of Au 2O 3. These findings suggest that the enhanced OER activity reported recently upon low-potential cycling of Au may be due to surface Fe impurities rather than to "superactive" Au(III) surfaquo species.« less

A New Strategy for Humidity Independent Oxide Chemiresistors: Dynamic Self-Refreshing of In2 O3 Sensing Surface Assisted by Layer-by-Layer Coated CeO2 Nanoclusters.

PubMed

Yoon, Ji-Wook; Kim, Jun-Sik; Kim, Tae-Hyung; Hong, Young Jun; Kang, Yun Chan; Lee, Jong-Heun

2016-08-01

The humidity dependence of the gas sensing characteristics of metal oxide semiconductors has been one of the greatest obstacles for gas sensor applications during the last five decades because ambient humidity dynamically changes with the environmental conditions. Herein, a new and novel strategy is reported to eliminate the humidity dependence of the gas sensing characteristics of oxide chemiresistors via dynamic self-refreshing of the sensing surface affected by water vapor chemisorption. The sensor resistance and gas response of pure In2 O3 hollow spheres significantly change and deteriorate in humid atmospheres. In contrast, the humidity dependence becomes negligible when an optimal concentration of CeO2 nanoclusters is uniformly loaded onto In2 O3 hollow spheres via layer-by-layer (LBL) assembly. Moreover, In2 O3 sensors LBL-coated with CeO2 nanoclusters show fast response/recovery, low detection limit (500 ppb), and high selectivity to acetone even in highly humid conditions (relative humidity 80%). The mechanism underlying the dynamic refreshing of the In2 O3 sensing surfaces regardless of humidity variation is investigated in relation to the role of CeO2 and the chemical interaction among CeO2 , In2 O3 , and water vapor. This strategy can be widely used to design high performance gas sensors including disease diagnosis via breath analysis and pollutant monitoring. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Is ozone, rather than PM2.5, actually the largest contributor to premature deaths associated with trans-continental transport of air pollution?

NASA Astrophysics Data System (ADS)

Henze, D. K.; Davila, Y.; Anenberg, S.; Malley, C.; Kuylenstierna, J. C. I.; Vallack, H.; Ashmore, M. R.; Turner, M.; Sudo, K.; Jonson, J. E.; Chin, M.; Doherty, R. M.

2017-12-01

While both ozone and PM2.5 contribute to a range of deleterious human health impacts, evaluations of regional and global burdens of disease associated with exposure to these pollutants have concluded that PM2.5 is the larger driver of premature deaths from degraded air quality. This is owing to both high PM2.5 concentrations in heavily populated areas and stronger concentration-response relationships between PM2.5 exposure and increased mortality risk. Meanwhile, both PM2.5 and O3 are formed and/or advected far downwind of their sources and contribute to long-range (trans-continental) pollution transport. Ozone most often makes greater contributions to long-range pollution transport in terms of percent changes in surface-level concentrations given its longer tropospheric lifetime than PM2.5. Combining these factors, previous works have identified PM2.5 as more frequently being the dominant long-range source of air pollution related premature deaths, closely followed by O3. Here we re-evaluate this question using several updates, drawing from ensembles of model simulations performed as part of Phase 2 of the Hemispheric Transport of Air Pollutants (HTAP) project. Most importantly, we use recently revised concentration-response relationships for respiratory (and, less confidently, cardiovascular) disease associated with long-term O3 exposure, which we have shown increases estimates of premature death owing to O3 several-fold, and integrated exposure response (IER) functions for PM2.5. Further, we attempt to overcome well-recognized biases in estimating PM2.5 exposure with global-scale models via assimilation of high resolution (0.1 x 0.1) maps of surface PM2.5 derived from satellite observations. Overall, we find that our revised estimates of long-range O3 and PM2.5 related premature deaths are most often dominated by O3. These findings provide additional incentives for considering the global-scale consequences of regional emissions controls of O3 precursors.

Different preparation methods and characterization of magnetic maghemite coated with chitosan

NASA Astrophysics Data System (ADS)

Hojnik Podrepšek, Gordana; Knez, Željko; Leitgeb, Maja

2013-06-01

The preparation of maghemite (γ-Fe2O3) micro- and nanoparticles coated with chitosan, used as carriers for immobilized enzymes, was investigated. γ-Fe2O3 nanoparticles were synthesized by coprecipitation of Fe2+ and Fe3+ ions in the presence of ammonium. They were coated with chitosan by the microemulsion process, suspension cross-linking technique, and covalent binding of chitosan on the γ-Fe2O3 surface. The methods distinguished the concentration of chitosan, concentration of acetic acid solution, concentration of a cross-linking agent, temperature of synthesis, pH of the medium, and time of synthesis. γ-Fe2O3 micro- and nanoparticles coated with chitosan prepared after three preparation methods were evaluated by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy analysis, energy dispersive spectrometry, thermogravimetric analysis, differential scanning calorimetry analysis, vibrating sample magnetometry, dynamic light scattering, laser diffraction granulometry, and X-ray diffractometry. These positive attributes demonstrated that these magnetic micro- and nanoparticles coated with chitosan may be used as a promising carrier for further diverse biomedical applications.

Theoretical study of room temperature ferromagnetism and band gap energy of pure and ion doped In2O3 nanoparticles

NASA Astrophysics Data System (ADS)

Apostolov, A. T.; Apostolova, I. N.; Wesselinowa, J. M.

2018-06-01

Using the s-d microscopic model including the electron-phonon interaction and the Green's function theory we have considered the origin of room temperature ferromagnetism (RTFM) in pure and ion doped In2O3 nanoparticles (NPs). The magnetization M increases with decreasing particle size. M of Fe, Tb and Mn doped In2O3 NPs is investigated, which increases, decreases and has a maximum, respectively, with increasing doping concentration. The RTFM is due to surface oxygen vacancies and different ionic radius of the dopants compared to that of the host ions. This differences lead to different strains which changes the exchange interaction constants. We have calculated the dependence of the band gap energy on the particle size in In2O3 NPs and the Fe concentration of Fe doped In2O3 NPs. The results are in good qualitative agreement with the experimental data.

Self-assembled monolayers of mercaptobenzoic acid and magnetite nanoparticles as an efficient support for development of tuberculosis genosensor.

PubMed

Costa, Maurilia P; Andrade, Cesar A S; Montenegro, Rosana A; Melo, Fabio L; Oliveira, Maria D L

2014-11-01

In this work, a genosensor for the electrochemical detection of genomic DNA from Mycobacterium tuberculosis was developed. The biosensor is based on self-assembled monolayers of mercaptobenzoic acid (MBA) and magnetite nanoparticles (Fe3O4Nps) on bare gold electrode for immobilization of DNA probe. The aim of this work was the development of a platform based on cysteine-coated magnetic Fe3O4Nps linked via the carboxylate group from MBA to the work electrode surface and subsequently to the DNA probe. The probe-genome interaction was evaluated using a [Fe(CN)6](4-)/[Fe(CN)6](3-) redox pair. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to evaluate the bioelectrochemical behavior of the sensor. Atomic force microscopy images showed Fe3O4Nps immobilized across the electrode surface. The interaction of the sensor with different genome DNA concentrations resulted in changes in the charge transfer resistance, indicating a possible use for tuberculosis detection at low concentrations (detection limit of 6ngμL(-1)). Copyright © 2014 Elsevier Inc. All rights reserved.

Phosphorus runoff from waste water treatment biosolids and poultry litter applied to agricultural soils.

PubMed

White, John W; Coale, Frank J; Sims, J Thomas; Shober, Amy L

2010-01-01

Differences in the properties of organic phosphorus (P) sources, particularly those that undergo treatment to reduce soluble P, can affect soil P solubility and P transport in surface runoff. This 2-yr field study investigated soil P solubility and runoff P losses from two agricultural soils in the Mid-Atlantic region after land application of biosolids derived from different waste water treatment processes and poultry litter. Phosphorus speciation in the biosolids and poultry litter differed due to treatment processes and significantly altered soil P solubility and dissolved reactive P (DRP) and bioavailable P (FeO-P) concentrations in surface runoff. Runoff total P (TP) concentrations were closely related to sediment transport. Initial runoff DRP and FeO-P concentrations varied among the different biosolids and poultry litter applied. Over time, as sediment transport declined and DRP concentrations became an increasingly important component of runoff FeO-P and TP, total runoff P was more strongly influenced by the type of biosolids applied. Throughout the study, application of lime-stabilized biosolids and poultry litter increased concentrations of soil-soluble P, readily desorbable P, and soil P saturation, resulting in increased DRP and FeO-P concentrations in runoff. Land application of biosolids generated from waste water treatment processes that used amendments to reduce P solubility (e.g., FeCl(3)) did not increase soil P saturation and reduced the potential for DRP and FeO-P transport in surface runoff. These results illustrate the importance of waste water treatment plant process and determination of specific P source coefficients to account for differential P availability among organic P sources.

[Characteristics of Dissolved CH₄ and N₂O Concentrations of Weihe River in Xinxiang Section in Spring].

PubMed

Hou, Cui-cui; Zhang, Fang; Li, Ying-chen; Wang, Qi-bo; Liu, Sai

2016-05-15

Distributions of CH₄ and N₂O concentrations in Weihe River in Xinxiang City were monitored in spring of 2015, and their influencing factors were discussed. The result showed that CH₄ and N₂O were super-saturated in surface water of Weihe River. The variation ranges of two gases' saturations in the surface water of Weihe River were 147.59-2667.85 (CH₄) and 4.06-188.25 (N₂O). In the urban area, significant correlation existed between N₂O and NH₄⁺-N concentrations (P < 0.01), but in the new district, dissolved N₂O concentration showed sharp increase because of the water input from the urban sewage plants, illustrating that the controlling mechanism on N₂O production varied as pollutant characteristics changed. Stepwise regression analysis showed that CH₄ concentrations could be explained by NH₄⁺-N concentrations and water temperature, and CH₄ concentrations in the surface water of Weihe River was significantly correlated with NH₄⁺-N concentrations (R² = 0.70, P < 0.01), suggesting that NH₄⁺-N was the key factor in regulating the production and assumption of CH₄oxidation in Weihe River in spring. Besides, this study showed that when there was less NO₃⁻-N but more NH₄⁺-N in river water, CH₄and N₂O concentrations would be positively correlated, indicating that different nitrogen sources would impact the coupling mechanism of CH₄and N₂O productions.

Comparative investigation of surface transfer doping of hydrogen terminated diamond by high electron affinity insulators

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

Verona, C.; Marinelli, Marco; Verona-Rinati, G.

We report on a comparative study of transfer doping of hydrogenated single crystal diamond surface by insulators featured by high electron affinity, such as Nb{sub 2}O{sub 5}, WO{sub 3}, V{sub 2}O{sub 5}, and MoO{sub 3}. The low electron affinity Al{sub 2}O{sub 3} was also investigated for comparison. Hole transport properties were evaluated in the passivated hydrogenated diamond films by Hall effect measurements, and were compared to un-passivated diamond films (air-induced doping). A drastic improvement was observed in passivated samples in terms of conductivity, stability with time, and resistance to high temperatures. The efficiency of the investigated insulators, as electron acceptingmore » materials in hydrogenated diamond surface, is consistent with their electronic structure. These surface acceptor materials generate a higher hole sheet concentration, up to 6.5 × 10{sup 13} cm{sup −2}, and a lower sheet resistance, down to 2.6 kΩ/sq, in comparison to the atmosphere-induced values of about 1 × 10{sup 13} cm{sup −2} and 10 kΩ/sq, respectively. On the other hand, hole mobilities were reduced by using high electron affinity insulator dopants. Hole mobility as a function of hole concentration in a hydrogenated diamond layer was also investigated, showing a well-defined monotonically decreasing trend.« less

Transport (electrical and thermal) properties and surface morphology of Y1-xCaxFeO3 (where x = 0.03 and 0.05) ceramics

NASA Astrophysics Data System (ADS)

Suthar, Lokesh; Bhadala, Falguni; Roy, M.; Jha, V. K.

2018-05-01

The electrical transport behaviour of polycrystalline Calcium doped Yttrium orthoferrite (Y1-xCaxFeO3, where x = 0.03 and 0.05) have been synthesized by high temperature Solid state reaction route. The I-V characteristics have been measured which revels that Y1-xCaxFeO3 (where x = 0.03 and 0.05), behaves like semiconductor and its conductivity increases with increase in doping concentration. The thermal analysis experiment shows no phase change with the minor weight loss which reflects the high temperature thermal stability of the materials. The surface morphology was analyzed using the AFM. The results are discussed in detail.

The improvement of SiO2 nanotubes electrochemical behavior by hydrogen atmosphere thermal treatment

NASA Astrophysics Data System (ADS)

Spataru, Nicolae; Anastasescu, Crina; Radu, Mihai Marian; Balint, Ioan; Negrila, Catalin; Spataru, Tanta; Fujishima, Akira

2018-06-01

Highly defected SiO2 nanotubes (SiO2-NT) were obtained by a simple sol-gel procedure followed by calcination. Boron-doped diamond (BDD) polycrystalline films coated with SiO2-NT were used as working electrodes and, unexpectedly, cyclic voltammetric experiments have shown that the concentration of both positive and negative defects at the surface is high enough to enable redox processes involving positively charged Ru(bpy)32+/3+ to occur. Conversely, no electrochemical activity was put into evidence for Fe(CN)63-/4- species, most likely as a result of the strong electrostatic repulsion exerted by the negatively charged SiO2 surface. The concentration of surface defects was further increased by a subsequent thermal treatment in a hydrogen atmosphere which, as EIS measurements have shown, significantly promotes Ru(bpy)32+ anodic oxidation. Digital simulation of the voltammetric responses demonstrated that this treatment does not lead to a similar increase of the number of electron-donor sites. It was also found that methanol anodic oxidation at hydrogenated SiO2-NT-supported platinum results in Tafel slopes of 116-220 mV decade-1, comparable to those reported for both conventional PtRu and Pt-oxide catalysts.

The effect of ozone on nicotine desorption from model surfaces:evidence for heterogeneous chemistry

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

Destaillats, Hugo; Singer, Brett C.; Lee, Sharon K.

Assessment of secondhand tobacco smoke exposure using nicotine as a tracer or biomarker is affected by sorption of the alkaloid to indoor surfaces and by its long-term re-emission into the gas phase. However, surface chemical interactions of nicotine have not been sufficiently characterized. Here, the reaction of ozone with nicotine sorbed to Teflon and cotton surfaces was investigated in an environmental chamber by monitoring nicotine desorption over a week following equilibration in dry or humid air (65-70 % RH). The Teflon and cotton surfaces had N{sub 2}-BET surface areas of 0.19 and 1.17 m{sup 2} g{sup -1}, and water massmore » uptakes (at 70 % RH) of 0 and 7.1 % respectively. Compared with dry air baseline levels in the absence of O{sub 3}, gas phase nicotine concentrations decrease, by 2 orders of magnitude for Teflon after 50 h at 20-45 ppb O{sub 3}, and by a factor of 10 for cotton after 100 h with 13-15 ppb O{sub 3}. The ratios of pseudo first-order rate constants for surface reaction (r) to long-term desorption (k) were r/k = 3.5 and 2.0 for Teflon and cotton surfaces, respectively. These results show that surface oxidation was competitive with desorption. Hence, oxidative losses could significantly reduce long-term re-emissions of nicotine from indoor surfaces. Formaldehyde, N-methylformamide, nicotinaldehyde and cotinine were identified as oxidation products, indicating that the pyrrolidinic N was the site of electrophilic attack by O{sub 3}. The presence of water vapor had no effect on the nicotine-O{sub 3} reaction on Teflon surfaces. By contrast, nicotine desorption from cotton in humid air was unaffected by the presence of ozone. These observations are consistent with complete inhibition of ozone-nicotine surface reactions in an aqueous surface film present in cotton but not in Teflon surfaces.« less

Adsorption of Eu(III) onto TiO2: effect of pH, concentration, ionic strength and soil fulvic acid.

PubMed

Tan, Xiaoli; Fang, Ming; Li, Jiaxing; Lu, Yi; Wang, Xiangke

2009-08-30

The effects of pH, initial Eu(III) concentration, ionic strength and fulvic acid (FA) on the adsorption of Eu(III) on TiO(2) are investigated by using batch techniques. The results indicate that the presence of FA strongly enhances the adsorption of Eu(III) on TiO(2) at low pH values. Besides, the adsorption of Eu(III) on TiO(2) is significantly dependent on pH values and independent of ionic strength. The adsorption of Eu(III) on TiO(2) is attributed to inner-sphere surface complexation. The diffuse layer model (DLM) is applied to simulate the adsorption data, and fits the experimental data well with the aid of FITEQL 3.2. X-ray photoelectron spectroscopy (XPS) is performed to study the species of Eu(III) adsorbed on the surfaces of TiO(2)/FA-TiO(2) hybrids at a molecular level, which suggest that FA act as "bridge" between Eu(III) and TiO(2) particles to enhance the ability to adsorb Eu(III) in solution.

The preservation of long-range transported nitrate in snow at Summit, Greenland (Invited)

NASA Astrophysics Data System (ADS)

Hastings, M. G.

2013-12-01

Nitrate is one of the major anions found in polar and alpine snow, both today and in the past. Deposition of nitrate to snow surfaces results from reactions of nitrogen oxides (NOx) with oxidants in the atmosphere, resulting in the production of HNO3 that is incorporated into precipitation or reacts on the surface of particles. Several factors motivate studying nitrate concentration in ice cores including reconstructing past levels of NOx, tropospheric oxidant concentrations and natural variability in NOx sources. The link between the atmospheric concentration of NOx and nitrate concentration in ice core records is problematic because post-depositional processing, such as photolysis and evaporation, can impact the concentration of nitrate in snow. Recent work has shown that the isotopic ratios of nitrate (15N/14N, 18O/16O, 17O/16O) can be a powerful tool for tracing post-depositional loss of nitrate from surface snow. The isotopic composition of nitrate has been shown to contain information about the source of the nitrate (i.e, NOx sources) and the oxidation processes that convert NOx to nitrate in the atmosphere prior to deposition. Results from a number of studies at Summit, Greenland reveal limited loss of nitrate from surface snow during highly photoactive periods, and the oxygen isotopic signatures in snow nitrate appear to be representative of atmospheric deposition of nitrate from outside of Summit. Higher than expected oxygen isotope ratios (18O/16O, 17O/16O) found in Summit summertime nitrate were expected to be dependent upon local photochemistry in which nitrate in the snow is photolyzed to NOx that is then oxidized above the snow by BrO to reform nitrate (i.e., BrONO2). However, the oxygen isotopic composition of nitrate collected at high time resolution in surface snow does not show any link to local gas phase concentrations of a number of species, including BrO. Furthermore, the combination of nitrogen and oxygen isotope data reveals interesting insights into the contributions of nitrate sources to Summit. There are several important implications of this work including that nitrate at Summit appears to be largely preserved in surface snow during photoactive periods, and that nitrate in snow at Summit also appears to be representative of long-range transported nitrate/NOx. The surface snow work is further substantiated by relationships found between and among seasonally-resolved ice core measurements of the isotopic composition of nitrate, nitrate concentration and a suite of chemical and elemental tracers. The seasonality observed in 15N/14N ratios in an ice core representing accumulation since 1760 C.E. cannot be explained by diffusion or other processes occurring in the firn over time. A marked negative trend in 15N/14N since industrialization, parallels a nearly three-fold increase in nitrate concentration as well as pronounced increases in tracers such as excess lead and non-sea-salt sulfur. This, along with independent estimates of oil burning and transport studies, indicate that North American oil combustion is the primary driver of the modern negative trend in 15N/14N of nitrate. The high, positive 15N/14N ratios found in pre-industrial ice link to biomass burning based upon concentrations of black carbon and ammonium.

Artifacts in measuring aerosol uptake kinetics: the roles of time, concentration and adsorption

NASA Astrophysics Data System (ADS)

Renbaum, L. H.; Smith, G. D.

2011-03-01

In laboratory studies of organic aerosol particles reacting with gas-phase oxidants, high concentrations of radicals are often used to study on the timescale of seconds reactions which may be occurring over days or weeks in the troposphere. Implicit in this approach is the assumption that radical concentration and time are interchangeable parameters, though this has not been established. Here, the kinetics of OH- and Cl-initiated oxidation reactions of model single-component liquid organic aerosols (squalane, brassidic acid and 2-octyldodecanoic acid) are studied by varying separately the radical concentration and the reaction time. Two separate flow tubes with residence times of 2 and 66 s are used, and [OH] and [Cl] are varied by adjusting either the laser photolysis fluence or the radical precursor concentration ([O3] or [Cl2], respectively) used to generate the radicals. It is found that the rates measured by varying the radical concentration and the reaction time are equal only if the precursor concentrations are the same in the two approaches. Further, the rates depend on the concentrations of the precursor species with a Langmuir-type functional form suggesting that O3 and Cl2 saturate the surface of the liquid particles. It is believed that the presence of O3 inhibits the rate of OH reaction, perhaps by reacting with OH radicals or blocking surface sites, while Cl2 enhances the rate of Cl reaction by participating in a radical chain mechanism. These results have important implications for laboratory experiments in which high concentrations of gas-phase oxidants are used to study atmospheric reactions over short timescales and may explain the variability in recent measurements of the reactive uptake of OH on squalane particles in reactor systems used in this and other laboratories.

Effects of selective handling of pyritic, acid-forming materials on the chemistry of pore gas and ground water at a reclaimed surface coal mine in Clarion County, PA, USA

USGS Publications Warehouse

Cravotta,, Charles A.; Dugas, Diana L.; Brady, Keith; Kovalchuck, Thomas E.

1994-01-01

A change from dragline to “selective handling” mining methods at a reclaimed surface coal mine in western Pennsylvania did not significantly affect concentrations of metals in ground water because oxidation of pyrite and dissolution of siderite were not abated. Throughout the mine, placement of pyritic material near the land surface facilitated the oxidation of pyrite, causing the consumption of oxygen (O2) and release of acid, iron, and sulfate ions. Locally in the unsaturated zone, water sampled within or near pyritic zones was acidic, with concentrations of sulfate exceeding 3,000 milligrams per liter (mg/L). However, acidic conditions generally did not persist below the water table because of neutralization by carbonate minerals. Dissolution of calcite, dolomite, and siderite in unsaturated and saturated zones produced elevated concentrations of carbon dioxide (CO2), alkalinity, calcium, magnesium, iron, and manganese. Alkalinity concentrations of 600 to 800 mg/L as CaCO3 were common in water samples from the unsaturated zone in spoil, and alkalinities of 100 to 400 mg/L as CaCO3 were common in ground-water samples from the underlying saturated zone in spoil and bedrock. Saturation indices indicated that siderite could dissolve in water throughout the spoil, but that calcite dissolution or precipitation could occur locally. Calcite dissolution could be promoted as a result of pyrite oxidation, gypsum precipitation, and calcium ion exchange for sodium. Calcite precipitation could be promoted by evapotranspiration and siderite dissolution, and corresponding increases in concentrations of alkalinity and other solutes. Partial pressures of O2 (Po2) and CO2 (Pco2) in spoil pore gas indicated that oxidation of pyrite and precipitation of ferric hydroxide, coupled with dissolution of calcite, dolomite, and siderite were the primary reactions affecting water quality. Highest vertical gradients in Po2, particularly in the near-surface zone (0-1 m), did not correlate with concentrations of total sulfur in spoil. This lack of correlation could indicate that total sulfur concentrations in spoil do not reflect the amount of reactive pyrite or that oxidation rates can be controlled more by rates of O2 diffusion than the amount of pyrite. Hence, if placed in O2-rich zones near the land surface, even small amounts of disseminated pyritic material can be relatively significant sources of acid and mineralized water.

Investigation of Ag-TiO2 nanostructures photocatalytic properties prepared by modified dip coating method

NASA Astrophysics Data System (ADS)

AlArfaj, Esam

2016-05-01

In this article, titanium dioxide and silver nanostructures were deposited on glass substrates using modified sol-gel methods and dip-coating technique. The films were characterised chemically and physically using different techniques (TLC, UV-Vis and XRD) and tested for environmental applications regarding degradation of aromatic hydrocarbons. The photocatalytic activity of the TiO2 nanostructures is tested with different small concentrations of phenol in water and reaction mechanisms discussed. Considerable enhancement is observed in the photodegradation activity of Ag-modified (3 wt.%) TiO2 compared to unmodified TiO2 nanostructures for phenol concentrations within the pseudo-first-order Langmuir-Hinshelwood (LH) model for reaction kinetics. The pseudo-first-order global degradation rate constant increased from <0.005 min-1 for TiO2 to 0.013 min-1 for 3 mol% Ag-modified TiO2. The enhancement is attributed to the incorporation of Ag which promotes the generation of reactive oxygen species and increases the carrier recombination life-time. In addition, Ag has been observed to extend the absorption to the visible region by its surface plasmon resonances and to suppress the anatase-rutile phase transformation. Moreover, TiO2 grain size prepared was found to be 10 nm which maximises the active surface area. For phenol initial concentrations as low as 0.0002 M, saturation trend in the degradation process occurred at 0.00014 M and the reaction rate can be fitted with half-order LH kinetics.

Comparison of photo-Fenton, O3/H2O2/UV and photocatalytic processes for the treatment of gray water.

PubMed

Hassanshahi, Nahid; Karimi-Jashni, Ayoub

2018-06-21

This research was carried out to compare and optimize the gray water treatment performance by the photo-Fenton, photocatalysis and ozone/H 2 O 2 /UV processes. Experimental design and optimization were carried out using Central Composite Design of Response Surface Methodology. The results of experiments showed that the most effective and influencing factors in photo-Fenton process were H 2 O 2 /Fe 2+ ratio, in ozone/H 2 O 2 /UV experiment were O 3 concentration, H 2 O 2 concentration, reaction time and pH and in photocatalytic process were TiO 2 concentration, pH and reaction time. The highest COD removal in photo-Fenton, ozone/H 2 O 2 /UV and photocatalytic process were 90%, 92% and 55%, respectively. The results were analyzed by design expert software and for all three processes second-order models were proposed to simulate the COD removal efficiency. In conclusion the ozone/H 2 O 2 /UV process is recommended for the treatment of gray water, since it was able to remove both COD and turbidity by 92% and 93%, respectively. Copyright © 2018 Elsevier Inc. All rights reserved.

Concentrated solar energy used for sintering magnesium titanates for electronic applications

NASA Astrophysics Data System (ADS)

Apostol, Irina; Rodríguez, Jose; Cañadas, Inmaculada; Galindo, Jose; Mendez, Senen Lanceros; de Abreu Martins, Pedro Libȃnio; Cunha, Luis; Saravanan, Kandasamy Venkata

2018-04-01

Solar energy is an important renewable source of energy with many advantages: it is unlimited, clean and free. The main objective of this work was to sinter magnesium titanate ceramics in a solar furnace using concentrated solar energy, which is a novel and original process. The direct conversion of solar power into high temperature makes this process simple, feasible and ecologically viable/environmentally sustainable. We performed the solar sintering experiments at Plataforma Solar de Almeria-CIEMAT, Spain. This process takes place in a vertical axis solar furnace (SF5-5 kW) hosting a mobile flat mirror heliostat, a fixed parabolic mirror concentrator, an attenuator and a test table the concentrator focus. We sintered (MgO)0.63(TiO2)0.37, (MgO)0.49(TiO2)0.51, (MgO)0.50(TiO2)0.50 ceramics samples in air at about 1100 °C for a duration of 16 min, 1 h, 2 h and 3 h in the solar furnace. The MgO/TiO2 ratio and the dwell time was varied in order to obtain phase pure MgTiO3 ceramic. We obtained a pure MgTiO3 geikielite phase by solar sintering of (MgO)0.63(TiO2)0.37 samples at 1100 °C (16 min-3 h). Samples of (MgO)0.63(TiO2)0.37, solar sintered at 1100 °C for 3 h, resulted in well-sintered, non-porous samples with good density (3.46 g/cm3). The sintered samples were analyzed by XRD for phase determination. The grain and surface morphology was observed using SEM. Electrical measurements were carried out on solar sintered samples. The effect of processing parameters on microstructure and dielectric properties were investigated and is presented.

Exposure assessment of workplace manufacturing titanium dioxide particles

NASA Astrophysics Data System (ADS)

Xu, Huadong; Zhao, Lin; Chen, Zhangjian; Zhou, Jingwen; Tang, Shichuan; Kong, Fanling; Li, Xinwei; Yan, Ling; Zhang, Ji; Jia, Guang

2016-10-01

With the widespread use of titanium dioxide (TiO2) human exposure is inevitable, but the exposure data on TiO2 are still limited. This study adopted off-line filter-based sampling combined with real-time activity-based monitoring to measure the concentrations in a workplace manufacturing TiO2 (primary diameter: 194 ± 108 nm). Mass concentrations (MCs) of aerosol particles in the packaging workshop (total dust: 3.17 mg/m3, nano dust: 1.22 mg/m3) were much higher than those in the milling workshop (total dust: 0.79 mg/m3, nano dust: 0.31 mg/m3) and executive office (total dust: 0.44 mg/m3, nano dust: 0.19 mg/m3). However, the MCs of TiO2 were at a relatively low level in the packaging workshop (total TiO2: 46.4 μg/m3, nano TiO2: 16.7 μg/m3) and milling workshop (total TiO2: 39.4 μg/m3, nano TiO2: 19.4 μg/m3) by ICP-MS. The number concentration (NC), surface area concentration (SAC) of aerosol particles potentially deposited in alveolar (SACA), and tracheobronchial (SACTB) regions of lungs in the packaging workshop were (1.04 ± 0.89) × 105 particles/cm3, 414.49 ± 395.07, and 86.01 ± 83.18 μm2/cm3, respectively, which were all significantly higher than those of the milling workshop [(0.12 ± 0.40) × 105 particles/cm3, 75.38 ± 45.23, and 17.60 ± 9.22 μm2/cm3, respectively] as well as executive office and outdoor background ( p < 0.05). Activity-related characteristics were found in both workshops, and the time-variant characteristics showed very similar trends for 3 days in the packaging workshop. Our study provides important data of TiO2 particles exposure in the workplace.

SEM and AFM studies of dip-coated CuO nanofilms.

PubMed

Dhanasekaran, V; Mahalingam, T; Ganesan, V

2013-01-01

Cupric oxide (CuO) semiconducting thin films were prepared at various copper sulfate concentrations by dip coating. The copper sulfate concentration was varied to yield films of thicknesses in the range of 445-685 nm by surface profilometer. X-ray diffraction patterns revealed that the deposited films were polycrystalline in nature with monoclinic structure of (-111) plane. The surface morphology and topography of monoclinic-phase CuO thin films were examined using scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. Surface roughness profile was plotted using WSxM software and the estimated surface roughness was about ∼19.4 nm at 30 mM molar concentration. The nanosheets shaped grains were observed by SEM and AFM studies. The stoichiometric compound formation was observed at 30 mM copper sulfate concentration prepared film by EDX. The indirect band gap energy of CuO films was increased from 1.08 to 1.20 eV with the increase of copper sulfate concentrations. Copyright © 2012 Wiley Periodicals, Inc.

Remote sensing of potential lunar resources. I - Near-side compositional properties

NASA Technical Reports Server (NTRS)

Johnson, Jeffrey R.; Larson, Stephen M.; Singer, Robert B.

1991-01-01

Using telescopic CCD multispectral images of the lunar near side and the results of 330-870 nm spectroscopy of selected regions, the compositional differences relevant to the locations of potential lunar resources (such as ilmenite, FeTiO3, and solar-wind-implanted He-3 and H) are estimated. The 400/560 nm CCD ratio images were converted to weight percent TiO2, and the values were used to construct a new TiO2 abundance map which can be used to estimate the areas potentially rich in ilmenite. A 950/560 nm CCD ratio mosaic of the full moon provides estimates of relative surface maturity. Since high He-3 concentrations correlate with mature ilmenite-rich soils, a combination of relative surface maturity maps and the TiO2 abundance maps can be used to estimate distributions of He-3 (and possibly H) on local scales.

Characterization, sorption, and exhaustion of metal oxide nanoparticles as metal adsorbents

NASA Astrophysics Data System (ADS)

Engates, Karen Elizabeth

Safe drinking water is paramount to human survival. Current treatments do not adequately remove all metals from solution, are expensive, and use many resources. Metal oxide nanoparticles are ideal sorbents for metals due to their smaller size and increased surface area in comparison to bulk media. With increasing demand for fresh drinking water and recent environmental catastrophes to show how fragile water supplies are, new approaches to water conservation incorporating new technologies like metal oxide nanoparticles should be considered as an alternative method for metal contaminant adsorbents from typical treatment methods. This research evaluated the potential of manufactured iron, anatase, and aluminum nanoparticles (Al2O3, TiO2, Fe2O3) to remove metal contaminants (Pb, Cd, Cu, Ni, Zn) in lab-controlled and natural waters in comparison to their bulk counterparts by focusing on pH, contaminant and adsorbent concentrations, particle size, and exhaustive capabilities. Microscopy techniques (SEM, BET, EDX) were used to characterize the adsorbents. Adsorption experiments were performed using 0.01, 0.1, or 0.5 g/L nanoparticles in pH 8 solution. When results were normalized by mass, nanoparticles adsorbed more than bulk particles but when surface area normalized the opposite was observed. Adsorption was pH-dependent and increased with time and solid concentration. Aluminum oxide was found to be the least acceptable adsorbent for the metals tested, while titanium dioxide anatase (TiO2) and hematite (alpha-Fe2O3) showed great ability to remove individual and multiple metals from pH 8 and natural waters. Intraparticle diffusion was likely part of the complex kinetic process for all metals using Fe2O3 but not TiO 2 nanoparticles within the first hour of adsorption. Adsorption kinetics for all metals tested were described by a modified first order rate equation used to consider the diminishing equilibrium metal concentrations with increasing metal oxides, showing faster adsorption rates for nanoparticles compared to bulk particles. Isotherms were best fit with most correlations of r=0.99 or better using the Langmuir-Freundlich equation which describes a heterogeneous surface with monolayer adsorption. Calculated rate constants and distribution coefficients (Kd) showed TiO2 nanoparticles were very good sorbents and more rapid in removing metals than other nanoparticles studied here and reported in the literature. Desorption studies concluded Pb, Cd, and Zn appear to be irreversibly sorbed to TiO2 surfaces at pH 8. TiO2 and Fe2O3 nanoparticles were capable of multiple metal loadings, with exhaustion for both adsorbents at pH 6. Exhaustion studies at pH 8 showed hematite exhausted after four consecutive cycles while anatase showed no exhaustion after 8 cycles. Their bulk counterparts exhausted in earlier cycles indicating the lack of ability to adsorb much of the multiple metals in solution. The increased surface area of TiO2 and Fe 2O3 nanoparticles, coupled with strong adsorption at the pH of most natural waters and resistance to desorption of some metals, may offer a potential remediation method for removal of metals from water in the future.

Effect of sucrose ester concentration on the interfacial characteristics and physical properties of sodium caseinate-stabilized oil-in-water emulsions.

PubMed

Zhao, Qiangzhong; Liu, Daolin; Long, Zhao; Yang, Bao; Fang, Min; Kuang, Wanmei; Zhao, Mouming

2014-05-15

The effect of sucrose ester (SE) concentration on interfacial tension and surface dilatational modulus of SE and sodium caseinate (NaCas)-SE solutions were investigated. The critical micelle concentration (CMC) of SE was presumed to be 0.05% by measuring interfacial tension of SE solution. The interfacial tension of NaCas-SE solution decreased with increased SE concentration. A sharp increase in surface dilatational modulus of NaCas solution was observed when 0.01% SE was added and a decline was occurred at higher SE level. The influence of SE concentration on droplet size and confocal micrograph, surface protein concentration, ζ-potential and rheological properties of oil-in-water (O/W) emulsions prepared with 1% NaCas was also examined. The results showed that addition of SE reduced droplet size and surface protein concentration of the O/W emulsions. The ζ-potential of the O/W emulsions increased initially and decreased afterward with increased SE concentration. All the O/W emulsions exhibited a shear-thinning behaviour and the data were well-fitted into the Herschel-Bulkley model. Copyright © 2013 Elsevier Ltd. All rights reserved.

Time distribution of adsorption entropy of gases on heterogeneous surfaces by reversed-flow gas chromatography.

PubMed

Katsanos, Nicholas A; Kapolos, John; Gavril, Dimitrios; Bakaoukas, Nicholas; Loukopoulos, Vassilios; Koliadima, Athanasia; Karaiskakis, George

2006-09-15

The reversed-flow gas chromatography (RF-GC) technique has been applied to measure the adsorption entropy over time, when gaseous pentane is adsorbed on the surface of two solids (gamma-alumina and a silica supported rhodium catalyst) at 393.15 and 413.15K, respectively. Utilizing experimental chromatographic data, this novel methodology also permits the simultaneous measurement of the local adsorption energy, epsilon, local equilibrium adsorbed concentration, c(s)(*), and local adsorption isotherm, theta(p, T, epsilon) in a time resolved way. In contrast with other inverse gas chromatographic methods, which determine the standard entropy at zero surface coverage, the present method operates over a wide range of surface coverage taking into account not only the adsorbate-adsorbent interaction, but also the adsorbate-adsorbate interaction. One of the most interesting observations of the present work is the fact that the interaction of n-pentane is spontaneous on the Rh/SiO(2) catalyst for a very short time interval compared to that on gamma-Al(2)O(3). This can explain the different kinetic behavior of each particular gas-solid system, and it can be attributed to the fact that large amounts of n-C(5)H(12) are present on the active sites of the Rh/SiO(2) catalyst compared to those on gamma-Al(2)O(3), as the local equilibrium adsorbed concentration values, c(s)(*), indicate.

Preparation and surface characteristics of Re3W matrix scandate cathode: An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Lai, Chen; Wang, Jinshu; Zhou, Fan; Liu, Wei; Hu, Peng; Wang, Changhao; Wang, Ruzhi; Miao, Naihua

2018-05-01

The Scandia doped thermionic cathodes have received great attention owing to their high electron emission density in past two decades. Here, Scandia doped Re3W matrix scandate (RS) cathodes are fabricated by using Sc2O3 doped Re3W powders that prepared by spray drying method. The micromorphology, surface composition and chemical states of RS cathode are investigated with various modern technologies. It reveals that the reduction temperature of RS powders is dramatically increased by Sc2O3. On the surface of RS cathode, a certain amount of Sc2O3 nanoparticles and barium salt submicron particles are observed. According to the in situ Auger electron spectroscopy analysis, the concentration ratio of Ba:Sc:O is determined to be 2.9:1.1:2.7. The X-ray photoelectron spectroscopy data indicates that low oxidation state of Sc is clearly observed in scandate cathodes. The high atomic ratio of Ba on RS cathode surface is suggested due to the high adsorption of Re3W to Ba. Moreover, RS cathode shows better adsorption to Sc by comparison with conventional tungsten matrix scandate cathode. For RS cathode, the main depletion of Sc is suggested to -OSc desorbing from RS cathode surface. RS cathode is expected to be an impressive thermionic cathode with good emission properties and ion anti-bombarding insensitivity.

Second-harmonic generation and theoretical studies of protonation at the water/α-TiO 2 (1 1 0) interface

NASA Astrophysics Data System (ADS)

Fitts, Jeffrey P.; Machesky, Michael L.; Wesolowski, David J.; Shang, Xiaoming; Kubicki, James D.; Flynn, George W.; Heinz, Tony F.; Eisenthal, Kenneth B.

2005-08-01

The pH of zero net surface charge (pH pzc) of the α-TiO 2 (1 1 0) surface was characterized using second-harmonic generation (SHG) spectroscopy. The SHG response was monitored during a series of pH titrations conducted at three NaNO 3 concentrations. The measured pH pzc is compared with a pH pzc value calculated using the revised MUltiSIte Complexation (MUSIC) model of surface oxygen protonation. MUSIC model input parameters were independently derived from ab initio calculations of relaxed surface bond lengths for a hydrated surface. Model (pH pzc 4.76) and experiment (pH pzc 4.8 ± 0.3) agreement establishes the incorporation of independently derived structural parameters into predictive models of oxide surface reactivity.

Removal of urea from dilute streams using RVC/nano-NiO x -modified electrode.

PubMed

Tammam, Reham H; Touny, Ahmed H; Saleh, Mahmoud M

2018-05-08

Reticulated vitreous carbon (RVC), a high surface area electrode (40 cm 2 /cm 3 ), has been modified with nickel oxide nanoparticles (nano-NiO x ) and used for electrochemical oxidation of urea from alkaline solution. For the cyclic voltammetry measurements, the used dimensions are 0.8 cm × 0.8 cm × 0.3 cm. The purpose was to offer high specific surface area using a porous open network structure to accelerate the electrochemical conversion. NiO x nanoparticles have been synthesized via an electrochemical route at some experimental conditions. The morphological, structural, and electrochemical properties of the RVC/nano-NiO x are characterized by using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), cyclic voltammetry (CV), and potentiostatic measurements. The fabricated electrode, RVC/nano-NiO x , demonstrates high electrocatalytic activity towards urea oxidation in an alkaline electrolyte. The onset potential of the RVC/nano-NiO x compared to that of the planar GC/NiO x is shifted to more negative value with higher specific activity. The different loadings of the NiO x have a substantial influence on the conversion of urea which has been evaluated from concentration-time curves. The urea concentration decreases with time to a limit dependent on the loading extent. Maximum conversion is obtained at 0.86 mg of NiO x per cm 3 of the RVC matrix.

Influences of the (NH2)2CO concentration on magnetic photocatalytic composites

NASA Astrophysics Data System (ADS)

Liŭ, Dan; Li, Ziheng; Wang, Wenquan; Liú, Dan; Wang, Guoqiang; Lin, Junhong; He, Yingqiao; Li, Xiangru

2016-11-01

Magnetic photocatalytic Fe3O4@TiO2 composites have been fabricated by changing the concentration of (NH2)2CO. Samples were named as low (NH2)2CO concentration group which the (NH2)2CO concentration in the synthesis process was below 2.25 mol/L and high (NH2)2CO concentration group which the (NH2)2CO concentration was above 2.5 mol/L. Photocatalytic degradation experiments of methyl orange showed that the final degradation rates of low (NH2)2CO concentration group samples were higher than that of high (NH2)2CO concentration group, even better than P25 at the same test conditions. And it was interesting that samples of low (NH2)2CO concentration group had smaller values of BET surface areas than that of high (NH2)2CO concentration group. It indicated that the improvement of photocatalytic activity which was effected by BET surface areas was not obvious. There were two main factors enhancing the photocatalytic property of low (NH2)2CO concentration group: First, diffusing reflection spectra showed that the low (NH2)2CO concentration group samples had lower reflectivity, this suggested that the structure improved the efficiency of light absorption; Second, NH4+ would take up the active sites on the surface of the TiO2 particles, the FT-IR test results showed that the samples of the low (NH2)2CO concentration group samples bonded less NH4+, thus leading to the higher photocatalytic activity. It had enlightenment role for optimizing the performance of photocatalytic materials.

Paramagnetic behavior of Co doped TiO{sub 2} nanocrystals controlled by self-purification mechanism

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

Anitha, B.; Khadar, M. Abdul, E-mail: mabdulkhadar@rediffmail.com; Banerjee, Alok

Doping in nanocrystals is a challenging process because of the self- purification mechanism which tends to segregate out the dopants resulting in a greater dopant concentration near the surface than at the interior of nanocrystals. In the present work nanocrystals of TiO{sub 2} doped with different atom % of Co were synthesized by peroxide gel method. XRD analysis confirmed the tetragonal anatase structure and HRTEM images showed the rod-like morphology of the samples. Raman modes of anatase phase of TiO{sub 2} along with weak intensity peaks of Co{sub 3}O{sub 4} for higher Co dopant concentrations were observed for the samples.more » EPR measurements revealed the presence of cobalt in +2 oxidation state in the TiO{sub 2} matrix. SQUID measurements indicated paramagnetic behavior of the Co doped TiO{sub 2} nanocrystals. The paramagnetic behavior is attributed to an increased concentration of Co{sup 2+} ions and an increased presence of Co{sub 3}O{sub 4} phase near the surface of the TiO{sub 2} nanocrystals due to self-purification mechanism. - Graphical abstract: Variation of the intensity ratios of XRD peaks as a function of atomic ratio of Co. Inset: variation of structure factor for (101) reflection as a function of atomic ratio of Co. Display Omitted - Highlights: • Co doped TiO{sub 2} nanocrystals were synthesized by peroxide gel method. • HRTEM images showed Co doped TiO{sub 2} nanocrystals to be rod-like. • EPR spectra showed +2 oxidation states for Co in the samples. • Co doped TiO{sub 2} nanocrystals showed paramagnetic behavior.« less

Highly Sensitive and Selective Ethanol Sensor Fabricated with In-Doped 3DOM ZnO.

PubMed

Wang, Zhihua; Tian, Ziwei; Han, Dongmei; Gu, Fubo

2016-03-02

ZnO is an important n-type semiconductor sensing material. Currently, much attention has been attracted to finding an effective method to prepare ZnO nanomaterials with high sensing sensitivity and excellent selectivity. A three-dimensionally ordered macroporous (3DOM) ZnO nanostructure with a large surface area is beneficial to gas and electron transfer, which can enhance the gas sensitivity of ZnO. Indium (In) doping is an effective way to improve the sensing properties of ZnO. In this paper, In-doped 3DOM ZnO with enhanced sensitivity and selectivity has been synthesized by using a colloidal crystal templating method. The 3DOM ZnO with 5 at. % of In-doping exhibits the highest sensitivity (∼88) to 100 ppm ethanol at 250 °C, which is approximately 3 times higher than that of pure 3DOM ZnO. The huge improvement to the sensitivity to ethanol was attributed to the increase in the surface area and the electron carrier concentration. The doping by In introduces more electrons into the matrix, which is helpful for increasing the amount of adsorbed oxygen, leading to high sensitivity. The In-doped 3DOM ZnO is a promising material for a new type of ethanol sensor.

Self-generated concentration and modulus gradient coating design to protect Si nano-wire electrodes during lithiation.

PubMed

Kim, Sung-Yup; Ostadhossein, Alireza; van Duin, Adri C T; Xiao, Xingcheng; Gao, Huajian; Qi, Yue

2016-02-07

Surface coatings as artificial solid electrolyte interphases have been actively pursued as an effective way to improve the cycle efficiency of nanostructured Si electrodes for high energy density lithium ion batteries, where the mechanical stability of the surface coatings on Si is as critical as Si itself. However, the chemical composition and mechanical property change of coating materials during the lithiation and delithiation process imposed a grand challenge to design coating/Si nanostructure as an integrated electrode system. In our work, we first developed reactive force field (ReaxFF) parameters for Li-Si-Al-O materials to simulate the lithiation process of Si-core/Al2O3-shell and Si-core/SiO2-shell nanostructures. With reactive dynamics simulations, we were able to simultaneously track and correlate the lithiation rate, compositional change, mechanical property evolution, stress distributions, and fracture. A new mechanics model based on these varying properties was developed to determine how to stabilize the coating with a critical size ratio. Furthermore, we discovered that the self-accelerating Li diffusion in Al2O3 coating forms a well-defined Li concentration gradient, leading to an elastic modulus gradient, which effectively avoids local stress concentration and mitigates crack propagation. Based on these results, we propose a modulus gradient coating, softer outside, harder inside, as the most efficient coating to protect the Si electrode surface and improve its current efficiency.

Oxidation of dimethylselenide by δMnO2: oxidation product and factors affecting oxidation rate

USGS Publications Warehouse

Wang, Bronwen; Burau, Richard G.

1995-01-01

Volatile dimethylselenide (DMSe) was transformed to a nonvolatile Se compound in a ??-MnO2 suspension. The nonvolatile product was a single compound identified as dimethylselenoxide based on its mass spectra pattern. After 24 h, 100% of the DMSe added to a ??-MnO2 suspension was converted to nonpurgable Se as opposed to 20%, 18%, and 4% conversion for chromate, permanganate, and the filtrate from the suspension, respectively. Manganese was found in solution after reaction. These results imply that the reaction between manganese oxide and DMSe was a heterogeneous redox reaction involving solid phase ??-MnO2 and solution phase DMSe. Oxidation of DMSe to dimethylselenoxide [OSe(CH3)2] by a ??-MnO2 suspension appears to be first order with respect to ??-MnO2, to DMSe, and to hydrogen ion with an overall rate law of d[OSe(CH3)2 ]/dt = 95 M-2 min-1 [MnO2]1[DMSe]1[H+]1 for the MnO2 concentration range of 0.89 ?? 10-3 - 2.46 ?? 10-3 M, the DMSe concentration range of 3.9 ?? 10-7 - 15.5 ?? 10-7 M Se, and a hydrogen ion concentation range of 7.4 ?? 10-6 -9.5 ?? 10-8 M. A general surface site adsorption model is consistent with this rate equation if the uncharged |OMnOH is the surface adsorption site. DMSe acts as a Lewis base, and the manganese oxide surface acts as a Lewis acid. DMSe adsorption to |OMnOH can be viewed as a Lewis acid/ base complex between the largely p orbitals of the DMSe lone pair and the unoccupied eg orbitals on manganese oxide. For such a complex, frontier molecular orbital theory predicts electron transfer to occur via an inner-sphere complex between the DMSe and the manganese oxide. ?? 1995 American Chemical Society.

Numerical study on the impacts of heterogeneous reactions on ozone formation in the Beijing urban area

NASA Astrophysics Data System (ADS)

Xu, Jun; Zhang, Yuanhang; Wang, Wei

2006-12-01

The air quality model CMAQ-MADRID (Community Multiscale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization and Dissolution) was employed to simulate summer O3 formation in Beijing China, in order to explore the impacts of four heterogeneous reactions on O3 formation in an urban area. The results showed that the impacts were obvious and exhibited the characteristics of a typical response of a VOC-limited regime in the urban area. For the four heterogeneous reactions considered, the NO2 and HO2 heterogeneous reactions have the most severe impacts on O3 formation. During the O3 formation period, the NO2 heterogeneous reaction increased new radical creation by 30%, raising the atmospheric activity as more NO→NO2 conversion occurred, thus causing the O3 to rise. The increase of O3 peak concentration reached a maximum value of 67 ppb in the urban area. In the morning hours, high NO titration reduced the effect of the photolysis of HONO, which was produced heterogeneously at night in the surface layer. The NO2 heterogeneous reaction in the daytime is likely one of the major reasons causing the O3 increase in the Beijing urban area. The HO2 heterogeneous reaction accelerated radical termination, resulting in a decrease of the radical concentration by 44% at the most. O3 peak concentration decreased by a maximum amount of 24 ppb in the urban area. The simulation results were improved when the heterogeneous reactions were included, with the O3 and HONO model results close to the observations.

Degradation of polycyclic aromatic hydrocarbons in a coking wastewater treatment plant residual by an O3/ultraviolet fluidized bed reactor.

PubMed

Lin, Chong; Zhang, Wanhui; Yuan, Mengyang; Feng, Chunhua; Ren, Yuan; Wei, Chaohai

2014-09-01

Coking wastewater treatment plant (CWWTP) represents a typical point source of polycyclic aromatic hydrocarbons (PAHs) to the water environment and threatens the safety of drinking water in downstream regions. To enhance the removal of residual PAHs from bio-treated coking wastewater, a pilot-scale O3/ultraviolet (UV) fluidized bed reactor (O3/UV FBR) was designed and different operating factors including UV irradiation intensity, pH, initial concentration, contact time, and hydraulic retention time (HRT) were investigated at an ozone level of 240 g h(-1) and 25 ± 3 °C. A health risk evaluation and cost analysis were also carried out under the continuous-flow mode. As far as we know, this is the first time an O3/UV FBR has been explored for PAHs treatment. The results indicated that between 41 and 75 % of 18 target PAHs were removed in O3/UV FBR due to synergistic effects of UV irradiation. Both increased reaction time and increased pH were beneficial for the removal of PAHs. The degradation of the target PAHs within 8 h can be well fitted by the pseudo-first-order kinetics (R (2) > 0.920). The reaction rate was also positively correlated with the initial concentrations of PAHs. The health risk assessment showed that the total amount of carcinogenic substance exposure to surface water was reduced by 0.432 g day(-1). The economic analysis showed that the O3/UV FBR was able to remove 18 target PAHs at a cost of US$0.34 m(-3). These results suggest that O3/UV FBR is efficient in removing residuals from CWWTP, thus reducing the accumulation of persistent pollutant released to surface water.

Measurements of HNO3 and N2O5 using ion drift-chemical ionization mass spectrometry during the MILAGRO/MCMA-2006 campaign

NASA Astrophysics Data System (ADS)

Zheng, J.; Zhang, R.; Fortner, E. C.; Volkamer, R. M.; Molina, L.; Aiken, A. C.; Jimenez, J. L.; Gaeggeler, K.; Dommen, J.; Dusanter, S.; Stevens, P. S.; Tie, X.

2008-11-01

An ion drift-chemical ionization mass spectrometer (ID-CIMS) was deployed in Mexico City between 7 and 31 March to measure gas-phase nitric acid (HNO3) and dinitrogen pentoxide (N2O5 during the Mexico City Metropolitan Area (MCMA)-2006 field campaign. The observation site was located at the Instituto Mexicano del Petróleo in the northern part of Mexico City urban area with major emissions of pollutants from residential, vehicular and industrial sources. Diurnally, HNO3 was less than 200 parts per trillion (ppt) during the night and early morning. The concentration of HNO3 increased steadily from around 09:00 a.m. central standard time (CST), reached a peak value of 0.5 to 3 parts per billion (ppb) in the early afternoon, and then declined sharply to less than half of the peak value near 05:00 p.m. CST. An inter-comparison between the ID-CIMS and an ion chromatograph/mass spectrometer (ICMS) showed a good agreement between the two HNO3 measurements (R2=0.75). The HNO3 mixing ratio was found to anti-correlate with submicron-sized aerosol nitrate, suggesting that the gas-particle partitioning process was a major factor in determining the gaseous HNO3 concentration. Losses by irreversible reactions with mineral dust and via dry deposition also could be important at this site. Most of the times during the MCMA 2006 field campaign, N2O5 was found to be below the detection limit (about 30 ppt for a 10 s integration time) of the ID-CIMS, because of high NO mixing ratio at the surface (>100 ppb) during the night. An exception occurred on 26 March 2006, when about 40 ppt N2O5 was observed during the late afternoon and early evening hours under cloudy conditions before the build-up of NO at the surface site. The results revealed that during the MCMA-2006 field campaign HNO3 was primarily produced from the reaction of OH with NO2 and regulated by gas/particle transfer and dry deposition. The production of HNO3 from N2O5 hydrolysis during the nighttime was small because of high NO and low O3 concentrations near the surface.

Lewis acid properties of alumina based catalysts: study by paramagnetic complexes of probe molecules

NASA Astrophysics Data System (ADS)

Fionov, Alexander V.

2002-06-01

Lewis acid properties of LiAl 5O 8/Al 2O 3 (2 wt.% Li) and MgAl 2O 4/Al 2O 3 (3 wt.% Mg) catalysts were studied by EPR of adsorbed probe molecules--anthraquinone and 2,2,6,6-tetramethylpiperidine- N-oxyl (TEMPO). The lesser (in comparison with γ-Al 2O 3) concentration and the strength of Lewis acid sites (LAS) formed on the surface of aluminate layer has been shown. The stability of this layer plays important role in the change of Lewis acid properties during the calcination of modified alumina. The lithium aluminate layer was stable at used calcination temperature, 773 K, meanwhile magnesium aluminate layer observed only at calcination temperature below 723 K. The increase of the calcination temperature to 773 K caused the segregation of MgAl 2O 4 on the surface resulted in the release of alumina surface and recovery of the Lewis acid properties. The differences in the LAS manifestations towards TEMPO and anthraquinone was discussed. The mechanism of the formation of anthraquinone paramagnetic complexes with LAS--three-coordinated aluminum ions--was proposed. This mechanism includes the formation of anthrasemiquinone, and then--anthrasemiquinone ion pair or triple ion. Fragments like -O-Al +-O- play the role of cations in these ion pairs and triple ions. Proposed mechanism can also be applied for the consideration of similar anthraquinone paramagnetic complexes on the surface of gallium oxide containing systems.

Dynamics of the metal-insulator transition of donor-doped SrTi O3

NASA Astrophysics Data System (ADS)

Meyer, René; Zurhelle, Alexander F.; De Souza, Roger A.; Waser, Rainer; Gunkel, Felix

2016-09-01

The electrical properties of donor-doped SrTi O3 (n -STO) are profoundly affected by an oxidation-induced metal-insulator transition (MIT). Here we employ dynamical numerical simulations to examine the high-temperature MIT of n -STO over a large range of time and length scales. The simulations are based on the Nernst-Planck equations, the continuity equations, and the Poisson equation, in combination with surface lattice disorder equilibria serving as time-dependent boundary conditions. The simulations reveal that n -STO, upon oxidation, develops a kinetic space charge region (SCR) in the near-surface region. The surface concentrations of the variously mobile defects (electrons, Sr vacancies, and O vacancies) are found to vary over time and to differ considerably from the values of the new equilibrium. The formation of the SCR in which electrons are strongly depleted occurs within nanoseconds, i.e., it yields a fast MIT in the near-surface region during the oxidation process. As a result of charge (over-)compensation by Sr vacancies incorporated at the surface of n -STO, this SCR is much more pronounced than conventionally expected. In addition, we find an anomalous increase of O vacancy concentration at the surface upon oxidation caused by the SCR. Our simulations show that the SCR fades in the long term as a result of the slow in-diffusion of Sr vacancies. We discuss implications for the electrical conductivity of n -STO crystals used as substrates for epitaxial oxide thin films, of n -STO thin films and interfaces, and of polycrystalline n -STO with various functionalities.

Field emission of silicon emitter arrays coated with sol-gel (Ba0.65Sr0.35)1-xLaxTiO3 thin films

NASA Astrophysics Data System (ADS)

Lu, H.; Pan, J. S.; Chen, X. F.; Zhu, W. G.

2007-07-01

(Ba0.65Sr0.35)1-xLaxTiO3 (BSLT) thin films with different La concentrations have been deposited on Si field emitter arrays (FEAs) using sol-gel technology for field electron emission applications. The films exhibit the perovskite structure at low La substitution level (x ≤0.5) and the pyrochlore phase at high La concentration (x ≥0.75). The 30-nm-thick BSLT (x =0.25) thin film has higher crystallinity of perovskite structure in the surface region. An x-ray photoelectron spectroscopy study indicates that the oxygen vacancy concentration decreases with La substitution. With respect to the undoped Ba0.65Sr0.35TiO3 thin film, the Fermi level shifts down for the BSLT sample with x =0.1 ascribed to the decreasing oxygen vacancy concentration, and then shifts up for the BSLT sample with x =0.25 attributed to the increasing La substitution level. In highly doped films with an x value over 0.5, it shifts down again associated with the second pyrochlore phase formation. The best enhancement in field emission is found for the BSLT-coated (x =0.25) Si FEAs due to the improved perovskite structure in the surface region and up-moved Fermi level of the coating.

Determination of stoichiometry and concentration of trace elements in thin BaxSr1-xTiO3 perovskite layers.

PubMed

Becker, J S; Boulyga, S F

2001-07-01

This paper describes an analytical procedure for determining the stoichiometry of BaxSr1-xTiO3 perovskite layers using inductively coupled plasma mass spectrometry (ICP-MS). The analytical results of mass spectrometry measurements are compared to those of X-ray fluorescence analysis (XRF). The performance and the limits of solid-state mass spectrometry analytical methods for the surface analysis of thin BaxSr1-xTiO3 perovskite layers sputtered neutral mass spectrometry (SNMS)--are investigated and discussed.

An ultrasensitive chemiluminescence aptasensor for thrombin detection based on iron porphyrin catalyzing luminescence desorbed from chitosan modified magnetic oxide graphene composite.

PubMed

Sun, Yuanling; Wang, Yanhui; Li, Jianbo; Ding, Chaofan; Lin, Yanna; Sun, Weiyan; Luo, Chuannan

2017-11-01

In this work, an ultrasensitive chemiluminescence (CL) aptasensor was prepared for thrombin detection based on iron porphyrin catalyzing luminol - hydrogen peroxide luminescence under alkaline conditions, and iron porphyrin was desorbed from chitosan modified magnetic oxide graphene composite (CS@Fe 3 O 4 @GO). Firstly, CS@Fe 3 O 4 @GO was prepared. CS@Fe 3 O 4 @GO has advantages of the good biocompatibility and positively charged on its surface of CS, the large specific surface area of GO and the easy separation characteristics of Fe 3 O 4 . GO, Fe 3 O 4 and CS@Fe 3 O 4 @GO were confirmed by transmission electron microscopy (TEM), scanning electron microscope (SEM), fourier transform infrared (FTIR) and X-ray powder diffraction (XRD). Then, thrombin aptamer (T-Apt) and hemin (HM, an iron porphyrin) were sequentially modified on the surface of CS@Fe 3 O 4 @GO to form CS@Fe 3 O 4 @GO@T-Apt@HM. The immobilization properties of CS@Fe 3 O 4 @GO to T-Apt and adsorption properties of CS@Fe 3 O 4 @GO@T-Apt to HM were sequentially researched through the curves of kinetics and the curves of thermodynamics. When thrombin existed in solutions, HM was desorbed from the surface of CS@Fe 3 O 4 @GO@T-Apt@HM owing to the strong specific recognition ability between thrombin and T-Apt, causing the changes of CL signal. Under optimized CL conditions, thrombin could be measured with the linear concentration range of 5.0×10 -15 -2.5×10 -10 mol/L. The detection limit was 1.5×10 -15 mol/L (3δ) while the relative standard deviation (RSD) was 3.2%. Finally, the CS@Fe 3 O 4 @GO@T-Apt@HM-CL aptasensor was used for the determination of thrombin in practical serum samples and recoveries ranged from 95% to 103%. Those satisfactory results revealed potential application of the CS@Fe 3 O 4 @GO@T-Apt@HM-CL aptasensor for thrombin detection in monitoring and diagnosis of human blood diseases. Copyright © 2017 Elsevier B.V. All rights reserved.

Transport of oxidized multi-walled carbon nanotubes through silica based porous media: influences of aquatic chemistry, surface chemistry, and natural organic matter.

PubMed

Yang, Jin; Bitter, Julie L; Smith, Billy A; Fairbrother, D Howard; Ball, William P

2013-12-17

This paper provides results from studies of the transport of oxidized multi-walled carbon nanotubes (O-MWCNTs) of varying surface oxygen concentrations under a range of aquatic conditions and through uniform silica glass bead media. In the presence of Na(+), the required ionic strength (IS) for maximum particle attachment efficiency (i.e., the critical deposition concentration, or CDC) increased as the surface oxygen concentration of the O-MWCNTs or pH increased, following qualitative tenets of theories based on electrostatic interactions. In the presence of Ca(2+), CDC values were lower than those with Na(+) present, but were no longer sensitive to surface oxygen content, suggesting that Ca(2+) impacts the interactions between O-MWCNTs and glass beads by mechanisms other than electrostatic alone. The presence of Suwannee River natural organic matter (SRNOM) decreased the attachment efficiency of O-MWCNTs in the presence of either Na(+) or Ca(2+), but with more pronounced effects when Na(+) was present. Nevertheless, low concentrations of SRNOM (<4 mg/L of dissolved organic carbon) were sufficient to mobilize all O-MWCNTs studied at CaCl2 concentrations as high as 10 mM. Overall, this study reveals that NOM content, pH, and cation type show more importance than surface chemistry in affecting O-MWCNTs deposition during transport through silica-based porous media.

Formation of apatite layers on modified canasite glass-ceramics in simulated body fluid.

PubMed

Miller, C A; Kokubo, T; Reaney, I M; Hatton, P V; James, P F

2002-03-05

Canasite glass-ceramics were modified by either increasing the concentration of calcium in the glass, or by the addition of P2O5. Samples of these novel materials were placed in simulated body fluid (SBF), along with a control material (commercial canasite), for periods ranging from 12 h to 28 days. After immersion, surface analysis was performed using thin film X-ray diffraction, Fourier transform infrared reflection spectroscopy, and scanning electron microscopy equipped with energy dispersive X-ray detectors. The concentrations of sodium, potassium, calcium, silicon, and phosphorus in the SBF solution were measured using inductively coupled plasma emission spectroscopy. No apatite was detected on the surface of commercial canasite, even after 28 days of immersion in SBF. A crystalline apatite layer was formed on the surface of a P2O5-containing canasite after 5 days, and after 3 days for calcium-enriched canasite. Ion release data suggested that the mechanism for apatite deposition was different for P2O5 and non-P2O5-containing glass-ceramics. Copyright 2001 John Wiley & Sons, Inc.

Ozone production in the New York City urban plume

NASA Astrophysics Data System (ADS)

Kleinman, Lawrence I.; Daum, Peter H.; Imre, Dan G.; Lee, Jai H.; Lee, Yin-Nan; Nunnermacker, Linda J.; Springston, Stephen R.; Weinstein-Lloyd, Judith; Newman, Leonard

2000-06-01

In the summer of 1996 the Department of Energy G-1 aircraft was deployed in the New York City metropolitan area as part of the North American Research Strategy for Tropospheric Ozone-Northeast effort to determine the causes of elevated O3 levels in the northeastern United States. Measurements of O3, O3 precursors, and other photochemically active trace gases were made upwind and downwind of New York City with the objective of characterizing the O3 formation process and its dependence on ambient levels of NOx and volatile organic compounds (VOCs). Four flights are discussed in detail. On two of these flights, winds were from the W-SW, which is the typical direction for an O3 episode. On the other two flights, winds were from the NW, which puts a cleaner area upwind of the city. The data presented include plume and background values of O3, CO, NOx, and NOy concentration and VOC reactivity. On the W-SW flow days O3 reached 110 ppb. According to surface observations the G-1 intercepted the plume close to the region where maximum O3 occurred. At this point the ratio NOx/NOy was 20-30%, indicating an aged plume. Plume values of CO/NOy agree to within 20% with emission estimates from the core of the New York City metropolitan area. Steady state photochemical calculations were performed using observed or estimated trace gas concentrations as constraints. According to these calculations the local rate of O3 production P(O3) in all four plumes is VOC sensitive, sometimes strongly so. The local sensitivity calculations show that a specified fractional decrease in VOC concentration yields a similar magnitude fractional decrease in P(O3). Imposing a decrease in NOx, however, causes P(O3) to increase. The question of primary interest from a regulatory point of view is the sensitivity of O3 concentration to changes in emissions of NOx and VOCs. A qualitative argument is given that suggests that the total O3 formed in the plume, which depends on the entire time evolution of the plume, is also VOC sensitive. Indicator ratios O3/NOz and H2O2/NOz mainly support the conclusion that plume O3 is VOC sensitive.

Synthesis and colloidal properties of anisotropic hydrothermal barium titanate

NASA Astrophysics Data System (ADS)

Yosenick, Timothy James

2005-11-01

Nanoparticles of high dielectric constant materials, especially BaTiO3, are required to achieve decreased layer thickness in multilayer ceramic capacitors (MLCCs). Tabular metal nanoparticles can produce thin metal layers with low surface roughness via electrophoretic deposition (EPD). To achieve similar results with dielectric layers requires the synthesis and dispersion of tabular BaTiO3 nanoparticles. The goal of this study was to investigate the deposition of thin BaTiO3 layers using a colloidal process. The synthesis, interfacial chemistry and colloidal properties of hydrothermal BaTiO3 a model particle system, was investigated. After characterization of the material system particulates were deposited to form thin layers using EPD. In the current study, the synthesis of BaTiO3 has been investigated using a hydrothermal route. TEM and AFM analyses show that the synthesized particles are single crystal with a majority of the particle having a <111> zone axis and {111} large face. The particles have a median thickness of 5.8 +/- 3.1 nm and face diameter of 27.1 +/- 12.3 nm. Particle growth was likely controlled by the formation of {111} twins and the synthesis pH which stabilizes the {111} face during growth. With limited growth in the <111> direction, the particles developed a plate-like morphology. Physical property characterization shows the powder was suitable for further processing with high purity, low hydrothermal defect concentration, and controlled stoichiometry. TEM observations of thermally treated powders indicate that the particles begin to loose the plate-like morphology by 900 °C. The aqueous passivation, dispersion, and doping of nanoscale BaTiO 3 powders was investigated. Passivation BaTiO3 was achieved through the addition of oxalic acid. The oxalic acid selectively adsorbs onto the particle surface and forms a chemically stable 2-3 nm layer of barium oxalate. The negative surface charge of the oxalate effectively passivated the BaTiO3 providing a surface suitable for the use of a cationic dispersant, polyethylenimine (PEI). Rheological properties indicate the presence of an oxalate-PEI interaction which can be detrimental to dispersion. With a better understanding of the aqueous surface chemistry of BaTiO3 the surface chemistry was manipulated to control the adsorption of aqueous soluble complexes of Co, Nb, and Bi, three common dopants in the processing of BaTiO3 Surface charge, TEM, and EDS analysis showed that while in suspension the dopants selectively absorbed onto the particle surface forming an engineered coating. (Abstract shortened by UMI.)

Pure dipolar-interacted CoFe{sub 2}O{sub 4} nanoparticles and their magnetic properties

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

Xu, Shi-tao; School of Physics and Electronic Information, Huaibei Normal University, Huaibei 235000; Ma, Yong-qing, E-mail: yqma@ahu.edu.cn

2015-02-15

Graphical abstract: The mono-dispersed CoFe{sub 2}O{sub 4} nanoparticles with the uniform size of 10.5 ± 2 nm were first synthesized and then they were embedded in amorphous SiO{sub 2} matrix with different CoFe{sub 2}O{sub 4} nanoparticles’ concentrations. The large coercivity (3056 Oe) and the remanence ratio (0.63) were obtained by suitably diluting CoFe{sub 2}O{sub 4} nanoparticles into the SiO{sub 2} matrix. The reciprocal of the absolute maximum of δm and the M{sub r}/M{sub s} ratio behave in the same trend (as shown in (e)), indicating that the M{sub r}/M{sub s} ratio was dominated by the interparticle dipolar interaction. The presentmore » work is meaningful for revealing the underlying mechanism in nano-scaled magnetic system and improving the magnetic performance. - Highlights: • The mono-dispersed CoFe{sub 2}O{sub 4} nanoparticles with the uniform size of 10.5 ± 2 nm were synthesized by the thermal decomposition of metals acetylacetonates in solvents with high boiling point. • The large coercivity (3056 Oe) and the remanence ratio (0.63) were obtained by diluting CoFe{sub 2}O{sub 4} nanoparticles into the SiO{sub 2} matrix with a suitable concentration. • The surface anisotropy and interparticle dipolar interaction affect the magnetic performance and magnetic ordering state. • It was observed that the M{sub r}/M{sub s} ratio was dominated by the interparticle dipolar interaction. - Abstract: The mono-dispersed and uniform CoFe{sub 2}O{sub 4} nanoparticles were synthesized by the thermal decomposition of Fe(acac){sub 3} and Co(acac){sub 2}. Then the CoFe{sub 2}O{sub 4} nanoparticles were diluted in amorphous SiO{sub 2} matrix with different CoFe{sub 2}O{sub 4} nanoparticles’ concentrations. All samples show the positive or negative exchange bias behavior, indicating the presence of canted spin layer at the CoFe{sub 2}O{sub 4} nanoparticles’ surface. The large effective anisotropy constant (3.38 × 10{sup 6} erg/cm{sup 3}) was observed, which can be attributed to the induced surface anisotropy by the canted surface spins. The reduced magnetization (M{sub r}/M{sub s}) was dominated by the interparticle dipolar interaction while the coercivity (H{sub c}) was determined by the synergistic effects of the surface anisotropy, interparticle dipolar interaction and interface effect. By suitably diluting CoFe{sub 2}O{sub 4} in the SiO{sub 2} matrix, the high H{sub c} (3056 Oe) and the M{sub r}/M{sub s} (0.63) can be obtained, which is larger than most of those reported before. The present work is meaningful for revealing the underlying mechanism in nano-scaled magnetic system and improving the magnetic performance.« less

Molecular dynamics simulations of the surface tension of oxygen-supersaturated water

NASA Astrophysics Data System (ADS)

Jain, S.; Qiao, L.

2017-04-01

In this work, non-reactive molecular dynamic simulations were conducted to determine the surface tension of water as a function of the concentration of the dissolved gaseous molecules (O2), which would in turn help to predict the pressure inside the nanobubbles under supersaturation conditions. Knowing the bubble pressure is a prerequisite for understanding the mechanisms behind the spontaneous combustion of the H2/O2 gases inside the nanobubbles. First, the surface tension of pure water was determined using the planar interface method and the Irving and Kirkwood formula. Next, the surface tension of water containing four different supersaturation concentrations (S) of O2 gas molecules was computed considering the curved interface of a nanobubble. The surface tension of water was found to decrease with an increase in the supersaturation ratio or the concentration of the dissolved O2 gas molecules.

Surface functionalization of chitosan-coated magnetic nanoparticles for covalent immobilization of yeast alcohol dehydrogenase from Saccharomyces cerevisiae

NASA Astrophysics Data System (ADS)

Li, Gui-yin; Zhou, Zhi-de; Li, Yuan-jian; Huang, Ke-long; Zhong, Ming

2010-12-01

A novel and efficient immobilization of yeast alcohol dehydrogenase (YADH, EC1.1.1.1) from Saccharomyces cerevisiae has been developed by using the surface functionalization of chitosan-coated magnetic nanoparticles (Fe 3O 4/KCTS) as support. The magnetic Fe 3O 4/KCTS nanoparticles were prepared by binding chitosan alpha-ketoglutaric acid (KCTS) onto the surface of magnetic Fe 3O 4 nanoparticles. Later, covalent immobilization of YADH was attempted onto the Fe 3O 4/KCTS nanoparticles. The effect of various preparation conditions on the immobilized YADH process such as immobilization time, enzyme concentration and pH was investigated. The influence of pH and temperature on the activity of the free and immobilized YADH using phenylglyoxylic acid as substrate has also been studied. The optimum reaction temperature and pH value for the enzymatic conversion catalyzed by the immobilized YADH were 30 °C and 7.4, respectively. Compared to the free enzyme, the immobilized YADH retained 65% of its original activity and exhibited significant thermal stability and good durability.

Impacts of Nitrate Input on Nitrous Oxide Production in Lake Sediments

NASA Astrophysics Data System (ADS)

Ruder, C. K.; Schade, J. D.

2016-12-01

Denitrification in lake sediments removes nitrogen from the ecosystem and produces the greenhouse gas nitrous oxide (N2O) as a byproduct. However, little is understood about the rates and controls of N2O production in lake sediments. Agricultural activity in lake catchments often results in the runoff of nitrogen fertilizers, leading to increased N inputs in the form of nitrate (NO3-). This study evaluates the influence of nitrate input on N2O concentrations in a series of lakes across a range of agricultural land use intensities. We measured N2O concentrations in lakes across seasons, and also used lake sediment samples to perform anaerobic incubations with NO3- additions, with and without the addition of acetylene (blocking conversion of N2O to N2), to assess denitrification potentials and the rate of N2O production in sediments. Our results suggest that N2O concentrations are strongly impacted by the availability of NO3- across all agricultural land use intensities, with incubation NO3- additions leading to a marked increase in N2O production. However, sediments reacted differently by site in incubations without experimental additions of NO3- or acetylene, with half of the study lakes experiencing net N2O production and half exhibiting net N2O consumption over the course of the 24-hour incubation period. These results suggest the potential influence of sediment organic matter as a control on N2O concentrations. The positive influence of NO3- on N2O production is supported by observational data at each of the study sites, though water column total nitrogen (TN) appears to be a better indicator of dissolved N2O concentrations than aqueous NO3-, perhaps due to variations in internal N recycling. This study concludes that agricultural runoff of NO3- has the potential to enhance sediment N2O production; however, further investigation into the effects of sediment organic matter on N2O production, analysis of N2O vertical diffusion efficiency to link production rates in the sediment to actual surface emissions, and microbial community comparisons between study sites are necessary to adequately model the impact of agricultural land use on emissions of N2O from lakes.

Investigation of trimethylacetic acid adsorption on stoichiometric and oxygen-deficient CeO 2 (111) surfaces

DOE PAGES

Sanghavi, Shail; Wang, Weina; Nandasiri, Manjula I.; ...

2016-05-12

We studied the interactions between the carboxylate anchoring group from trimethylacetic acid (TMAA) and CeO 2(111) surfaces as a function of oxygen stoichiometry using in situ X-ray photoelectron spectroscopy (XPS). The stoichiometric CeO 2(111) surface was obtained by annealing the thin film under 2.0 × 10 –5 Torr of oxygen at ~550 °C for 30 min. In order to reduce the CeO 2(111) surface, the thin film was annealed under ~5.0 × 10 –10 Torr vacuum conditions at 550 °C, 650 °C, 750 °C and 850 °C for 30 min to progressively increase the oxygen defect concentration on the surface.more » The saturated TMAA coverage on the CeO 2(111) surface determined from XPS elemental composition is found to increase with increasing oxygen defect concentration. This is attributed to the increase of under-coordinated cerium sites on the surface with the increase in the oxygen defect concentrations. Furthermore, XPS results were in agreement with periodic density functional theory (DFT) calculations and indicate a stronger binding between the carboxylate group from TMAA and the oxygen deficient CeO 2–δ(111) surface through dissociative adsorption.« less

Impact of the 2008 Global Recession on Air Quality over the United States: Implications for Surface Ozone Levels from Changes in NOx Emissions

NASA Technical Reports Server (NTRS)

Tong, Daniel; Pan, Li; Chen, Weiwei; Lamsal, Lok; Lee, Pius; Tang, Youhua; Kim, Hyuncheol; Kondragunta, Shobha; Stajner, Ivanka

2016-01-01

Satellite and ground observations detected large variability in nitrogen oxides (NOx) during the 2008 economic recession, but the impact of the recession on air quality has not been quantified. This study combines observed NOx trends and a regional chemical transport model to quantify the impact of the recession on surface ozone (O3) levels over the continental United States. The impact is quantified by simulating O3 concentrations under two emission scenarios: business-as-usual (BAU) and recession. In the BAU case, the emission projection from the Cross-State Air Pollution Rule is used to estimate the would-be NOx emission level in 2011. In the recession case, the actual NO2 trends observed from Air Quality System ground monitors and the Ozone Monitoring Instrument on the Aura satellite are used to obtain realistic changes in NOx emissions. The model prediction with the recession effect agrees better with ground O3 observations over time and space than the prediction with the BAU emission. The results show that the recession caused a 12ppbv decrease in surface O3 concentration over the eastern United States, a slight increase (0.51ppbv) over the Rocky Mountain region, and mixed changes in the Pacific West. The gain in air quality benefits during the recession, however, could be quickly offset by the much slower emission reduction rate during the post-recession period.

Influence of alumina coating on characteristics and effects of SiO2 nanoparticles in algal growth inhibition assays at various pH and organic matter contents.

PubMed

Van Hoecke, Karen; De Schamphelaere, Karel A C; Ramirez-Garcia, Sonia; Van der Meeren, Paul; Smagghe, Guy; Janssen, Colin R

2011-08-01

Silica nanoparticles (NPs) belong to the industrially most important NP types. In a previous study it was shown that amorphous SiO(2) NPs of 12.5 and 27.0 nm are stable in algal growth inhibition assays and that their ecotoxic effects are related to NP surface area. Here, it was hypothesized and demonstrated that an alumina coating completely alters the particle-particle, particle-test medium and particle-algae interactions of SiO(2) NPs. Therefore, stability and surface characteristics, dissolution, nutrient adsorption and effects on algal growth rate of both alumina coated SiO(2) NPs and bare SiO(2) NPs in OECD algal test medium as a function of pH (6.0-8.6) and natural organic matter (NOM) contents (0-12 mg C/l) were investigated. Alumina coated SiO(2) NPs aggregated in all media and adsorbed phosphate depending on pH and NOM concentration. On the other hand, no aggregation or nutrient adsorption was observed for the bare SiO(2) NPs. Due to their positive surface charge, alumina coated SiO(2) NPs agglomerated with Pseudokirchneriella subcapitata. Consequently, algal cell density measurements based on cell counts were unreliable and hence fluorescent detection of extracted chlorophyll was the preferred method. Alumina coated SiO(2) NPs showed lower toxicity than bare SiO(2) NPs at concentrations ≥46 mg/l, except at pH 6.0. At low concentrations, no clear pH effect was observed for alumina coated SiO(2) NPs, while at higher concentrations phosphate deficiency could have contributed to the higher toxicity of those particles at pH 6.0-6.8 compared to higher pH values. Bare SiO(2) NPs were not toxic at pH 6.0 up to 220 mg/l. Addition of NOM decreased toxicity of both particles. For SiO(2) NPs the 48 h 20% effect concentration of 21.8 mg/l increased 2.6-21 fold and a linear relationship was observed between NOM concentration and effective concentrations. No effect was observed for alumina coated SiO(2) NPs in presence of NOM up to 1000 mg/l. All experiments point out that the alumina coating completely altered NP interactions. Due to the difference in surface composition the SiO(2) NPs, which had the smallest surface area, were more toxic to the alga than the alumina coated SiO(2) NPs. Hence, surface modification can dominate the effect of surface area on toxicity. Copyright © 2011 Elsevier Ltd. All rights reserved.

Ozone concentrations and ultraviolet fluxes on Earth-like planets around other stars.

PubMed

Segura, Antígona; Krelove, Kara; Kasting, James F; Sommerlatt, Darrell; Meadows, Victoria; Crisp, David; Cohen, Martin; Mlawer, Eli

2003-01-01

Coupled radiative-convective/photochemical modeling was performed for Earth-like planets orbiting different types of stars (the Sun as a G2V, an F2V, and a K2V star). O(2) concentrations between 1 and 10(-5) times the present atmospheric level (PAL) were simulated. The results were used to calculate visible/near-IR and thermal-IR spectra, along with surface UV fluxes and relative dose rates for erythema and DNA damage. For the spectral resolution and sensitivity currently planned for the first generation of terrestrial planet detection and characterization missions, we find that O(2) should be observable remotely in the visible for atmospheres containing at least 10(-2) PAL of O(2). O(3) should be visible in the thermal-IR for atmospheres containing at least 10(-3) PAL of O(2). CH(4) is not expected to be observable in 1 PAL O(2) atmospheres like that of modern Earth, but it might be observable at thermal-IR wavelengths in "mid-Proterozoic-type" atmospheres containing approximately 10(-1) PAL of O(2). Thus, the simultaneous detection of both O(3) and CH(4) - considered to be a reliable indication of life - is within the realm of possibility. High-O(2) planets orbiting K2V and F2V stars are both better protected from surface UV radiation than is modern Earth. For the F2V case the high intrinsic UV luminosity of the star is more than offset by the much thicker ozone layer. At O(2) levels below approximately 10(-2) PAL, planets around all three types of stars are subject to high surface UV fluxes, with the F2V planet exhibiting the most biologically dangerous radiation environment. Thus, while advanced life is theoretically possible on high-O(2) planets around F stars, it is not obvious that it would evolve as it did on Earth.

Biocompatibility of Mg Ion Doped Hydroxyapatite Films on Ti-6Al-4V Surface by Electrochemical Deposition.

PubMed

Lee, Kang; Choe, Han-Cheol

2016-02-01

In this study, we prepared magnesium (Mg) doped nano-phase hydroxyapatite (HAp) films on the TiO2 nano-network surface using electrochemical deposition method. Ti-6Al-4V ELI surface was anodized in 5 M NaOH solution at 0.3 A for 10 min. Nano-network TiO2 surface were formed by these anodization steps which acted as templates and anchorage for growth of the Mg doped HAp during subsequent pulsed electrochemical deposition process at 85 degrees C. The phase and morphologies of HAp deposits were influenced by the Mg ion concentration.

Ammonia and greenhouse gas concentrations at surfaces of simulated beef cattle bedded manure packs

USDA-ARS?s Scientific Manuscript database

Bedding is used in livestock operations to facilitate manure management and provide comfort for the animal. The research objective was to determine differences in ammonia (NH3), carbon dioxide (CO2), nitrous oxide (N2O) and methane (CH4) concentrations from simulated beef cattle bedded manure packs ...

Optimalization activity of ZnO NR/TiO2 NR-P3HT as an active layer based on hybrid bulk heterojunction on dye sensitized solar cell (DSSC)

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

Saputri, Liya Nikmatul Maula Zulfa; Ramelan, Ari Handono; Hanif, Qonita Awliya

2016-04-19

Dye sensitized solar cell (DSSC) with metal inorganic and conjugated organic polymer mixture, ZnO NR/TiO{sub 2} NR-P3HT as an active layer based on hybrid bulk heterojunction has been studied. The hybrid material was used to optimize DSSC performs for better efficiency than only TiO{sub 2} as an electrode. Synthesis of TiO{sub 2} nanorods (NR) was conducted by ball milling 1000 rpm for 4 hours and strong base reaction by hydrothermal process at 120 °C overnight. And the ZnO NR was synthesized from Zn(NO{sub 3}){sub 2}.4H{sub 2}O precusor by hydrotermal process at 90 °C for 5 hours and calcined on various temperaturemore » s of 400, 600, and 800 °C. ZnO NR was coated into an Tndium Tin Oxide (TTO) glass to collecting electron s effectively, where TiO{sup 2} NR were incorporated with poly(3 -hexylthiophene) (P3HT) on various concentration s of 5, 10, 15 mg/mL to obtain a larger surface area. Material characterization were performed by X -Ray Diffraction (XRD) and Uv-Vis spectrophotometer. For an application of DSSC were measured by T-V Keithley Multimeter and the efficiency of DSSC at various P3HT’s concentrations of 5, 10, 15 mg/mL were 7.44 × 10{sup −3}, 0.0114, 0.0104, respectively. The maximum efficiency of DSSC was showed when TiO{sup 2} NR-P3HT’s concentration was 10 mg/mL.« less

Study of different 3-aminopropyl triethoxysilane (APTES) concentration on TiO2 particles based IDE for cervical cancer detection

NASA Astrophysics Data System (ADS)

Raqeema, S.; Hashim, U.; Azizah, N.; Nadzirah, Sh.; Arshad, M. K. Md; Ruslinda, A. R.; Gopinath, Subash C. B.

2017-03-01

HPV that also called Human Papillomaviruses is the major cause of the cervical cancer. HPV 16 and HPV 18 are the two types of HPV are the most HPV-associated cancers and responsible as a high-risk HPV. Cervical cancer taken about 70 percent of all cases due HPV infections. Cervical malignancy for the most part development on a lady's cervix and its was developed slowly as cancer disease. TiO2 particles give better performance and low cost of the biosensor. The used of 3-aminopropyl triethoxysilane (APTES) will be more efficient for DNA nanochip. APTES used as absorption reaction to immobilize organic biomolecules on the inorganic surface. Besides, APTES give better functionalization of the adsorption mechanism on IDE. The surface functionalized for immobilizing the DNA, which is the combination of the DNA probe and the HPV target produce high sensitivity andfast detection of the IDE. The Current-Voltage (IV) characteristic proved the sensitivity of the DNA nanochip increase as the concentration varied from 0% concentration to 24% of APTES concentration.

Structural, surface wettability and antibacterial properties of HPMC-ZnO nanocomposite

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

Rao, B. Lakshmeesha; Asha, S.; Madhukumar, R.

The developed hydroxypropyl methylcellulose (HPMC)/Zinc oxide (ZnO) nanocomposite films were examined for structural property and surface wettability using X-ray diffraction and contact angle measurement. Antibacterial activity of these films was evaluated as a function of ZnO concentration. The microstructuralline parameters ( and (g in %)) decreased with increasing concentration of ZnO nanoparticles and there was increase in hydrophilicity. Addition of ZnO nanoparticles in films resulted in antimicrobial activity against tested microorganisms.

X-ray absorption spectroscopy investigations on oxidized Ni/Au contacts to p-GaN.

PubMed

Jan, J C; Asokan, K; Chiou, J W; Pong, W F; Tseng, P K; Chen, L C; Chen, F R; Lee, J F; Wu, J S; Lin, H J; Chen, C T

2001-03-01

X-ray absorption spectroscopy was used to investigate the electronic structure of as-deposited and oxidized Ni/Au contacts to p-GaN and to elucidate the mechanism responsible for low impedance. X-ray absorption near edge spectra of Ni K- and L3,2-edges clearly indicate formation of NiO on the sample surface after annealing. The reason for low impedance may be attributed to increase in hole concentration and existence of p-NiO layer on the surface.

Photocatalytic reduction of NO with NH3 using Si-doped TiO2 prepared by hydrothermal method.

PubMed

Jin, Ruiben; Wu, Zhongbiao; Liu, Yue; Jiang, Boqiong; Wang, Haiqiang

2009-01-15

A series of Si-doped TiO2 (Si/TiO2) photocatalysts supported on woven glass fabric were prepared by hydrothermal method for photocatalytic reduction of NO with NH3. The photocatalytic activity tests were carried out in a continuous Pyrex reactor with the flow rate of 2000mL/min under UV irradiation (luminous flux: 1.1x10(4)lm, irradiated catalyst area: 160cm2). The photocatalysts were characterized by X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) spectrophotometer, transmission electron microscopy (TEM), photoluminescence (PL) and temperature-programmed desorption (TPD). The experiment results showed that NO conversion on Si/TiO2 at 323K could exceed 60%, which was about 50% higher than that on Degussa P25 and pure TiO2. With the doping of Si, photocatalysts with smaller crystal size, larger surface area and larger pore volume were obtained. It was also found that Ti-O-Si bands were formed on the surface of Si/TiO2 and that the surface hydroxyl concentration was greatly increased. As a result, total acidity and NH3 chemisorption amount were enhanced for Si/TiO2 leading to its photocatalytic activity improvement.

Preparation and Thermo-Physical Properties of Fe2O3-Propylene Glycol Nanofluids.

PubMed

Shylaja, A; Manikandan, S; Suganthi, K S; Rajan, K S

2015-02-01

Iron oxide (Fe2O3) nanoparticles were prepared from ferric chloride and ferrous sulphate by precipitation reaction. Fe2O3-propylene glycol nanofluid was prepared by dispersing Fe2O3 nanoparticles in propylene glycol through stirred bead milling, shear homogenization and probe ultrasonication. The nanofluid was characterized through measurement of viscosity, particle size distribution and thermal conductivity. The interactions between Fe2O3 nanoparticles and propylene glycol on the nanoparticle surfaces lead to reduction in viscosity, the magnitude of which increases with nanoparticle concentration (0-2 vol%) at room temperature. The thermal conductivity enhancement for 2 vol% nanofluid was about 21% at room temperature, with liquid layering being the major contributor for thermal conductivity enhancement.

Performance of selective catalytic reduction of NO with NH3 over natural manganese ore catalysts at low temperature.

PubMed

Wang, Tao; Zhu, Chengzhu; Liu, Haibo; Xu, Yongpeng; Zou, Xuehua; Xu, Bin; Chen, Tianhu

2018-02-01

Natural manganese ore catalysts for selective catalytic reduction (SCR) of NO with NH 3 at low temperature in the presence and absence of SO 2 and H 2 O were systematically investigated. The physical and chemical properties of catalysts were characterized by X-ray diffraction, Brunauer-Emmett-Teller (BET) specific surface area, NH 3 temperature-programmed desorption (NH 3 -TPD) and NO-TPD methods. The results showed that natural manganese ore from Qingyang of Anhui Province had a good low-temperature activity and N 2 selectivity, and it could be a novel catalyst in terms of stability, good efficiency, good reusability and lower cost. The NO conversion exceeded 85% between 150°C and 300°C when the initial NO concentration was 1000 ppm. The activity was suppressed by adding H 2 O (10%) or SO 2 (100 or 200 ppm), respectively, and its activity could recover while the SO 2 supply is cut off. The simultaneous addition of H 2 O and SO 2 led to the increase of about 100% in SCR activity than bare addition of SO 2 . The formation of the amorphous MnO x , high concentration of lattice oxygen and surface-adsorbed oxygen groups and a lot of reducible species as well as adsorption of the reactants brought about excellent SCR performance and exhibited good SO 2 and H 2 O resistance.

PVA and PEG functionalised LSMO nanoparticles for magnetic fluid hyperthermia application

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

Jadhav, S.V.; Nikam, D.S.; Khot, V.M.

2015-04-15

La{sub 0.7}Sr{sub 0.3}MnO{sub 3} magnetic nanoparticles are synthesized by a solution combustion method and functionalised with polyvinyl alcohol and polyethylene glycol. The induction heating characteristics of coated magnetic nanoparticles (42 °C) were observed at a reasonably low concentration (5 mg/mL). Remarkably, coated magnetic nanoparticles exhibited a promisingly high specific absorption rate with varying magnetic field and constant frequency. The surface analysis is carried out by X-ray photoelectron spectroscopy. A reduction in the agglomeration of the particles was observed when the magnetic nanoparticles were functionalised with polyvinyl alcohol or polyethylene glycol and can be confirmed by transmission electron microscopy and dynamicmore » light scattering studies. Vibrating sample magnetometer measurements indicate superparamagnetic behaviour at room temperature before and after coating. Colloidal stability revealed a considerably higher zeta potential value for coated system. In vitro cytotoxicity test of the magnetic nanoparticles indicates that coated nanoparticles have no significant effect on cell viability within the tested concentrations (1–5 mg mL{sup -1}) as compared to uncoated La{sub 0.7}Sr{sub 0.3}MnO{sub 3}. All these findings explore the potentiality of La{sub 0.7}Sr{sub 0.3}MnO{sub 3} nanoparticles for magnetic fluid hyperthermia. - Highlights: • Surface functionalization of LSMO nanoparticles — first time with PVA • Surface functionalization of LSMO nanoparticles — first time with PEG • BSA protein — first time used as dispersion medium for stability of LSMO nanoparticles • The heating ability observed at low concentration • Improved efficiency of magnetic fluid hyperthermia treatment with surfactants.« less

Evaluating a Space-Based Indicator of Surface Ozone-NOx-VOC Sensitivity Over Midlatitude Source Regions and Application to Decadal Trends

EPA Science Inventory

Determining effective strategies for mitigating surface ozone (O3) pollution requires knowledge of the relative ambient concentrations of its precursors, NOx, and VOCs. The space-based tropospheric column ratio of formaldehyde to NO2 (FNR) has been used as an indicator to identif...

Microbial Oxidation of Fe2+ and Pyrite Exposed to Flux of Micromolar H2O2 in Acidic Media

PubMed Central

Ma, Yingqun; Lin, Chuxia

2013-01-01

At an initial pH of 2, while abiotic oxidation of aqueous Fe2+ was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe2+ could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe2+ to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe2+-Fe3+ conversion rate in the solution (due to reduced microbial activity) weakened the Fe3+-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria. PMID:23760258

Microbial Oxidation of Fe2+ and Pyrite Exposed to Flux of Micromolar H2O2 in Acidic Media

NASA Astrophysics Data System (ADS)

Ma, Yingqun; Lin, Chuxia

2013-06-01

At an initial pH of 2, while abiotic oxidation of aqueous Fe2+ was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe2+ could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe2+ to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe2+-Fe3+ conversion rate in the solution (due to reduced microbial activity) weakened the Fe3+-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria.

Electron Spin Resonance (ESR) detection of active oxygen species and organic phases in Martian soils

NASA Technical Reports Server (NTRS)

Tsay, Fun-Dow; Kim, Soon Sam; Liang, Ranty H.

1989-01-01

The presence of active oxygen species (O(-), O2(-), O3(-)) and other strong oxidants (Fe2O3 and Fe3O4) was invoked in interpretations of the Viking biological experiments and a model was also suggested for Martian surface chemistry. The non-biological interpretations of the biological results gain futher support as no organic compounds were detected in the Viking pyrolysis-gas chromatography mass spectrometer (GCSM) experiments at concentrations as low as 10 ppb. Electron spin resonance (ESR) measures the absorption of microwaves by a paramagnetic and/or ferromagnetic center in the presence of an external field. In many instances, ESR has the advantage of detailed submicroscopic identification of the transient species and/or unstable reaction intermediates in their environments. Since the higly active oxygen species (O(-), O2(-), O3(-), and R-O-O(-)) are all paramagnetic in nature, they can be readily detected in native form by the ESR method. Active oxygen species likely to occur in the Martian surface samples were detected by ESR in UV-irradiated samples containing MgO. A miniaturized ESR spectrometer system can be developed for the Mars Rover Sample Return Mission. The instrument can perform the following in situ Martian samples analyses: detection of active oxygen species; characterization of Martian surface chemistry and photooxidation processes; and searching for organic compounds in the form of free radicals preserved in subsoils, and detection of microfossils with Martian carbonate sediments.

Direct Heteroepitaxial Growth of ZnO over GaN Crystal in Aqueous Solution

NASA Astrophysics Data System (ADS)

Hamada, Takahiro; Ito, Akihiro; Nagao, Nobuaki; Suzuki, Nobuyasu; Fujii, Eiji; Tsujimura, Ayumu

2013-04-01

We report on the structural and electrical properties of ZnO films grown on surface-treated GaN/Al2O3 substrates by chemical bath deposition. X-ray diffraction analysis indicated that the ZnO films had a single-crystalline wurtzite structure with c-axis orientation. The ZnO film exhibited n-type conduction with a carrier concentration of 6.9 ×1018 cm-3, an electron mobility of 41 cm2/(V.s), and a resistivity of 2.2 ×10-2 Ω.cm. A low specific contact resistivity of 4.3 ×10-3 Ω.cm2 was obtained at the ZnO/n-GaN interface. Additionally, the ZnO film exhibited high transparency in the visible and infrared region.

Spatial and Temporal Variability of Ground and Satellite Column Measurements of NO2 and O3 over the Atlantic Ocean During the Deposition of Atmospheric Nitrogen to Coastal Ecosystems Experiment

NASA Technical Reports Server (NTRS)

Martins, Douglas K.; Najjar, Raymond G.; Tzortziou, Maria; Abuhassan, Nader; Thompson, Anne M.; Kollonige, Debra E.

2016-01-01

In situ measurements of O3 and nitrogen oxides (NO + NO2=NOx) and remote sensing measurements of total column NO2 and O3 were collected on a ship in the North Atlantic Ocean as part of the Deposition of Atmospheric Nitrogen to Coastal Ecosystems (DANCE) campaign in July August 2014,100 km east of the mid-Atlantic United States. Relatively clean conditions for both surface in situ mixing ratio and total column O3 and NO2 measurements were observed throughout the campaign. Increased surface and column NO2 and O3 amounts were observed when a terrestrial air mass was advected over the study region. Relative to ship-based total column measurements using a Pandora over the entire study, satellite measurements overestimated total column NO2 under these relatively clean atmospheric conditions over offshore waters by an average of 16. Differences are most likely due to proximity, or lack thereof, to surface emissions; spatial averaging due to the field of view of the satellite instrument; and the lack of sensitivity of satellite measurements to the surface concentrations of pollutants. Total column O3 measurements from the shipboard Pandora showed good correlation with the satellite measurements(r 0.96), but satellite measurements were 3 systematically higher than the ship measurements, in agreement with previous studies. Derived values of boundary layer height using the surface in situ and total column measurements of NO2 are much lower than modeled and satellite-retrieved boundary layer heights, which highlight the differences in the vertical distribution between terrestrial and marine environments.

Three-dimensional ordered macroporous bismuth vanadates: PMMA-templating fabrication and excellent visible light-driven photocatalytic performance for phenol degradation.

PubMed

Liu, Yuxi; Dai, Hongxing; Deng, Jiguang; Zhang, Lei; Au, Chak Tong

2012-04-07

Three-dimension ordered macroporous (3D-OM) bismuth vanadates with a monoclinic crystal structure and high surface area (18-24 m(2) g(-1)) have been prepared using ascorbic acid (AA)- or citric acid (CA)-assisted poly(methyl methacrylate) (PMMA)-templating strategy with bismuth nitrate and ammonium metavanadate as the metal sources, HNO(3) as the pH adjuster and ethylene glycol and methanol as the solvent. The materials were characterized by a number of analytical techniques. The photocatalytic performance of the porous BiVO(4) samples was evaluated for the degradation of phenol in the presence of a small amount of H(2)O(2) under visible light illumination. The effects of the initial phenol concentration and the H(2)O(2) amount on the photocatalytic activity of the photocatalyst were examined. It is shown that the chelating agent, AA or CA, and the amount in which it is added had a significant impact on the quality of the 3D-OM structure, with a "(Bi + V):chelating agent" molar ratio of 2:1 being the most appropriate. Among the as-prepared BiVO(4) samples, the one with a surface area of ca. 24 m(2) g(-1) showed the best visible light-driven photocatalytic performance for phenol degradation (phenol conversion = ca. 94% at phenol concentration = 0.1 mmol L(-1) and in the presence of 0.6 mL H(2)O(2)). A higher phenol conversion could be achieved within the same reaction time if the phenol concentration in the aqueous solution was lowered, but an excess amount of H(2)O(2) was not a favorable factor for the enhancement of the catalytic activity. It is concluded that the excellent photocatalytic activity of 3D-OM BiVO(4) is due to the high quality 3D-OM structured BiVO(4) that has a high surface area and surface oxygen vacancy density. We are sure that the 3D-OM material is a promising photocatalyst for the removal of organics from wastewater under visible light illumination. This journal is © The Royal Society of Chemistry 2012

Preparation and Characterization of ZnO Nanoparticles Supported on Amorphous SiO2

PubMed Central

Chen, Ying; Ding, Hao; Sun, Sijia

2017-01-01

In order to reduce the primary particle size of zinc oxide (ZnO) and eliminate the agglomeration phenomenon to form a monodisperse state, Zn2+ was loaded on the surface of amorphous silica (SiO2) by the hydrogen bond association between hydroxyl groups in the hydrothermal process. After calcining the precursors, dehydration condensation among hydroxyl groups occurred and ZnO nanoparticles supported on amorphous SiO2 (ZnO–SiO2) were prepared. Furthermore, the SEM and TEM observations showed that ZnO nanoparticles with a particle size of 3–8 nm were uniformly and dispersedly loaded on the surface of amorphous SiO2. Compared with pure ZnO, ZnO–SiO2 showed a much better antibacterial performance in the minimum inhibitory concentration (MIC) test and the antibacterial properties of the paint adding ZnO–SiO2 composite. PMID:28796157

Impact of future land cover changes on HNO3 and O3 surface dry deposition

NASA Astrophysics Data System (ADS)

Verbeke, T.; Lathière, J.; Szopa, S.; de Noblet-Ducoudré, N.

2015-07-01

Dry deposition is a key component of surface-atmosphere exchange of compounds, acting as a sink for several chemical species. Meteorological factors, chemical properties of the trace gas considered and land surface properties are strong drivers of dry deposition efficiency and variability. Under both climatic and anthropogenic pressure, the vegetation distribution over the Earth has been changing a lot over the past centuries, and could be significantly altered in the future. In this study, we perform a modeling investigation of the potential impact of land-cover changes between present-day (2006) and the future (2050) on dry deposition rates, with special interest for ozone (O3) and nitric acid vapor (HNO3), two compounds which are characterized by very different physico-chemical properties. The 3-D chemistry transport model LMDz-INCA is used, considering changes in vegetation distribution based on the three future projections RCPs 2.6, 4.5 and 8.5. The 2050 RCP 8.5 vegetation distribution leads to a rise up to 7 % (+0.02 cm s-1) in VdO3 and a decrease of -0.06 cm s-1 in VdHNO3 relative to the present day values in tropical Africa, and up to +18 and -15 % respectively in Australia. When taking into account the RCP 4.5 scenario, which shows dramatic land cover change in Eurasia, VdHNO3 increases by up to 20 % (annual-mean value) and reduces VdO3 by the same magnitude in this region. When analyzing the impact of dry deposition change on atmospheric chemical composition, our model calculates that the effect is lower than 1 ppb on annual mean surface ozone concentration, for both for the RCP8.5 and RCP2.6 scenarios. The impact on HNO3 surface concentrations is more disparate between the two scenarios, regarding the spatial repartition of effects. In the case of the RCP 4.5 scenario, a significant increase of the surface O3 concentration reaching locally up to 5 ppb (+5 %) is calculated on average during the June-August period. This scenario induces also an increase of HNO3 deposited flux exceeding locally 10 % for monthly values. Comparing the impact of land-cover change to the impact of climate change, considering a 0.93 °C increase of global temperature, on dry deposition velocities, we estimate that the strongest increase over lands occurs in the North Hemisphere during winter especially in Eurasia, by +50 % (+0.07 cm s-1) for VdO3 and +100 % (+0.9 cm s-1) for VdHNO3. However, different regions are affected by both changes, with climate change impact on deposition characterized by a latitudinal gradient, while the land-cover change impact is much more heterogeneous depending on vegetation distribution modification described in the future RCP scenarios. The impact of long-term land-cover changes on dry deposition is shown to be non-negligible and should be therefore considered in biosphere-atmospheric chemistry interaction studies in order to have a fully consistent picture.

Synthesis of Au/TiO2 Core-Shell Nanoparticles from Titanium Isopropoxide and Thermal Resistance Effect of TiO2 Shell

NASA Astrophysics Data System (ADS)

Kwon, Hyun-Woo; Lim, Young-Min; Tripathy, Suraj Kumar; Kim, Byoung-Gyu; Lee, Min-Sang; Yu, Yeon-Tae

2007-04-01

On the synthesis of Au/TiO2 core-shell structure nanoparticles, the effect of the concentration of Ti4+ on the morphology and optical property of Au/TiO2 core-shell nanoparticles was examined. A gold colloid was prepared by mixing HAuCl4\\cdot4H2O and C6H5Na3\\cdot2H2O. Titanium stock solution was prepared by mixing solutions of titanium(IV) isopropoxide (TTIP) and triethanolamine (TEOA). The concentration of the Ti4+ stock solution was adjusted to 0.01-0.3 mM, and then the gold colloid was added to the Ti4+ stock solution. Au/TiO2 core-shell structure nanoparticles could be prepared by the hydrolysis of the Ti4+ stock solution at 80 °C. The size of the as-prepared Au nanoparticles was 15 nm. The thickness of the TiO2 shell on the surface of gold particles was about 10 nm. The absorption peak of the Au/TiO2 core-shell nanoparticles shifted towards the red end of the spectrum by about 3 nm because of the formation of the TiO2 shell on the surface of the gold particles. The crystal structure of the TiO2 shell showed an anatase phase. The increase in the Au crystallite size of the Au/TiO2 nanoparticles with increasing heat treatment temperature is smaller than that in the pure Au nanoparticles. This may be due to the encapsulation of Au particles with the TiO2 shell that prevents the growth of the nanoparticle nucleation.

Photocatalytic activity of Pt-TiO2 films supported on hydroxylated fly ash cenospheres under visible light

NASA Astrophysics Data System (ADS)

Wang, Bing; Yang, Zewei; An, Hao; Zhai, Jianping; Li, Qin; Cui, Hao

2015-01-01

TiO2 was coated on the surface of hydroxylated fly ash cenospheres (FACs) by the sol-gel method. Platinum (Pt) was then deposited on these TiO2/FAC particles by a photoreduction method to form PTF photocatalyst. The photocatalytic activity of PTF for the degradation of methylene blue (MB) under visible-light irradiation was determined. The PTF sample that was calcined at 450 °C and had a Pt/TiO2 mass ratio of 1.5% exhibited the optimal photocatalytic activity for degradation of MB with a catalyst concentration of 3 g L-1. MB was photodecomposed by PTF in aqueous solution more effectively at alkali pH than at acidic pH, because more MB molecules were adsorbed on the surface of PTF under alkaline conditions than that under acidic. The effect of various inorganic anions (HCO3-, F-, SO42-, NO3-, and Cl-) on the photodegradation of MB by PTF was also investigated. Addition of anions with a concentration of 5 mM enhanced the photocatalytic efficiency of PTF because of the improved adsorption of MB. This effect weakened as the anion concentration was increased, which was attributed to the ability of the anions to scavenge hydroxyl radicals and holes. Our results indicated that the photodegradation of MB took place mainly on the catalyst surface. The generation of hydroxyl radicals in the photocatalytic reaction was measured by the fluorescence method. KI was used to determine the participation of holes in the photocatalytic reaction. Both hydroxyl radicals and valence-band holes were detected in the PTF system. Recycling tests revealed that calcination of the used PTF helped to regain its photocatalytic activity.

Most probable number methodology for quantifying dilute concentrations and fluxes of Escherichia coli O157:H7 in surface waters.

PubMed

Jenkins, M B; Endale, D M; Fisher, D S; Gay, P A

2009-02-01

To better understand the transport and enumeration of dilute densities of Escherichia coli O157:H7 in agricultural watersheds, we developed a culture-based, five tube-multiple dilution most probable number (MPN) method. The MPN method combined a filtration technique for large volumes of surface water with standard selective media, biochemical and immunological tests, and a TaqMan confirmation step. This method determined E. coli O157:H7 concentrations as low as 0.1 MPN per litre, with a 95% confidence level of 0.01-0.7 MPN per litre. Escherichia coli O157:H7 densities ranged from not detectable to 9 MPN per litre for pond inflow, from not detectable to 0.9 MPN per litre for pond outflow and from not detectable to 8.3 MPN per litre for within pond. The MPN methodology was extended to mass flux determinations. Fluxes of E. coli O157:H7 ranged from <27 to >10(4) MPN per hour. This culture-based method can detect small numbers of viable/culturable E. coli O157:H7 in surface waters of watersheds containing animal agriculture and wildlife. This MPN method will improve our understanding of the transport and fate of E. coli O157:H7 in agricultural watersheds, and can be the basis of collections of environmental E. coli O157:H7.

Coefficient of friction and wear rate effects of different composite nanolubricant concentrations on Aluminium 2024 plate

NASA Astrophysics Data System (ADS)

Zawawi, N. N. M.; Azmi, W. H.; Redhwan, A. A. M.; Sharif, M. Z.

2017-10-01

Wear of sliding parts and operational machine consistency enhancement can be avoided with good lubrication. Lubrication reduce wear between two contacting and sliding surfaces and decrease the frictional power losses in compressor. The coefficient of friction and wear rate effects study were carried out to measure the friction and anti-wear abilities of Al2O3-SiO2 composite nanolubricants a new type of compressor lubricant to enhanced the compressor performances. The tribology test rig employing reciprocating test conditions to replicate a piston ring contact in the compressor was used to measure the coefficient of friction and wear rate. Coefficient of friction and wear rate effects of different Al2O3-SiO2/PAG composite nanolubricants of Aluminium 2024 plate for 10-kg load at different speed were investigated. Al2O3 and SiO2 nanoparticles were dispersed in the Polyalkylene Glycol (PAG 46) lubricant using two-steps method of preparation. The result shows that the coefficient friction and wear rate of composite nanolubricants decreased compared to pure lubricant. The maximum reduction achievement for friction of coefficient and wear rate by Al2O3-SiO2 composite nanolubricants by 4.78% and 12.96% with 0.06% volume concentration. Therefore, 0.06% volume concentration is selected as the most enhanced composite nanolubricants with effective coefficient of friction and wear rate reduction compared to other volume concentrations. Thus, it is recommended to be used as the compressor lubrication to enhanced compressor performances.

A Laughing Gas Greenhouse for the Proterozoic?

NASA Astrophysics Data System (ADS)

Roberson, A. L.; Roadt, J.; Halevy, I.; Kasting, J. F.

2010-12-01

An anoxic, sulfidic ‘Canfield ocean’ during the Proterozoic (0.75-2.3 Ga) would have had limited trace metal abundances because of the low solubility of metal sulfides. The limitation on copper, specifically, would have had a significant impact on marine denitrification. Copper is needed for the enzyme that controls the final step of denitrification, from N2O to N2. Today, only about 5-6 percent of denitrification results in release of N2O. If all denitrification stopped at N2O during the Proterozoic, the N2O flux could have been 15-20 times higher than today. Other parts of the nitrogen cycle should have been able to operate at rates comparable to today, as catalysts for these reactions should have existed. The high N2O flux should have created higher atmospheric N2O concentrations; although this effect may have been offset by faster rates of N2O photolysis if O2 concentrations were lower than today. N2O concentrations of 0.3 to 30 ppmv, along with methane levels of 30-100 ppm, could have kept the surface warm during the Proterozoic without necessitating high CO2 levels. The high methane concentrations were a consequence of lack of dissolved O2 and sulfate in the deep ocean, which should have led to a high CH4 flux from marine sediments. A second oxygenation event at the end of the Proterozoic would have resulted in a shift to a more modern ocean and, consequently, more modern concentrations of atmospheric N2O and CH4.

Room Temperature Radiolytic Synthesized Cu@CuAlO2-Al2O3 Nanoparticles

PubMed Central

Abedini, Alam; Saion, Elias; Larki, Farhad; Zakaria, Azmi; Noroozi, Monir; Soltani, Nayereh

2012-01-01

Colloidal Cu@CuAlO2-Al2O3 bimetallic nanoparticles were prepared by a gamma irradiation method in an aqueous system in the presence of polyvinyl pyrrolidone (PVP) and isopropanol respectively as a colloidal stabilizer and scavenger of hydrogen and hydroxyl radicals. The gamma irradiation was carried out in a 60Co gamma source chamber with different doses up to 120 kGy. The formation of Cu@CuAlO2-Al2O3 nanoparticles was observed initially by the change in color of the colloidal samples from colorless to brown. Fourier transform infrared spectroscopy (FTIR) confirmed the presence of bonds between polymer chains and the metal surface at all radiation doses. Results of transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDX), and X-ray diffraction (XRD) showed that Cu@CuAlO2-Al2O3 nanoparticles are in a core-shell structure. By controlling the absorbed dose and precursor concentration, nanoclusters with different particle sizes were obtained. The average particle diameter increased with increased precursor concentration and decreased with increased dose. This is due to the competition between nucleation, growth, and aggregation processes in the formation of nanoclusters during irradiation. PMID:23109893

Room temperature radiolytic synthesized Cu@CuAlO(2)-Al(2)O(3) nanoparticles.

PubMed

Abedini, Alam; Saion, Elias; Larki, Farhad; Zakaria, Azmi; Noroozi, Monir; Soltani, Nayereh

2012-01-01

Colloidal Cu@CuAlO(2)-Al(2)O(3) bimetallic nanoparticles were prepared by a gamma irradiation method in an aqueous system in the presence of polyvinyl pyrrolidone (PVP) and isopropanol respectively as a colloidal stabilizer and scavenger of hydrogen and hydroxyl radicals. The gamma irradiation was carried out in a (60)Co gamma source chamber with different doses up to 120 kGy. The formation of Cu@CuAlO(2)-Al(2)O(3) nanoparticles was observed initially by the change in color of the colloidal samples from colorless to brown. Fourier transform infrared spectroscopy (FTIR) confirmed the presence of bonds between polymer chains and the metal surface at all radiation doses. Results of transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDX), and X-ray diffraction (XRD) showed that Cu@CuAlO(2)-Al(2)O(3) nanoparticles are in a core-shell structure. By controlling the absorbed dose and precursor concentration, nanoclusters with different particle sizes were obtained. The average particle diameter increased with increased precursor concentration and decreased with increased dose. This is due to the competition between nucleation, growth, and aggregation processes in the formation of nanoclusters during irradiation.

Growth and Survival of Perchlorate-Reducing Bacteria in Media Containing Elevated Perchlorate Concentrations and UV-C Conditions

NASA Technical Reports Server (NTRS)

Bywaters, K. F.; Mckay, C. P.; Quinn, R. C.

2017-01-01

Introduction: The identification of perchlorate (ClO4(-)) on Mars has led to the possibility that complete redox couples are available for microbial metabolism in contemporary surface environments. Perchlorate-reducing bacteria (PRB) utilize ClO4(-) and chlorate (ClO3(-)) as terminal electron acceptors due to the high reduction potential. Additionally, ClO4(-) salts have been suggested as a possible source of brines on Mars and spectral evidence indicates that the hydration of ClO4(-) salts in the regolith of Martian is linked to the surface recurring slope lineae (RSL). For these reasons PRB may serve as analog organisms for possible life on Mars. However, there is very little information on the viability of PRB in aqueous environments that contain high levels of perchlorate Microorganisms on or near the surface of Mars, such as in the RSL, would potentially be exposed to high-salinity and high ultraviolet radiation environments. Under these extreme conditions, microorganisms must possess mechanisms for maintaining continued high genome fidelity. To assess possible microbial viability in contemporary Mars analog environments we are investigating the tolerance of two PRB strains in aqueous conditions under high UV-C conditions and high ClO4(-) concentrations.

Comparison Between Dielectric Barrier Discharge Plasma and Ozone Regenerations of Activated Carbon Exhausted with Pentachlorophenol

NASA Astrophysics Data System (ADS)

Qu, Guangzhou; Liang, Dongli; Qu, Dong; Huang, Yimei; Li, Jie

2014-06-01

In this study, two regeneration methods (dielectric barrier discharge (DBD) plasma and ozone (O3) regeneration) of saturated granular activated carbon (GAC) with pentachlorophenol (PCP) were compared. The results show that the two regeneration methods can eliminate contaminants from GAC and recover its adsorption properties to some extent. Comparing the DBD plasma with O3 regeneration, the adsorption rate and the capacity of the GAC samples after DBD plasma regeneration are greater than those after O3 regeneration. O3 regeneration decreases the specific surface area of GAC and increases the acidic surface oxygen groups on the surface of GAC, which causes a decrease in PCP on GAC uptake. With increasing regeneration cycles, the regeneration efficiencies of the two methods decrease, but the decrease in the regeneration efficiencies of GAC after O3 regeneration is very obvious compared with that after DBD plasma regeneration. Furthermore, the equilibrium data were fitted by the Freundlich and Langmuir models using the non-linear regression technique, and all the adsorption equilibrium isotherms fit the Langmuir model fairly well, which demonstrates that the DBD plasma and ozone regeneration processes do not appear to modify the adsorption process, but to shift the equilibrium towards lower adsorption concentrations. Analyses of the weight loss of GAC show that O3 regeneration has a lower weight loss than DBD plasma regeneration.

Deposition temperature dependence of material and Si surface passivation properties of O{sub 3}-based atomic layer deposited Al{sub 2}O{sub 3}-based films and stacks

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

Bordihn, Stefan, E-mail: s.bordihn2@q-cells.com; Mertens, Verena; Müller, Jörg W.

2014-01-15

The material composition and the Si surface passivation of aluminum oxide (Al{sub 2}O{sub 3}) films prepared by atomic layer deposition using Al(CH{sub 3}){sub 3} and O{sub 3} as precursors were investigated for deposition temperatures (T{sub Dep}) between 200 °C and 500 °C. The growth per cycle decreased with increasing deposition temperature due to a lower Al deposition rate. In contrast the material composition was hardly affected except for the hydrogen concentration, which decreased from [H] = 3 at. % at 200 °C to [H] < 0.5 at. % at 400 °C and 500 °C. The surface passivation performance was investigated after annealing at 300 °C–450 °C and also after firing stepsmore » in the typical temperature range of 800 °C–925 °C. A similar high level of the surface passivation performance, i.e., surface recombination velocity values <10 cm/s, was obtained after annealing and firing. Investigations of Al{sub 2}O{sub 3}/SiN{sub x} stacks complemented the work and revealed similar levels of surface passivation as single-layer Al{sub 2}O{sub 3} films, both for the chemical and field-effect passivation. The fixed charge density in the Al{sub 2}O{sub 3}/SiN{sub x} stacks, reflecting the field-effect passivation, was reduced by one order of magnitude from 3·10{sup 12} cm{sup −2} to 3·10{sup 11} cm{sup −2} when T{sub Dep} was increased from 300 °C to 500 °C. The level of the chemical passivation changed as well, but the total level of the surface passivation was hardly affected by the value of T{sub Dep}. When firing films prepared at of low T{sub Dep}, blistering of the films occurred and this strongly reduced the surface passivation. These results presented in this work demonstrate that a high level of surface passivation can be achieved for Al{sub 2}O{sub 3}-based films and stacks over a wide range of conditions when the combination of deposition temperature and annealing or firing temperature is carefully chosen.« less

Giant dielectric response and low dielectric loss in Al{sub 2}O{sub 3} grafted CaCu{sub 3}Ti{sub 4}O{sub 12} ceramics

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

Rajabtabar-Darvishi, A.; Center for Surface and Nanoanalytics; Bayati, R., E-mail: reza.bayati@intel.com, E-mail: mbayati@ncsu.edu, E-mail: wdfei@hit.edu.cn

2015-03-07

This study sheds light on the effect of alumina on dielectric constant and dielectric loss of novel CaCu{sub 3}Ti{sub 4}O{sub 12} composite ceramics. Alumina, at several concentrations, was deposited on the surface of CaCu{sub 3}Ti{sub 4}O{sub 12} particles via sol-gel technique. The dielectric constant significantly increased for all frequencies and the dielectric loss substantially decreased for low and intermediate frequencies. These observations were attributed to the change in characteristics of grains and grain boundaries. It was found that the insulating properties of the grain boundaries are improved following the addition of Al{sub 2}O{sub 3}. The relative density of CaCu{sub 3}Ti{submore » 4}O{sub 12}/Al{sub 2}O{sub 3} composite ceramics decreased compared to the pure CaCu{sub 3}Ti{sub 4}O{sub 12} and the grain size was greatly changed with the alumina content affecting the dielectric properties. With the addition of alumina into CaCu{sub 3}Ti{sub 4}O{sub 12}, tighter interfaces formed. The 6%- and 10%-alumina ceramics showed the minimum dielectric loss and the maximum dielectric constant, respectively. Both the dielectric constant and loss tangent decreased in the 20%-alumina ceramic due to the formation of CuO secondary phase. It was revealed that Al serves as an electron acceptor decreasing the electron concentration, if Al{sup 3+} ions substitute for Ti{sup 4+} ions, and as an electron donor increasing the electron concentration, if Al{sup 3+} ions substitute for Ca{sup 2+} ions. We established a processing-microstructure-properties paradigm which opens new avenues for novel applications of CaCu{sub 3}Ti{sub 4}O{sub 12}/Al{sub 2}O{sub 3} composite ceramics.« less

O2(a1Δg) + Mg, Fe, and Ca: Experimental kinetics and formulation of a weak collision, multiwell master equation with spin-hopping

NASA Astrophysics Data System (ADS)

Plane, J. M. C.; Whalley, C. L.; Frances-Soriano, L.; Goddard, A.; Harvey, J. N.; Glowacki, D. R.; Viggiano, A. A.

2012-07-01

The first excited electronic state of molecular oxygen, O2(a1Δg), is formed in the upper atmosphere by the photolysis of O3. Its lifetime is over 70 min above 75 km, so that during the day its concentration is about 30 times greater than that of O3. In order to explore its potential reactivity with atmospheric constituents produced by meteoric ablation, the reactions of Mg, Fe, and Ca with O2(a) were studied in a fast flow tube, where the metal atoms were produced either by thermal evaporation (Ca and Mg) or by pulsed laser ablation of a metal target (Fe), and detected by laser induced fluorescence spectroscopy. O2(a) was produced by bubbling a flow of Cl2 through chilled alkaline H2O2, and its absolute concentration determined from its optical emission at 1270 nm (O2(a1Δg - X3Σg-). The following results were obtained at 296 K: k(Mg + O2(a) + N2 → MgO2 + N2) = (1.8 ± 0.2) × 10-30 cm6 molecule-2 s-1; k(Fe + O2(a) → FeO + O) = (1.1 ± 0.1) × 10-13 cm3 molecule-1 s-1; k(Ca + O2(a) + N2 → CaO2 + N2) = (2.9 ± 0.2) × 10-28 cm6 molecule-2 s-1; and k(Ca + O2(a) → CaO + O) = (2.7 ± 1.0) × 10-12 cm3 molecule-1 s-1. The total uncertainty in these rate coefficients, which mostly arises from the systematic uncertainty in the O2(a) concentration, is estimated to be ±40%. Mg + O2(a) occurs exclusively by association on the singlet surface, producing MgO2(1A1), with a pressure dependent rate coefficient. Fe + O2(a), on the other hand, shows pressure independent kinetics. FeO + O is produced with a probability of only ˜0.1%. There is no evidence for an association complex, suggesting that this reaction proceeds mostly by near-resonant electronic energy transfer to Fe(a5F) + O2(X). The reaction of Ca + O2(a) occurs in an intermediate regime with two competing pressure dependent channels: (1) a recombination to produce CaO2(1A1), and (2) a singlet/triplet non-adiabatic hopping channel leading to CaO + O(3P). In order to interpret the Ca + O2(a) results, we utilized density functional theory along with multireference and explicitly correlated CCSD(T)-F12 electronic structure calculations to examine the lowest lying singlet and triplet surfaces. In addition to mapping stationary points, we used a genetic algorithm to locate minimum energy crossing points between the two surfaces. Simulations of the Ca + O2(a) kinetics were then carried out using a combination of both standard and non-adiabatic Rice-Ramsperger-Kassel-Marcus (RRKM) theory implemented within a weak collision, multiwell master equation model. In terms of atmospheric significance, only in the case of Ca does reaction with O2(a) compete with O3 during the daytime between 85 and 110 km.

Facile synthesis and unique physicochemical properties of three-dimensionally ordered macroporous magnesium oxide, gamma-alumina, and ceria-zirconia solid solutions with crystalline mesoporous walls.

PubMed

Li, Huining; Zhang, Lei; Dai, Hongxing; He, Hong

2009-05-18

Three-dimensionally (3D) ordered macroporous (3DOM) MgO, gamma-Al(2)O(3), Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) with polycrystalline mesoporous walls have been successfully fabricated with the triblock copolymer EO(106)PO(70)EO(106) (Pluronic F127) and regularly packed monodispersive polymethyl methacrylate (PMMA) microspheres as the template and magnesium, aluminum, cerium and zirconium nitrate(s), or aluminum isopropoxide as the metal source. The as-synthesized metal oxides were characterized by means of techniques such as X-ray diffraction (XRD), thermogravimetric analysis/differential scanning calorimetry (TGA/DSC), Fourier transform infrared (FT-IR), high-resolution scanning electron microscopy (HRSEM), high-resolution transmission electron microscopy/selected area electron diffraction (HRTEM/SAED), BET, carbon dioxide temperature-programmed desorption (CO(2)-TPD), and hydrogen temperature-programmed reduction (H(2)-TPR). It is shown that the as-fabricated MgO, gamma-Al(2)O(3), Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) samples possessed single-phase polycrystalline structures and displayed a 3DOM architecture; the MgO, Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) samples exhibited worm-hole-like mesoporous walls, whereas the gamma-Al(2)O(3) samples exhibited 3D ordered mesoporous walls. The solvent (ethanol or water) nature and concentration, metal precursor, surfactant, and drying condition have an important impact on the pore structure and surface area of the final product. The introduction of surfactant F127 to the synthesis system could significantly enhance the surface areas of the 3DOM metal oxides. With PMMA and F127 in a 40% ethanol solution, one can generate well-arrayed 3DOM MgO with a surface area of 243 m(2)/g and 3DOM Ce(0.6)Zr(0.4)O(2) with a surface area of 100 m(2)/g; with PMMA and F127 in an ethanol-HNO(3) solution, one can obtain 3DOM gamma-Al(2)O(3)with a surface area of 145 m(2)/g. The 3DOM MgO and 3DOM gamma-Al(2)O(3) samples showed excellent CO(2) adsorption behaviors, whereas the 3DOM Ce(0.6)Zr(0.4)O(2) sample exhibited exceptional low-temperature reducibility. The unique physicochemical properties associated with the copresence of 3DOM and mesoporous walls make these porous materials ideal candidates for applications in heterogeneous catalysis and CO(2) adsorption.

Observations of biogenic isoprene emissions and atmospheric chemistry components at the Savé super site in Benin, West Africa, during the DACCIWA field campaign.

NASA Astrophysics Data System (ADS)

Jambert, Corinne; Pacifico, Federica; Delon, Claire; Lohou, Fabienne; Reinares Martinez, Irene; Brilouet, Pierre-Etienne; Derrien, Solene; Dione, Cheikh; Brosse, Fabien; Gabella, Omar; Pedruzzo Bagazgoitia, Xavier; Durand, Pierre

2017-04-01

Tropospheric oxidation of VOCs (Volatile Organic Compounds), including isoprene, in the presence of NOx and sunlight leads to the formation of O3 and Secondary Organic Aerosols (SOA). Changes in NO or VOCs sources will consequently modify their atmospheric concentrations and thus, the rate of O3 production and SOA formation. NOx have also an impact on the abundance of the hydroxyl radical (OH) which determines the lifetime of some pollutants and greenhouse gases. Anthropogenic emissions of pollutants from mega cities located on the Guinean coast in South West Africa are likely to increase in the next decades due to a strong anthropogenic pressure and to land use changes at the regional or continental scale. The consequences on regional air quality and on pollutant deposition onto surfaces may have some harmful effects on human and ecosystem health. Furthermore, the regional climate and water cycle are affected by changes in atmospheric chemistry. When transported northward on the African continent, polluted air masses meet biogenic emissions from rural areas which contributes to increase ozone and SOA production, in high temperature and solar radiation conditions, highly favourable to enhanced photochemistry. During the Dynamics-aerosol-chemistry-cloud interactions in West Africa (DACCIWA) field campaign, we measured the atmospheric chemical composition and the exchanges of trace components in a hinterland area of Benin, at the Savé super-site (8°02'03" N, 2°29'11″ E). The observations, monitored in June and July 2016, in a rural mixed agricultural area, include near surface concentrations of ozone (O3), carbon monoxide (CO), nitrogen oxides (NOx) and isoprene, isoprene fluxes and meteorological parameters. We observed hourly average concentrations of O3 up to 50 ppb, low NOx concentrations (ca. 1 ppb and CO concentrations between 75 and 300 ppb. An 8 m tower was equipped with a Fast Isoprene Sensor and sonic anemometer to measure isoprene concentrations and determine isoprene fluxes with eddy-covariance technique over a mixed (patched maize, manioc and anacardium) agricultural plot. We discuss the influence of meteorological conditions on biogenic emissions (i.e. isoprene fluxes) and on ambient atmospheric chemistry (i.e. isoprene, NOx, O3 and CO concentrations observed on the site). We also studied the impact of remote anthropogenic emissions from cities on the Guinean southern coast on local chemistry.

Unconventional Synthesis of γ-Fe2O3: Excellent Low-Concentration Ethanol Sensing Performance

NASA Astrophysics Data System (ADS)

Naskar, Atanu; Narjinary, Mousumi; Kundu, Susmita

2017-01-01

This study reports on a simple unconventional procedure for synthesis of γ-Fe2O3 nanopowder and its fabrication as a resistive ethanol sensor. γ-Fe2O3 powder having an average particle size of ˜15 nm was prepared by thermal decomposition of iron(III) acetylacetonate. Platinum incorporation (0.5-1.5 wt.%) was also carried out for enhancing sensing performance. The powders were characterized using an x-ray diffractometer, x-ray photoelectron spectroscopy, Brunauer-Emmett-Teller surface area, field area scanning electron microscopy, transmission electron microscopy along with energy dispersion x-ray analyses. Sensor fabricated from pure γ-Fe2O3 exhibited excellent ethanol sensing performance at concentrations down to 1 ppm, having a great demand in medical diagnosis and food-processing industries. The response observed for pure γ-Fe2O3 (˜75% for 1 ppm ethanol) was enhanced ˜10% after 1 wt.% Pt impregnation. Sensors were quite stable and selective towards ethanol vapour detection. A possible mechanism for high sensing performance has been discussed.

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

Sabah, Fayroz A., E-mail: fayroz-arif@yahoo.com; Department of Electrical Engineering, College of Engineering, Al-Mustansiriya University, Baghdad; Ahmed, Naser M., E-mail: naser@usm.my

The copper sulphide (CuS) thin films were grown with good adhesion by spray pyrolysis deposition (SPD) on Ti, ITO and glass substrates at 200 °C. The distance between nozzle and substrate is 30 cm. The composition was prepared by mixing copper chloride CuCl{sub 2}.2H{sub 2}O as a source of Cu{sup 2+} and sodium thiosulfate Na{sub 2}S{sub 2}O{sub 3}.5H{sub 2}O as a source of and S{sup 2−}. Two concentrations (0.2 and 0.4 M) were used for each CuCl{sub 2} and Na{sub 2}S{sub 2}O{sub 3} to be prepared and then sprayed (20 ml). The process was started by spraying the solution formore » 3 seconds and after 10 seconds the cycle was repeated until the solution was sprayed completely on the hot substrates. The structural characteristics were studied using X-ray diffraction; they showed covellite CuS hexagonal crystal structure for 0.2 M concentration, and covellite CuS hexagonal crystal structure with two small peaks of chalcocite Cu{sub 2}S hexagonal crystal structure for 0.4 M concentration. Also the surface and electrical characteristics were investigated using Field Emission Scanning Electron Microscopy (FESEM) and current source device, respectively. The surface study for the CuS thin films showed nanorods to be established for 0.2 M concentration and mix of nanorods and nanoplates for 0.4 M concentration. The electrical study showed ohmic behavior and low resistivity for these films. Hall Effect was measured for these thin films, it showed that all samples of CuS are p- type thin films and ensured that the resistivity for thin films of 0.2 M concentration was lower than that of 0.4 M concentration; and for the two concentrations CuS thin film deposited on ITO had the lowest resistivity. This leads to the result that the conductivity was high for CuS thin film deposited on ITO substrate, and the conductivity of the three thin films of 0.2 M concentration was higher than that of 0.4 M concentration.« less

Tuning the relative concentration ratio of bulk defects to surface defects in TiO2 nanocrystals leads to high photocatalytic efficiency.

PubMed

Kong, Ming; Li, Yuanzhi; Chen, Xiong; Tian, Tingting; Fang, Pengfei; Zheng, Feng; Zhao, Xiujian

2011-10-19

TiO(2) nanocrystals with tunable bulk/surface defects were synthesized and characterized with TEM, XRD, BET, positron annihilation, and photocurrent measurements. The effect of defects on photocatalytic activity was studied. It was found for the first time that decreasing the relative concentration ratio of bulk defects to surface defects in TiO(2) nanocrystals could significantly improve the separation efficiency of photogenerated electrons and holes, thus significantly enhancing the photocatalytic efficiency.

Analysis of Recent European Surface Ozone Trends Considering Site Representativeness and Mete-orology

NASA Astrophysics Data System (ADS)

Henne, S.; Fleming, Z.; Brunner, D.; Klausen, J.; Buchmann, B.

2009-04-01

Recent trends of surface ozone (O3) within Europe vary substantially depending on the location and surroundings of a measurement site. The influence of long-range transport from North America and Asia, changes in stratosphere-troposphere exchange, increase in lower stratospheric O3 and changes in advection patterns are possible drivers for the observed O3 trends. O3 concentrations greatly depend on meteorology (temperature and radiation) and local to regional emissions of precursor gases and therefore on the representativeness of a site (e.g. background vs. urban site) and regional emission trends. We investigated the representativeness of 1264 "rural" and "suburban" background sites (as available through the European Environment Agency (EEA )Airbase database) by analysing population density, land cover and topography in the surrounding of the sites. A hierarchical clustering method was applied to derive an independent site categorization. The two area types as specified by EEA are split into 7 categories: elevated, lowered, remote, rural, rural/coastal, rural/polluted, suburban. Furthermore, we analysed the trend of surface O3 and Ox (O3+NO2) for the mentioned sites based on the above site categorization, local meteorology and precursor emission trends. Of the 1264 sites 161 possess sufficiently long and complete O3 data series suitable for robust trend estimation, while for 100 sites both O3 and NO2 data are available. We present a strategy for further data exclusion based on available data quality information and a break detection algorithm. First results of the trend analysis applying different statistical approaches are discussed.

Non-enzymatic detection of glucose in fruits using TiO2-Mn3O4 hybrid nano interface

NASA Astrophysics Data System (ADS)

Jayanth Babu, K.; Sasya, Madhurantakam; Nesakumar, Noel; Shankar, Prabakaran; Gumpu, Manju Bhargavi; Ramachandra, Bhat Lakshmishri; Kulandaisamy, Arockia Jayalatha; Rayappan, John Bosco Balaguru

2017-08-01

Consumption of fruits leads to increase in glucose level in blood for diabetic patients, which in turn leads to peripheral, vascular, ocular complications and cardiac diseases. In this context, a non-enzymatic hybrid glucose biosensor was fabricated for the first time to detect glucose by immobilizing titanium oxide-manganese oxide (TiO2-Mn3O4) nanocomposite and chitosan membrane on to the surface of Pt working electrode (Pt/TiO2-Mn3O4/chitosan). TiO2-Mn3O4 nanocomposite catalyzed the oxidation of glucose to gluconolactone in the absence of glucose oxidase enzyme with high electron transfer rate, good biocompatibility and large surface coverage. Electrochemical measurements revealed the excellent sensing response of the developed biosensor towards glucose with a high sensitivity of 7.073 µA mM-1, linearity of 0.01-0.1 mM, low detection limit of 0.01 µM, reproducibility of 1.5% and stability of 98.8%. The electrochemical parameters estimated from the anodic process were subjected to linear regression models for the detection of unknown concentration of glucose in different fruit samples.

Giant tunnelling electroresistance in metal/ferroelectric/semiconductor tunnel junctions by engineering the Schottky barrier

PubMed Central

Xi, Zhongnan; Ruan, Jieji; Li, Chen; Zheng, Chunyan; Wen, Zheng; Dai, Jiyan; Li, Aidong; Wu, Di

2017-01-01

Recently, ferroelectric tunnel junctions have attracted much attention due to their potential applications in non-destructive readout non-volatile memories. Using a semiconductor electrode has been proven effective to enhance the tunnelling electroresistance in ferroelectric tunnel junctions. Here we report a systematic investigation on electroresistance of Pt/BaTiO3/Nb:SrTiO3 metal/ferroelectric/semiconductor tunnel junctions by engineering the Schottky barrier on Nb:SrTiO3 surface via varying BaTiO3 thickness and Nb doping concentration. The optimum ON/OFF ratio as great as 6.0 × 106, comparable to that of commercial Flash memories, is achieved in a device with 0.1 wt% Nb concentration and a 4-unit-cell-thick BaTiO3 barrier. With this thinnest BaTiO3 barrier, which shows a negligible resistance to the tunnelling current but is still ferroelectric, the device is reduced to a polarization-modulated metal/semiconductor Schottky junction that exhibits a more efficient control on the tunnelling resistance to produce the giant electroresistance observed. These results may facilitate the design of high performance non-volatile resistive memories. PMID:28513590

Giant tunnelling electroresistance in metal/ferroelectric/semiconductor tunnel junctions by engineering the Schottky barrier

NASA Astrophysics Data System (ADS)

Xi, Zhongnan; Ruan, Jieji; Li, Chen; Zheng, Chunyan; Wen, Zheng; Dai, Jiyan; Li, Aidong; Wu, Di

2017-05-01

Recently, ferroelectric tunnel junctions have attracted much attention due to their potential applications in non-destructive readout non-volatile memories. Using a semiconductor electrode has been proven effective to enhance the tunnelling electroresistance in ferroelectric tunnel junctions. Here we report a systematic investigation on electroresistance of Pt/BaTiO3/Nb:SrTiO3 metal/ferroelectric/semiconductor tunnel junctions by engineering the Schottky barrier on Nb:SrTiO3 surface via varying BaTiO3 thickness and Nb doping concentration. The optimum ON/OFF ratio as great as 6.0 × 106, comparable to that of commercial Flash memories, is achieved in a device with 0.1 wt% Nb concentration and a 4-unit-cell-thick BaTiO3 barrier. With this thinnest BaTiO3 barrier, which shows a negligible resistance to the tunnelling current but is still ferroelectric, the device is reduced to a polarization-modulated metal/semiconductor Schottky junction that exhibits a more efficient control on the tunnelling resistance to produce the giant electroresistance observed. These results may facilitate the design of high performance non-volatile resistive memories.

Ozone impacts of gas-aerosol uptake in global chemistry transport models

NASA Astrophysics Data System (ADS)

Stadtler, Scarlet; Simpson, David; Schröder, Sabine; Taraborrelli, Domenico; Bott, Andreas; Schultz, Martin

2018-03-01

The impact of six heterogeneous gas-aerosol uptake reactions on tropospheric ozone and nitrogen species was studied using two chemical transport models, the Meteorological Synthesizing Centre-West of the European Monitoring and Evaluation Programme (EMEP MSC-W) and the European Centre Hamburg general circulation model combined with versions of the Hamburg Aerosol Model and Model for Ozone and Related chemical Tracers (ECHAM-HAMMOZ). Species undergoing heterogeneous reactions in both models include N2O5, NO3, NO2, O3, HNO3, and HO2. Since heterogeneous reactions take place at the aerosol surface area, the modelled surface area density (Sa) of both models was compared to a satellite product retrieving the surface area. This comparison shows a good agreement in global pattern and especially the capability of both models to capture the extreme aerosol loadings in east Asia. The impact of the heterogeneous reactions was evaluated by the simulation of a reference run containing all heterogeneous reactions and several sensitivity runs. One reaction was turned off in each sensitivity run to compare it with the reference run. The analysis of the sensitivity runs confirms that the globally most important heterogeneous reaction is the one of N2O5. Nevertheless, NO2, HNO3, and HO2 heterogeneous reactions gain relevance particularly in east Asia due to the presence of high NOx concentrations and high Sa in the same region. The heterogeneous reaction of O3 itself on dust is of minor relevance compared to the other heterogeneous reactions. The impacts of the N2O5 reactions show strong seasonal variations, with the biggest impacts on O3 in springtime when photochemical reactions are active and N2O5 levels still high. Evaluation of the models with northern hemispheric ozone surface observations yields a better agreement of the models with observations in terms of concentration levels, variability, and temporal correlations at most sites when the heterogeneous reactions are incorporated. Our results are loosely consistent with results from earlier studies, although the magnitude of changes induced by N2O5 reaction is at the low end of estimates, which seems to fit a trend, whereby the more recent the study the lower the impacts of these reactions.

In vitro bioactivity of novel tricalcium silicate ceramics.

PubMed

Zhao, Wenyuan; Chang, Jiang; Wang, Junying; Zhai, Wanyin; Wang, Zheng

2007-05-01

In this study, bone-like apatite-formation ability of tricalcium silicate (Ca(3)SiO(5)) ceramics in simulated body fluid (SBF) was evaluated and the in vitro degradability was investigated by soaking in Ringer's solution. The effect of ionic products from Ca(3)SiO(5) dissolution on osteobalsts proliferation was investigated. The result indicated that hydroxyapatite (HA) was formed on the surface of the Ca(3)SiO(5) ceramics after soaking in SBF for 1 day, and Ca(3)SiO(5) ceramics could degraded in Ringer's solution. The Si ions from Ca(3)SiO(5) dissolution at certain concentration range significantly stimulated osteoblasts proliferation. Our results show that Ca(3)SiO(5) ceramics possess bone-like apatite-formation ability and degradability, and can release soluble ionic products to stimulate cell proliferation.

Thermal stability of γ-Fe2O3 nanoparticles and their employment for sensing of acetone vapours

NASA Astrophysics Data System (ADS)

Luby, Š.; Ivančo, J.; Jergel, M.; Švec, P., Jr.; Kotlár, M.; Kostiuk, D.; Halahovets, J.; Kollár, J.; Mosnáček, J.; Majková, E.

2017-12-01

Stability of γ-Fe2O3 nanoparticles-based films upon an isochronal annealing in air was investigated by x-ray diffraction, differential scanning calorimetry, and thermogravimetry. The γ-α transformation temperature increased owing to the nanoscaling of Fe2O3; the higher stability of the γ phase was explained on the ground of the surface free energy of nanoparticles (with the size of about 6.4 nm). Further, chemiresistors based on the Fe2O3 nanoparticle bilayer prepared by the Langmuir-Schaefer method were fabricated and examined in terms of their sensitivity to acetone vapours down to 500 ppb concentration in air.

Characterization of the NOx-Ox relationship in a mountain gap rural area of interchange of air masses southeast of the Metropolitan Area of Mexico City

NASA Astrophysics Data System (ADS)

Ruiz Suarez, L.; Garcia-Yee, J.; Torres-JArdon, R.; Barrera Huertas, H.; Torres-Jaramillo, A.; Ortinez, A.

2013-05-01

Varying levels of oxidants (Ox = O3 + NO2) with respect to NOx were registered at three sites in a mountain southeast of the Mexico City Metropolitan Area (MCMA) in February and March 2011. The Ox-NOx ratio was used to gain a better understanding of the photochemical and transport processes happening over this mountain pass. Relatively high concentrations of O3 (moving average concentrations of 8 hours) exceeded maximum levels of the World Health Organization, and the European Union. The cumulative exceedances above background level of O3 in the one month-long campaign also exceeded the three months accumulative UN-ECE AOT40 critical level for crop protection. It was observed that the level of Ox in the mountain gap sites consisted of two contributions: One, independent of NOx emissions, extremely dominant and considered equivalent to the regional background O3 concentration; the second and much smaller was dependent of NOx local concentrations. Evidence was found that the oxidation of NO provided the major contribution of NO2 to Ox, rather than direct NO2 emissions. The contribution of regional Ox dominated from midmorning to noon when the boundary layer height began to increase due to sunlight heating of the surface leading to the mixing of higher concentrations of O3 above the nighttime thermal inversion. After noon, when the ozone vertical distribution was uniform, the Ox and O3 concentrations reached their maximum; they were very similar with very low levels of NO2. The analysis of wind data collected at the monitoring sites showed that from mid-morning to early afternoon, a northerly weak flow was common. Afterwards stronger southerly winds became dominant bringing in O3 rich air parcels into the atmospheric basin where MCMA is located. The high regional ozone concentrations add evidence for the need of coordinated air quality management policies for the complete central part of Mexico. Keywords: mountain gap, oxidant, ground level ozone, Central Mexico

Effect of surface passivation on corrosion resistance and antibacterial properties of Cu-bearing 316L stainless steel

NASA Astrophysics Data System (ADS)

Zhao, Jinlong; Xu, Dake; Shahzad, M. Babar; Kang, Qiang; Sun, Ying; Sun, Ziqing; Zhang, Shuyuan; Ren, Ling; Yang, Chunguang; Yang, Ke

2016-11-01

The resistance for pitting corrosion, passive film stability and antibacterial performance of 316L-Cu SS passivated by nitric acid solution containing certain concentration of copper sulfate, were studied by electrochemical cyclic polarization, electrochemical impedance spectroscopy (EIS) and co-culture with bacteria. Inductively coupled plasma mass spectrometry (ICP-MS) was used to analyze the Cu2+ ions release from 316L-Cu SS surface. XPS analysis proved that the enrichment of CuO, Cr2O3 and Cr(OH)3 on the surface of specimen could simultaneously guarantee a better corrosion resistance and stable antibacterial properties. The biocompatibility evaluation determined by RTCA assay also indicated that the 316L-Cu SS after antibacterial passivation was completely biocompatible.

Depth profiling of superconducting thin films using rare gas ion sputtering with laser postionization

NASA Astrophysics Data System (ADS)

Pallix, J. B.; Becker, C. H.; Missert, N.; Char, K.; Hammond, R. H.

1988-02-01

Surface analysis by laser ionization (SALI) has been used to examine a high-Tc superconducting thin film of nominal composition YBa2Cu3O7 deposited on SrTiO3 (100) by reactive magnetron sputtering. The main focus of this work was to probe the compositional uniformity and the impurity content throughout the 1800 Å thick film having critical current densities of 1 to 2×106 A/cm2. SALI depth profiles show this film to be more uniform than thicker films (˜1 μm, prepared by electron beam codeposition) which were studied previously, yet the data show that some additional (non-superconducting) phases derived from Y, Ba, Cu, and O are still present. These additional phases are studied by monitoring the atomic and diatomic-oxide photoion profiles and also the depth profiles of various clusters (e.g. Y2O2+, Y2O3+, Y3O4+, Ba2O+, Ba2O2+, BaCu+, BaCuO+, YBaO2+, YSrO2+, etc.). A variety of impurities are observed to occur throughout the film including rather large concentrations of Sr. Hydroxides, F, Cl, and COx are evident particularly in the sample's near surface region (the top ˜100 Å).

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

Formation of CO2, H2 and condensed carbon from siderite dissolution in the 200-300 °C range and at 50 MPa

NASA Astrophysics Data System (ADS)

Milesi, Vincent; Guyot, François; Brunet, Fabrice; Richard, Laurent; Recham, Nadir; Benedetti, Marc; Dairou, Julien; Prinzhofer, Alain

2015-04-01

Laboratory experiments were conducted to investigate the chemical processes governing the carbon speciation associated to hydrothermal decomposition of siderite. Experiments were carried out in sealed gold capsules using synthetic siderite and deionised water. The samples were reacted at 200 and 300 °C, under a pressure of 50 MPa. Siderite dissolved to reach the 3FeCO3 + H2O = Fe3O4 + 3CO2 + H2 equilibrium and magnetite, Fe3O4, was produced accordingly. The gas phase was dominated by CO2, H2 and CH4, the latter being in strong thermodynamic disequilibrium with CO2. Contrary to the other gas products, H2 concentration was found to decrease with run duration. TEM observations showed the occurrence of condensed carbon phases at the surfaces of magnetite and residual siderite grains. Thermodynamic calculations predict the formation of condensed carbon in the experiments according to the reaction: CO2 + 2H2 ⇒ C + 2H2O, which accounted for the observed H2 concentration decrease up to the point where H2 and CO2 activities were buffered by the graphite-siderite-magnetite assemblage. The well-organized structure of the carbon coating around magnetite emphasizes the high catalytic potential of magnetite surface for carbon reduction and polymerization. The formation of such C-rich phases may represent a potential source of CH4 by hydrogenation. On the other hand, the catalysis of Fischer-Tropsch type reactions may be poisoned by the presence of carbon coating on mineral surfaces. In any case, this study also demonstrates that abiotic H2 generation by water reduction, widely studied in recent years in ultrabasic contexts, can also occur in sedimentary contexts where siderite is present. We show that, in the latter case, natural H2 concentration will be buffered by a condensed carbon phase associated with magnetite.

Alternative Dielectric Films for rf MEMS Capacitive Switches Deposited using Atomic Layer Deposited Al2O3/ZnO Alloys

DTIC Science & Technology

2006-07-02

A s c c s r t h s l © K 1 b c A a e t s C t o 0 d Sensors and Actuators A 135 (2007) 262–272 Alternative dielectric films for rf MEMS capacitive...Zn concentrations in the alloy films , which was lower than expected. Atomic force microscopy images evealed an average surface roughness of 0.27 nm...that was independent of deposition temperature and film composition. The dielectric constants of he Al2O3/ZnO ALD alloys films were calculated to be

Enhanced surface transfer doping of diamond by V{sub 2}O{sub 5} with improved thermal stability

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

Crawford, Kevin G., E-mail: k.crawford.2@research.gla.ac.uk; Moran, David A. J.; Cao, Liang

2016-01-25

Surface transfer doping of hydrogen-terminated diamond has been achieved utilising V{sub 2}O{sub 5} as a surface electron accepting material. Contact between the oxide and diamond surface promotes the transfer of electrons from the diamond into the V{sub 2}O{sub 5} as revealed by the synchrotron-based high resolution photoemission spectroscopy. Electrical characterization by Hall measurement performed before and after V{sub 2}O{sub 5} deposition shows an increase in hole carrier concentration in the diamond from 3.0 × 10{sup 12} to 1.8 × 10{sup 13 }cm{sup −2} at room temperature. High temperature Hall measurements performed up to 300 °C in atmosphere reveal greatly enhanced thermal stability of the hole channelmore » produced using V{sub 2}O{sub 5} in comparison with an air-induced surface conduction channel. Transfer doping of hydrogen-terminated diamond using high electron affinity oxides such as V{sub 2}O{sub 5} is a promising approach for achieving thermally stable, high performance diamond based devices in comparison with air-induced surface transfer doping.« less

Electrodeposition and characterization of Ni-Mo-ZrO2 composite coatings

NASA Astrophysics Data System (ADS)

Laszczyńska, A.; Winiarski, J.; Szczygieł, B.; Szczygieł, I.

2016-04-01

Ni-Mo-ZrO2 composite coatings were produced by electrodeposition technique from citrate electrolytes containing dispersed ZrO2 nanopowder. The influence of deposition parameters i.e. concentration of molybdate and ZrO2 nanoparticles in the electrolyte, bath pH and deposition current density on the composition and surface morphology of the coating has been investigated. The structure, microhardness and corrosion properties of Ni-Mo-ZrO2 composites with different molybdenum and ZrO2 content have been also examined. It was found that ZrO2 content in the deposit is increased by rising the nanoparticles concentration in the plating solution up to 20 g dm-3. An increase in molybdate concentration in the electrolyte affects negatively the amount of codeposited ZrO2 nanoparticles. The correlation between the deposition current efficiency and ZrO2 content in the composite coating has been also observed. A decrease in deposition current efficiency leads to deposition of Ni-Mo-ZrO2 composite with low nanoparticles content. This may be explained by formation of higher amounts of gas bubbles on the cathode surface, which prevent the adsorption of ZrO2 nanoparticles on the growing deposit. The XRD analysis revealed that all the studied Ni-Mo-ZrO2 coatings were composed of a single, nanocrystalline phase with FCC structure. It was found that the incorporation of ZrO2 nanoparticles into Ni-Mo alloy matrix affects positively the microhardness and also slightly improves the corrosion properties of Ni-Mo alloy coating.

Nonmethane Hydrocarbons and Ozone in the Rural Southeast United States National Parks: A Model Sensitivity Analysis and Its Comparison with Measurement

NASA Astrophysics Data System (ADS)

Kang, D.; Aneja, V. P.; Mathur, R.; Ray, J. D.

2001-12-01

A comprehensive modeling analysis is conducted using the Multiscale Air Quality SImulation Platform (MAQSIP) focusing on nonmethane hydrocarbons and ozone in three southeast United States national parks for a 15-day time period (July 14th to July 29th, 1995) characterized by high O3 surface concentrations. Nine emission scenarios including the base scenario are analyzed. Model predictions are compared with and contrasted against observed data at the three locations for the same time period. Model predictions (base scenario) tend to give lower daily maximum O3 concentrations than observation by 10.8% at Cove Mountain, Great Smoke Mountains National Park (GRSM), 26.8% at Mammoth Cave National Park (MACA), and 17.6% at Big Meadows, Shenandoah National Park (SHEN). Overall mean ozone concentrations are very similar at GRSM and SHEN (observed data at MACA are not available). Model predicted concentrations of lumped paraffin compounds match the observed values on the same order, while the observed concentrations for other species (isoprene, ethene, surrogate olefin, surrogate toluene, and surrogate xylene) are usually an order of magnitude higher than the predictions. Sensitivity analyses indicate each location has its own characteristics in terms of the capacity of volatile organic compounds (VOCs) to produce O3, but a maximum VOC capacity point (MVCP) exists at all locations that changes the influence of VOCs on O3 from production to destruction. Analysis of individual model process budgets shows that more than 50% of daytime O3 concentrations at these rural locations are transported from other areas, local chemistry is the second largest contributor (13% to 42%), all other processes combined contribute less than 10% of the daytime O3 concentrations. Local emissions (>99%) are predominantly responsible for VOCs at all locations, while vertical diffusion (>70%) is the predominant process to move VOCs away from the modeling grid. Dry deposition ( ~ 10%) and chemistry (2 to 13%) processes are also responsible for the removal of VOCs. Metrics such as O3 production efficiency of VOC emissions (VOPE), VOC potential for O3 production (VPOP), and MVCP are devised to quantitatively measure the different characteristics of O3 production and VOCs in these rural environments. Implications of this model exercise in understanding O3 production in rural atmospheres are analyzed and discussed. Even though this study is focusing on three United States National Parks, the research results and conclusions may be applicable to other rural atmospheres.

Reconciling "Whiffs" of O2 with the Archean MIF S Record: Insights from Sulfide Oxidation Experiments

NASA Astrophysics Data System (ADS)

Johnson, A.; Reinhard, C. T.; Romaniello, S. J.; Greaney, A. T.; Garcia-Robledo, E.; Revsbech, N. P.; Canfield, D. E.; Lyons, T. W.; Anbar, A. D.

2016-12-01

The Archean-Proterozoic transition is marked by the first appreciable accumulation of O2 in Earth's oceans and atmosphere at 2.4 billion years ago (Ga). However, this Great Oxidation Event (GOE) is not the first evidence for O2 in Earth's surface environment. Paleoredox proxies preserved in ancient marine shales (Mo, Cr, Re, U) suggest transient episodes of oxidative weathering before the GOE, perhaps as early as 3.0 Ga. One marine shale in particular, the 2.5 Ga Mount McRae Shale of Western Australia, contains a euxinic interval with Mo enrichments up to 50 ppm. This enrichment is classically interpreted as the result of oxidative weathering of sulfides on the continental surface. However, prior weathering models based on experiments suggested that sulfides require large amounts of O2 [>10-4 present atmospheric level (PAL) pO2] to produce this weathering signature, in conflict with estimates of Archean pO2 from non-mass-dependent (NMD) sulfur isotope anomalies (<10-5 PAL pO2). To reconcile these datasets, we conducted aqueous oxidation experiments of pyrite and molybdenite from 3 - 700 nM O2 (equivalent at equilibrium to 10-5 - 10-3 PAL) to measure oxidation kinetics as a function of the concentration of dissolved O2. We measured rates by injecting oxygenated water at a steady flow rate and monitoring dissolved O2 concentrations with LUMOS sensors. Our data extend the O2 range explored in pyrite oxidation experiments by three orders of magnitude and provide the first rates for molybdenite oxidation at O2 concentrations potentially analogous to those characteristic of the Archean atmosphere. Our results show that pyrite and molybdenite oxidize significantly more rapidly at lower O2 levels than previously thought. As a result, our revised weathering model demonstrates that the Mo enrichments observed in late Archean marine shales are potentially attainable at extremely low atmospheric pO2 values (e.g., <10-5 PAL), reconciling large sedimentary Mo enrichments with co-occurring NMD sulfur isotope anomalies.

Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

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

Loring, John S.; Chen, Jeffrey; Benezeth, Pascale

Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM,more » TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, the implication of these results is that mineral trapping in scCO2 dominated fluids will be insignificant and limited to surface complexation unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.« less

Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

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

Loring, John S.; Chen, Jeffrey; Benezeth Ep Gisquet, Pascale

Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM,more » TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, these results suggest that mineral carbonation in scCO2 dominated fluids near the wellbore and adjacent to caprocks will be insignificant and limited to surface complexation, unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.« less

Effects of inorganic carbon on the nitrous oxide emissions and microbial diversity of an anaerobic ammonia oxidation reactor.

PubMed

Zhang, Wenjie; Wang, Dunqiu; Jin, Yue

2018-02-01

Inorganic carbon (IC) is important for anaerobic ammonium oxidation (anammox). In this study, the effects of the IC concentration on N 2 O emissions and microbial diversity in an anammox reactor were investigated. N 2 O emissions were positively correlated with IC concentrations, and IC concentrations in the range of 55-130 mg/L were optimal, considering the nitrogen removal rate and N 2 O emissions. High IC concentrations resulted in the formation of CaCO 3 on the surface of anammox granules, which impacted the diffusion conditions of the substrate. Microbial community analysis indicated that high IC concentrations decreased the populations of specific bacteria, such as Achromobacter spanius strain YJART-7, Achromobacter xylosoxidans strain IHB B 6801, and Denitratisoma oestradiolicum clone 20b_15. D. oestradiolicum clone 20b_15 appeared to be the key contributor to N 2 O emissions. High N 2 O emissions may result from changes in organic carbon sources, which lead to denitrification by D. oestradiolicum clone 20b_15. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ab initio understanding of magnetic properties in Zn2+ substitution of Fe3O4 ultra-thin film with dilute Zn substitution

NASA Astrophysics Data System (ADS)

Huang, Zhaocong; Chen, Qian; Jiang, Sheng; Dong, Shuai; Zhai, Ya

2018-05-01

The mechanism of the magnetic properties on the Zn2+ substituted Fe3O4 film have been investigated based on first principle calculations. It is found that the surface effect plays an important role in the occupation of Zn ion, and in turn changes the magnetic moment. It may also destroy the half metallic behavior of Fe3O4 film even if the Zn2+ concentration only is one Zn2+ per unit cell (4%), which is different from that in bulk material.

Characterization and improved solar light activity of vanadium doped TiO2/diatomite hybrid catalysts.

PubMed

Wang, Bin; Zhang, Guangxin; Leng, Xue; Sun, Zhiming; Zheng, Shuilin

2015-03-21

V-doped TiO2/diatomite composite photocatalysts with different vanadium concentrations were synthesized by a modified sol-gel method. The diatomite was responsible for the well dispersion of TiO2 nanoparticles on the matrix and consequently inhibited the agglomeration. V-TiO2/diatomite hybrids showed red shift in TiO2 absorption edge with enhanced absorption intensity. Most importantly, the dopant energy levels were formed in the TiO2 bandgap due to V(4+) ions substituted to Ti(4+) sites. The 0.5% V-TiO2/diatomite photocatalyst displayed narrower bandgap (2.95 eV) compared to undoped sample (3.13 eV) and other doped samples (3.05 eV) with higher doping concentration. The photocatalytic activities of V doped TiO2/diatomite samples for the degradation of Rhodamine B under stimulated solar light illumination were significantly improved compared with the undoped sample. In our case, V(4+) ions incorporated in TiO2 lattice were responsible for increased visible-light absorption and electron transfer to oxygen molecules adsorbed on the surface of TiO2 to produce superoxide radicals ˙O2(-), while V(5+) species presented on the surface of TiO2 particles in the form of V2O5 contributed to e(-)-h(+) separation. In addition, due to the combination of diatomite as support, this hybrid photocatalyst could be separated from solution quickly by natural settlement and exhibited good reusability. Copyright © 2014 Elsevier B.V. All rights reserved.

Parametric studies of diethyl phosphoramidate photocatalytic decomposition over TiO2.

PubMed

Sun, Bo; Vorontsov, Alexander V; Smirniotis, Panagiotis G

2011-02-28

The present study is focused on influences of parameters including pH, temperature, TiO(2) catalyst concentration, and reactant concentration on the rate of photocatalytic diethyl phosphoramidate (DEPA) decomposition with Hombikat UV 100 (HK) and Degussa P25 (P25) TiO(2). Total mineralization of DEPA is observed. Two regimes of pH, namely in acid and near-neutral environments were found where maximum total carbon (TC) decomposition was observed. The electrostatic effects on adsorption over the TiO(2) surface explain the above phenomena. The maximum rate is observed for P25 at DEPA concentration 1.3 mM whereas the rate grows continuously with DEPA concentration rise for HK. The temperature dependence of TC decomposition rate in the range of 15-63°C with both HK and P25 follows the Arrhenius equation. The activation energy for total carbon decomposition with HK and P25 are 29.5±1.0 and 24.3±3.1 kJ/mol, respectively. The decomposition rate of DEPA is larger over P25 than over HK. The rate over P25 increases faster than that with HK for each unit of the titania added when the TiO(2) concentration is less than 375 mg/l. The higher light absorption and particles aggregation of P25 are responsible for the decrease of reaction rate we observed at catalyst concentration above a certain level. In contrast, the rate over HK increases monotonically with the concentration of the photocatalyst used. Copyright © 2010 Elsevier B.V. All rights reserved.

Fabrication and characterization of PbO2 electrode modified with [Fe(CN)6](3-) and its application on electrochemical degradation of alkali lignin.

PubMed

Hao, Xu; Quansheng, Yuan; Dan, Shao; Honghui, Yang; Jidong, Liang; Jiangtao, Feng; Wei, Yan

2015-04-09

PbO2 electrode modified by [Fe(CN)6](3-) (marked as FeCN-PbO2) was prepared by electro-deposition method and used for the electrochemical degradation of alkali lignin (AL). The surface morphology and the structure of the electrodes were characterized by scanning electronic microscopy (SEM) and X-ray diffraction (XRD), respectively. The stability and electrochemical activity of FeCN-PbO2 electrode were characterized by accelerated life test, linear sweep voltammetry, electrochemical impedance spectrum (EIS) and AL degradation. The results showed that [Fe(CN)6](3-) increased the average grain size of PbO2 and formed a compact surface coating. The service lifetime of FeCN-PbO2 electrode was 287.25 h, which was longer than that of the unmodified PbO2 electrode (100.5h). The FeCN-PbO2 electrode showed higher active surface area and higher oxygen evolution potential than that of the unmodified PbO2 electrode. In electrochemical degradation tests, the apparent kinetics coefficient of FeCN-PbO2 electrode was 0.00609 min(-1), which was higher than that of unmodified PbO2 electrode (0.00419 min(-1)). The effects of experimental parameters, such as applied current density, initial AL concentration, initial pH value and solution temperature, on electrochemical degradation of AL by FeCN-PbO2 electrode were evaluated. Copyright © 2015 Elsevier B.V. All rights reserved.

Mono- and bimetallic nanoparticles decorated KTaO3 photocatalysts with improved Vis and UV-Vis light activity

NASA Astrophysics Data System (ADS)

Krukowska, Anna; Trykowski, Grzegorz; Winiarski, Michal Jerzy; Klimczuk, Tomasz; Lisowski, Wojciech; Mikolajczyk, Alicja; Pinto, Henry P.; Zaleska-Medynska, Adriana

2018-05-01

Novel mono- and bimetallic nanoparticles (MNPs and BNPs) decorated surface of perovskite-type KTaO3 photocatalysts were successfully synthesized by hydrothermal reaction of KTaO3 followed by photodeposition of MNPs/BNPs. The effect of noble metal type (MNPs = Au, Ag, Pt, Pd, Rh, Ru or BNPs = Au/Pt, Ag/Pd, Rh/Ru), amount of metal precursor (0.5, 1.0, 1.5 or 2.0 wt%) as well as photoreduction method (simultaneous (both) or subsequent (seq) deposition of two metals) on the physicochemical and photocatalytic properties of MNPs- and BNPs-KTaO3 have been investigated. All as-prepared photocatalysts were subsequently characterized by UV-Vis diffuse reflectance spectroscopy (DRS), Brunauer-Emmett-Teller (BET) specific surface area and pore size distribution measurement, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (PXRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) emission spectroscopy. The crystal structure was performed using visualization for electronic and structural analysis (VESTA). The photocatalytic activity under Vis light irradiation was estimated in phenol degradation in aqueous phase and toluene removal in gas phase, while under UV-Vis light irradiation was measured amount of H2 generation from formic acid solution. The absorption properties of O2 and H2O molecules on KTaO3(1 0 0) surface supported by Au or Au/Pt NPs was also investigated using density-functional theory (DFT). The experimental results show that, both MNPs-KTaO3 and BNPs-KTaO3 exhibit greatly enhanced pollutant decomposition efficiency under Vis light irradiation and highly improved H2 production under UV-Vis light irradiation compared with pristine KTaO3. MNPs deposition on KTaO3 surface effects by disperse metal particle size ranging from 11 nm (Ru NPs) to 112 nm (Au NPs). Simultaneous addition of Au/Pt precursors results in formation of agglomerated larger metal nanoparticles (50-100 nm) on KTaO3 surface than subsequent deposition of Au/Pt with composition of concentrated smaller metal nanoparticles (>50 nm) on KTaO3 surface. The 0.5 Au/1.5 Pt-KTaO3_both and 2.0 Rh-KTaO3 reveal the highest Vis-induced activity among prepared samples in aqueous phase (14.75% of phenol decomposition after 90 min of irradiation) and gas phase (41.98% of toluene removal after 60 min of irradiation), respectively. The theoretical calculations confirmed that adsorption energy of O2 and H2O molecules was increased after loading of Au or Au/Pt NPs on KTaO3(1 0 0) surface. Control tests with scavengers show that O2rad - radical is significantly involved in phenol oxidation under Vis light irradiation, which proposed mechanism is based on direct electron transfer from MNPs/BNPs to conduction band of KTaO3. The highest amount of H2 evaluation is obtained also by 0.5 Au/1.5 Pt-KTaO3_both after 240 min of UV-Vis light irradiation (76.53 μmol/min), which is eleven times higher than for pristine KTaO3 (6.69 μmol/min). Moreover, the most photocatalytic samples for each model reaction present good repeatability and stability after subsequent three cycles. Summarized, MNPs- and BNPs-KTaO3 are promising material in advanced applications of photocatalysis.

The role of precursor gases and meteorology on temporal evolution of O₃ at a tropical location in northeast India.

PubMed

Bhuyan, Pradip Kumar; Bharali, Chandrakala; Pathak, Binita; Kalita, Gayatry

2014-05-01

South Asia, particularly the Indo-Gangetic Plains and foothills of the Himalayas, has been found to be a major source of pollutant gases and particles affecting the regional as well as the global climate. Inventories of greenhouse gases for the South Asian region, particularly the sub-Himalayan region, have been inadequate. Hence, measurements of the gases are important from effective characterization of the gases and their climate effects. The diurnal, seasonal, and annual variation of surface level O3 measured for the first time in northeast India at Dibrugarh (27.4° N, 94.9° E, 111 m amsl), a sub-Himalayan location in the Brahmaputra basin, from November 2009 to May 2013 is presented. The effect of the precursor gases NO x and CO measured simultaneously during January 2012-May 2013 and the prevailing meteorology on the growth and decay of O3 has been studied. The O3 concentration starts to increase gradually after sunrise attaining a peak level around 1500 hours LT and then decreases from evening till sunrise next day. The highest and lowest monthly maximum concentration of O3 is observed in March (42.9 ± 10.3 ppb) and July (17.3 ± 7.0 ppb), respectively. The peak in O3 concentration is preceded by the peaks in NO x and CO concentrations which maximize during the period November to March with peak values of 25.2 ± 21.0 ppb and 1.0 ± 0.4 ppm, respectively, in January. Significant nonlinear correlation is observed between O3 and NO, NO2, and CO. National Atmospheric and Oceanic Administration Hybrid Single-Particle Lagrangian Integrated Trajectory back-trajectory and concentration weighted trajectory analysis carried out to delineate the possible airmass trajectory and to identify the potential source region of NO x and O3 concentrations show that in post-monsoon and winter, majority of the trajectories are confined locally while in pre-monsoon and monsoon, these are originated at the Indo-Gangetic plains, Bangladesh, and Bay of Bengal.

Wintertime ozone fluxes and profiles above a subalpine spruce-fir forest

Treesearch

Karl Zeller

2000-01-01

High rural concentrations of ozone (O3) are thought to be stratospheric in origin, advected from upwind urban sources, or photochemically generated locally by natural trace gas emissions. Ozone is known to be transported vertically downward from the above-canopy atmospheric surface layer and destroyed within stomata or on other biological and mineral surfaces. However...

Surface ozone in the Lake Tahoe Basin

Treesearch

Joel D. Burley; Sandra Theiss; Andrzej Bytnerowicz; Alan Gertler; Susan Schilling; Barbara Zielinska

2015-01-01

Surface ozone (O3) concentrations were measured in and around the Lake Tahoe Basin using both active monitors (2010) and passive samplers (2002, 2010). The 2010 data from active monitors indicate average summertime diurnal maxima of approximately 50–55 ppb. Some site-to-site variability is observed within the Basin during the well-mixed hours of...

Realizing a facile and environmental-friendly fabrication of high-performance multi-crystalline silicon solar cells by employing ZnO nanostructures and an Al2O3 passivation layer

PubMed Central

Chen, Hong-Yan; Lu, Hong-Liang; Sun, Long; Ren, Qing-Hua; Zhang, Hao; Ji, Xin-Ming; Liu, Wen-Jun; Ding, Shi-Jin; Yang, Xiao-Feng; Zhang, David Wei

2016-01-01

Nowadays, the multi-crystalline silicon (mc-Si) solar cells dominate the photovoltaic industry. However, the current acid etching method on mc-Si surface used by firms can hardly suppress the average reflectance value below 25% in the visible light spectrum. Meanwhile, the nitric acid and the hydrofluoric contained in the etching solution is both environmental unfriendly and highly toxic to human. Here, a mc-Si solar cell based on ZnO nanostructures and an Al2O3 spacer layer is demonstrated. The eco-friendly fabrication is realized by low temperature atomic layer deposition of Al2O3 layer as well as ZnO seed layer. Moreover, the ZnO nanostructures are prepared by nontoxic and low cost hydro-thermal growth process. Results show that the best passivation quality of the n+ -type mc-Si surface can be achieved by balancing the Si dangling bond saturation level and the negative charge concentration in the Al2O3 film. Moreover, the average reflectance on cell surface can be suppressed to 8.2% in 400–900 nm range by controlling the thickness of ZnO seed layer. With these two combined refinements, a maximum solar cell efficiency of 15.8% is obtained eventually. This work offer a facile way to realize the environmental friendly fabrication of high performance mc-Si solar cells. PMID:27924911

Realizing a facile and environmental-friendly fabrication of high-performance multi-crystalline silicon solar cells by employing ZnO nanostructures and an Al2O3 passivation layer

NASA Astrophysics Data System (ADS)

Chen, Hong-Yan; Lu, Hong-Liang; Sun, Long; Ren, Qing-Hua; Zhang, Hao; Ji, Xin-Ming; Liu, Wen-Jun; Ding, Shi-Jin; Yang, Xiao-Feng; Zhang, David Wei

2016-12-01

Nowadays, the multi-crystalline silicon (mc-Si) solar cells dominate the photovoltaic industry. However, the current acid etching method on mc-Si surface used by firms can hardly suppress the average reflectance value below 25% in the visible light spectrum. Meanwhile, the nitric acid and the hydrofluoric contained in the etching solution is both environmental unfriendly and highly toxic to human. Here, a mc-Si solar cell based on ZnO nanostructures and an Al2O3 spacer layer is demonstrated. The eco-friendly fabrication is realized by low temperature atomic layer deposition of Al2O3 layer as well as ZnO seed layer. Moreover, the ZnO nanostructures are prepared by nontoxic and low cost hydro-thermal growth process. Results show that the best passivation quality of the n+ -type mc-Si surface can be achieved by balancing the Si dangling bond saturation level and the negative charge concentration in the Al2O3 film. Moreover, the average reflectance on cell surface can be suppressed to 8.2% in 400-900 nm range by controlling the thickness of ZnO seed layer. With these two combined refinements, a maximum solar cell efficiency of 15.8% is obtained eventually. This work offer a facile way to realize the environmental friendly fabrication of high performance mc-Si solar cells.

Performance characteristics of MM5-SMOKE-CMAQ for a summer photochemical episode in southeast England, United Kingdom

NASA Astrophysics Data System (ADS)

Yu, Y.; Sokhi, R. S.; Kitwiroon, N.; Middleton, D. R.; Fisher, B.

In this study a modelling system consisting of Mesoscale Model (MM5), Sparse Matrix Operator Kernel Emissions (SMOKE) and Community Multiscale Air Quality (CMAQ) model has been applied to a summer photochemical period in southeast England, UK. Ozone (O 3), nitrogen dioxide (NO 2) and particulate matter (PM 2.5) concentrations modelled with different horizontal grid resolutions (9 and 3 km) were evaluated against available ground-level observations from the UK Automatic Urban and Rural Network (AURN) and London Air Quality Network (LAQN) for the period of 24-28 June 2001 with a focus on O 3 predictions. This effort, which represents the first comprehensive performance evaluation of the modelling system over a UK domain, reveals that CMAQ's ability to reproduce surface O 3 observations varies with O 3 concentrations. It underpredicts O 3 mixing ratios on high-O 3 days and overpredicts the maximum and minimum hourly O 3 values for most low-O 3 days. Model sensitivity analysis with doubled anthropogenic NO x or volatile organic compounds (VOC) emissions and analysis of the daylight-averaged levels of OX (sum of O 3 and NO 2) as a function of NO x revealed that the undereprediction of peak O 3 concentrations on high-O 3 days is caused by the underprediction of regional contribution and to a lesser extent local production, which might be related to the underestimation of European emissions in EMEP inventory and the lacked reactivity of the modelled atmosphere. CMAQ systematically underpredicts hourly NO 2 mixing ratios but captures the temporal variations. The normalized mean bias for hourly NO 2, although much larger than that for O 3, falls well within the generally accepted range of -20% to -50%. CMAQ with both resolutions (9 and 3 km) significantly underpredicts PM 2.5 mass concentrations and fails to reproduce its temporal variations. While model performance for O 3 and PM 2.5 are not very sensitive to model grid resolutions, a better agreement between modelled and measured hourly NO 2 mixing ratios was achieved with higher resolution. Further investigation into the uncertainties in meteorological input, uncertainties in emissions, as well as representation of physical and chemical processes (e.g. chemical mechanism) in the model is needed to identify the causes for the discrepancies between observations and predictions.

Gold Nanoparticle-Quantum Dot Fluorescent Nanohybrid: Application for Localized Surface Plasmon Resonance-induced Molecular Beacon Ultrasensitive DNA Detection

NASA Astrophysics Data System (ADS)

Adegoke, Oluwasesan; Park, Enoch Y.

2016-11-01

In biosensor design, localized surface plasmon resonance (LSPR)-induced signal from gold nanoparticle (AuNP)-conjugated reporter can produce highly sensitive nanohybrid systems. In order to retain the physicochemical properties of AuNPs upon conjugation, high colloidal stability in aqueous solution is needed. In this work, the colloidal stability with respect to the zeta potential (ZP) of four negatively charged thiol-functionalized AuNPs, thioglycolic (TGA)-AuNPs, 3-mercaptopropionic acid (MPA)-AuNPs, l-cysteine-AuNPs and l-glutathione (GSH)-AuNPs, and a cationic cyteamine-capped AuNPs was studied at various pHs, ionic strength, and NP concentration. A strong dependence of the ZP charge on the nanoparticle (NP) concentration was observed. High colloidal stability was exhibited between pH 3 and 9 for the negatively charged AuNPs and between pH 3 and 7 for the cationic AuNPs. With respect to the ionic strength, high colloidal stability was exhibited at ≤104 μM for TGA-AuNPs, l-cysteine-AuNPs, and GSH-AuNPs, whereas ≤103 μM is recommended for MPA-AuNPs. For the cationic AuNPs, very low ionic strength of ≤10 μM is recommended due to deprotonation at higher concentration. GSH-AuNPs were thereafter bonded to SiO2-functionalized alloyed CdZnSeS/ZnSe1.0S1.3 quantum dots (SiO2-Qdots) to form a plasmon-enhanced AuNP-SiO2-Qdots fluorescent nanohybrid. The AuNP-SiO2-Qdots conjugate was afterward conjugated to a molecular beacon (MB), thus forming an ultrasensitive LSPR-induced SiO2-Qdots-MB biosensor probe that detected a perfect nucleotide DNA sequence at a concentration as low as 10 fg/mL. The limit of detection was 11 fg/mL (1.4 fM) while the biosensor probe efficiently distinguished between single-base mismatch and noncomplementary sequence target.

Effect of soil humic and fulvic acids, pH and ionic strength on Th(IV) sorption to TiO2 nanoparticles.

PubMed

Tan, Xiaoli; Wang, Xiangke; Chen, Changlun; Sun, Aihua

2007-04-01

Thorium is considered as a chemical analog of other tetravalent actinides. Herein, the sorption of Th(IV) on TiO(2) in the presence or absence of soil fulvic acid (FA)/humic acid (HA) as a function of pH, ionic strength and FA/HA concentration has been studied by a batch method. The morphology was characterized by scanning electron microscopy (SEM). The results indicate that sorption of Th(IV) on TiO(2) increases from 0% to approximately 94% at pH 1 approximately 4, and then maintains level with increasing pH values. Both FA and HA have a positive effect on Th(IV) sorption at low pH values and the contribution of FA on Th(IV) sorption is rather higher than that of HA at pH<4. The sorption is weakly dependent on the concentration of KNO(3) in solution, but the cations K(+), Na(+) and Li(+) influence Th(IV) sorption more obviously. The batch results indicate that the inner sphere complex formation is formed at bare surfaces or FA/HA-bound TiO(2) particle surfaces. Results of SEM analysis show that the particle sizes of TiO(2), Th-TiO(2) and Th-HA-TiO(2) colloids are quite different. Surface complexation may be considered as the main sorption mechanism.

Collateral geochemical impacts of agricultural nitrogen enrichment from 1963 to 1985: a southern Wisconsin ground water depth profile.

PubMed

Browne, Bryant A; Kraft, George J; Bowling, Juliane M; Devita, William M; Mechenich, David J

2008-01-01

In this study, we used chlorofluorocarbon (CFC) age-dating to investigate the geochemistry of N enrichment within a bedrock aquifer depth profile beneath a south central Wisconsin agricultural landscape. Measurement of N(2)O and excess N(2) allowed us to reconstruct the total NO(3)(-) and total nitrogen (TN) leached to ground water and was essential for tracing the separate influences of soil nitrification and ground water denitrification in the collateral geochemical chronology. We identify four geochemical impacts due to a steady ground water N enrichment trajectory (39 +/- 2.2 micromol L(-1) yr(-1), r(2) = 0.96) over two decades (1963-1985) of rapidly escalating N use. First, as a by-product of soil nitrification, N(2)O entered ground water at a stable (r(2) = 0.99) mole ratio of 0.24 +/- 0.007 mole% (N(2)O-N/NO(3)-N). The gathering of excess N(2)O in ground water is a potential concern relative to greenhouse gas emissions and stratospheric ozone depletion after it discharges to surface water. Second, excess N(2) measurements revealed that NO(3)(-) was a prominent, mobile, labile electron acceptor comparable in importance to O(2.) Denitrification transformed 36 +/- 15 mole% (mol mol(-1) x 100) of the total N within the profile to N(2) gas, delaying exceedance of the NO(3)(-) drinking water standard by approximately 6 yr. Third, soil acids produced from nitrification substantially increased the concentrations of major, dolomitic ions (Ca, Mg, HCO(3)(-)) in ground water relative to pre-enrichment conditions. By 1985, concentrations approximately doubled; by 2006, CFC age-date projections suggest concentrations may have tripled. Finally, the nitrification induced mobilization of Ca may have caused a co-release of P from Ca-rich soil surfaces. Dissolved P increased from an approximate background value of 0.02 mg L(-1) in 1963 to 0.07 mg L(-1) in 1985. The CFC age-date projections suggest the concentration could have reached 0.11 mg L(-1) in ground water recharge by 2006. These results highlight an intersection of the N and P cycles potentially important for managing the quality of ground water discharged to surface water.

The formation of tungsten doped Al2O3/ZnO coatings on aluminum by plasma electrolytic oxidation and their application in photocatalysis

NASA Astrophysics Data System (ADS)

Stojadinović, Stevan; Vasilić, Rastko; Radić, Nenad; Tadić, Nenad; Stefanov, Plamen; Grbić, Boško

2016-07-01

Tungsten doped Al2O3/ZnO coatings are formed by plasma electrolytic oxidation of aluminum substrate in supporting electrolyte (0.1 M boric acid + 0.05 M borax + 2 g/L ZnO) with addition of different concentrations of Na2WO4·2H2O. The morphology, crystal structure, chemical composition, and light absorption characteristics of formed surface coatings are investigated. The X-ray diffraction and X-ray photoelectron spectroscopy results indicate that formed surface coatings consist of alpha and gamma phase of Al2O3, ZnO, metallic tungsten and WO3. Obtained results showed that incorporated tungsten does not have any influence on the absorption spectra of Al2O3/ZnO coatings, which showed invariable band edge at about 385 nm. The photocatalytic activity of undoped and tungsten doped Al2O3/ZnO coatings is estimated by the photodegradation of methyl orange. The photocatalytic activity of tungsten doped Al2O3/ZnO coatings is higher thanof undoped Al2O3/ZnO coatings; the best photocatalytic activity is ascribed to coatings formed in supporting electrolyte with addition of 0.3 g/L Na2WO4·2H2O. Tungsten in Al2O3/ZnO coatings acts as a charge trap, thus reducing the recombination rate of photogenerated electron-hole pairs. The results of PL measurements are in agreement with photocatalytic activity. Declining PL intensity corresponds to increasing photocatalytic activity of the coatings, indicating slower recombination of electron-hole pairs.

Hydrogen peroxide and glucose concentration measurement using optical fiber grating sensors with corrodible plasmonic nanocoatings

PubMed Central

Zhang, Xuejun; Wu, Ze; Liu, Fu; Fu, Qiangqiang; Chen, Xiaoyong; Xu, Jian; Zhang, Zhaochuan; Huang, Yunyun; Tang, Yong; Guo, Tuan; Albert, Jacques

2018-01-01

We propose and demonstrate hydrogen peroxide (H2O2) and glucose concentration measurements using a plasmonic optical fiber sensor. The sensor utilizes a tilted fiber Bragg grating (TFBG) written in standard single mode communication fiber. The fiber is over coated with an nm-scale film of silver that supports surface plasmon resonances (SPRs). Such a tilted grating SPR structure provides a high density of narrow spectral resonances (Q-factor about 105) that overlap with the broader absorption band of the surface plasmon waves in the silver film, thereby providing an accurate tool to measure small shifts of the plasmon resonance frequencies. The H2O2 to be detected acts as an oxidant to etch the silver film, which has the effect of gradually decreasing the SPR attenuation. The etching rate of the silver film shows a clear relationship with the H2O2 concentration so that monitoring the progressively increasing attenuation of a selected surface plasmon resonance over a few minutes enables us to measure the H2O2 concentration with a limit of detection of 0.2 μM. Furthermore, the proposed method can be applied to the determination of glucose in human serum for a concentration range from 0 to 12 mM (within the physiological range of 3-8 mM) by monitoring the H2O2 produced by an enzymatic oxidation process. The sensor does not require accurate temperature control because of the inherent temperature insensitivity of TFBG devices referenced to the core mode resonance. A gold mirror coated on the fiber allows the sensor to work in reflection, which will facilitate the integration of the sensor with a hypodermic needle for in vitro measurements. The present study shows that Ag-coated TFBG-SPR can be applied as a promising type of sensing probe for optical detection of H2O2 and glucose detection in human serum. PMID:29675315

Hydrogen peroxide and glucose concentration measurement using optical fiber grating sensors with corrodible plasmonic nanocoatings.

PubMed

Zhang, Xuejun; Wu, Ze; Liu, Fu; Fu, Qiangqiang; Chen, Xiaoyong; Xu, Jian; Zhang, Zhaochuan; Huang, Yunyun; Tang, Yong; Guo, Tuan; Albert, Jacques

2018-04-01

We propose and demonstrate hydrogen peroxide (H 2 O 2 ) and glucose concentration measurements using a plasmonic optical fiber sensor. The sensor utilizes a tilted fiber Bragg grating (TFBG) written in standard single mode communication fiber. The fiber is over coated with an nm-scale film of silver that supports surface plasmon resonances (SPRs). Such a tilted grating SPR structure provides a high density of narrow spectral resonances (Q-factor about 10 5 ) that overlap with the broader absorption band of the surface plasmon waves in the silver film, thereby providing an accurate tool to measure small shifts of the plasmon resonance frequencies. The H 2 O 2 to be detected acts as an oxidant to etch the silver film, which has the effect of gradually decreasing the SPR attenuation. The etching rate of the silver film shows a clear relationship with the H 2 O 2 concentration so that monitoring the progressively increasing attenuation of a selected surface plasmon resonance over a few minutes enables us to measure the H 2 O 2 concentration with a limit of detection of 0.2 μM. Furthermore, the proposed method can be applied to the determination of glucose in human serum for a concentration range from 0 to 12 mM (within the physiological range of 3-8 mM) by monitoring the H 2 O 2 produced by an enzymatic oxidation process. The sensor does not require accurate temperature control because of the inherent temperature insensitivity of TFBG devices referenced to the core mode resonance. A gold mirror coated on the fiber allows the sensor to work in reflection, which will facilitate the integration of the sensor with a hypodermic needle for in vitro measurements. The present study shows that Ag-coated TFBG-SPR can be applied as a promising type of sensing probe for optical detection of H 2 O 2 and glucose detection in human serum.

Microbial oxidation of Fe²⁺ and pyrite exposed to flux of micromolar H₂O₂ in acidic media.

PubMed

Ma, Yingqun; Lin, Chuxia

2013-01-01

At an initial pH of 2, while abiotic oxidation of aqueous Fe(2+) was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe(2+) could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe(2+) to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe(2+)-Fe(3+) conversion rate in the solution (due to reduced microbial activity) weakened the Fe(3+)-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria.

Monte Carlo simulations of coupled diffusion and surface reactions during the aqueous corrosion of borosilicate glasses

DOE PAGES

Kerisit, Sebastien; Pierce, Eric M.; Ryan, Joseph V.

2014-09-19

Borosilicate nuclear waste glasses develop complex altered layers as a result of coupled processes such as hydrolysis of network species, condensation of Si species, and diffusion. However, diffusion has often been overlooked in Monte Carlo models of the aqueous corrosion of borosilicate glasses. Therefore, in this paper three different models for dissolved Si diffusion in the altered layer were implemented in a Monte Carlo model and evaluated for glasses in the compositional range (75 - x) mol% SiO 2 (12.5 + x/2) mol% B 2O 3 and (12.5 + x/2) mol% Na 2O, where 0 ≤ x ≤ 20%, andmore » corroded in static conditions at a surface-area-to-volume ratio of 1000 m -1. The three models considered instantaneous homogenization (M1), linear concentration gradients (M2), and concentration profiles determined by solving Fick's 2nd law using a finite difference method (M3). Model M3 revealed that concentration profiles in the altered layer are not linear and show changes in shape and magnitude as corrosion progresses, unlike those assumed in model M2. Furthermore, model M3 showed that, for borosilicate glasses with a high forward dissolution rate compared to the diffusion rate, the gradual polymerization and densification of the altered layer is significantly delayed compared to models M1 and M2. Finally, models M1 and M2 were found to be appropriate models only for glasses with high release rates such as simple borosilicate glasses with low ZrO 2 content.« less

Photocatalytic degradation of ofloxacin and evaluation of the residual antimicrobial activity.

PubMed

Peres, M S; Maniero, M G; Guimarães, J R

2015-03-01

Ofloxacin is an antimicrobial agent frequently found in significant concentrations in wastewater and surface water. Its continuous introduction into the environment is a potential risk to non-target organisms or to human health. In this study, ofloxacin degradation by UV/TiO2 and UV/TiO2/H2O2, antimicrobial activity (E. coli) of samples subjected to these processes, and by-products formed were evaluated. For UV/TiO2, the degradation efficiency was 89.3% in 60 min of reaction when 128 mg L(-1) TiO2 were used. The addition of 1.68 mmol L(-1) hydrogen peroxide increased degradation to 97.8%. For UV/TiO2, increasing the catalyst concentration from 4 to 128 mg L(-1) led to an increase in degradation efficiency. For both processes, the antimicrobial activity was considerably reduced throughout the reaction time. The structures of two by-products are presented: m/z 291 (9-fluoro-3-methyl-10-(methyleneamino)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid) and m/z 157 ((Z)-2-formyl-3-((2-oxoethyl)imino)propanoic acid).

In situ growth of CuInS2 nanocrystals on nanoporous TiO2 film for constructing inorganic/organic heterojunction solar cells

PubMed Central

2013-01-01

Inorganic/organic heterojunction solar cells (HSCs) have attracted increasing attention as a cost-effective alternative to conventional solar cells. This work presents an HSC by in situ growth of CuInS2(CIS) layer as the photoabsorption material on nanoporous TiO2 film with the use of poly(3-hexylthiophene) (P3HT) as hole-transport material. The in situ growth of CIS nanocrystals has been realized by solvothermally treating nanoporous TiO2 film in ethanol solution containing InCl3 · 4H2O, CuSO4 · 5H2O, and thioacetamide with a constant concentration ratio of 1:1:2. InCl3 concentration plays a significant role in controlling the surface morphology of CIS layer. When InCl3 concentration is 0.1 M, there is a layer of CIS flower-shaped superstructures on TiO2 film, and CIS superstructures are in fact composed of ultrathin nanoplates as ‘petals’ with plenty of nanopores. In addition, the nanopores of TiO2 film are filled by CIS nanocrystals, as confirmed using scanning electron microscopy image and by energy dispersive spectroscopy line scan analysis. Subsequently, HSC with a structure of FTO/TiO2/CIS/P3HT/PEDOT:PSS/Au has been fabricated, and it yields a power conversion efficiency of 1.4%. Further improvement of the efficiency can be expected by the optimization of the morphology and thickness of CIS layer and the device structure. PMID:23947562

Improvement of Transparent Conducting Performance on Oxygen-Activated Fluorine-Doped Tin Oxide Electrodes Formed by Horizontal Ultrasonic Spray Pyrolysis Deposition.

PubMed

Koo, Bon-Ryul; Oh, Dong-Hyeun; Riu, Doh-Hyung; Ahn, Hyo-Jin

2017-12-27

In this study, highly transparent conducting fluorine-doped tin oxide (FTO) electrodes were fabricated using the horizontal ultrasonic spray pyrolysis deposition. In order to improve their transparent conducting performances, we carried out oxygen activation by adjusting the ratio of O 2 /(O 2 +N 2 ) in the carrier gas (0%, 20%, and 50%) used during the deposition process. The oxygen activation on the FTO electrodes accelerated the substitution concentration of F (F O • ) into the oxygen sites in the FTO electrode while the oxygen vacancy (V O • • ) concentration was reduced. In addition, due to growth of pyramid-shaped crystallites with (200) preferred orientations, this oxygen activation caused the formation of a uniform surface structure. As a result, compared to others, the FTO electrode prepared at 50% O 2 showed excellent electrical and optical properties (sheet resistance of ∼4.0 ± 0.14 Ω/□, optical transmittance of ∼85.3%, and figure of merit of ∼5.09 ± 0.19 × 10 -2 Ω -1 ). This led to a superb photoconversion efficiency (∼7.03 ± 0.20%) as a result of the improved short-circuit current density. The photovoltaic performance improvement can be defined by the decreased sheet resistance of FTO used as a transparent conducting electrode in dye-sensitized solar cells (DSSCs), which is due to the combined effect of the high carrier concentration by the improved F O • concentration on the FTO electrodes and the fasted Hall mobility by the formation of a uniform FTO surface structure and distortion relaxation on the FTO lattices resulting from the reduced V O • • • concentration.

The electrical, elemental, optical, and surface properties of Si-doped ZnO thin films prepared by thermionic vacuum arc

NASA Astrophysics Data System (ADS)

Mohammadigharehbagh, Reza; Özen, Soner; Yudar, Hafizittin Hakan; Pat, Suat; Korkmaz, Şadan

2017-09-01

The purpose of this work is to study the properties of Si-doped ZnO (SZO) thin films, which were prepared using the non-reactive thermionic vacuum arc technique. The analysis of the elemental, optical, and surface properties of ZnO:Si thin films was carried out using energy dispersive x-ray spectroscopy, UV-VIS spectrophotometry, atomic force microscopy, and scanning electron microscopy, respectively. The current-voltage measurement was employed in order to study the electrical properties of the films. The effect of Si doping on the physical properties of ZnO films was investigated. The film thicknesses were measured as 55 and 35 nm for glass and PET substrates, respectively. It was clearly observed from the x-ray diffraction results that the Si and ZnO peaks were present in the coated SZO films for all samples. The morphological studies showed that the deposited surfaces are homogenous, dense, and have a uniform surface, with the existence of some cracks only on the glass substrate. The elemental composition has confirmed the existence of Zn, Si, and O elements within the prepared films. Using a UV-VIS spectrophotometer, the optical parameters such as transmittance, absorbance, refractive index, and reflectance were calculated. It should be noted that the transparency and refractive indices obtained from the measurements decrease with increasing Si concentration. The obtained optical bandgap values using transmittance spectra were determined to be 3.74 and 3.84 eV for the glass and PET substrates, respectively. An increase in the bandgap results demonstrates that the Si doping concentration is comparable to the pure ZnO thin films. The current versus voltage curves revealed the ohmic nature of the films. Subsequently, the development and fabrication of excellent transparent conducting electrodes enabled the appropriate use of Si-doped ZnO thin films.

Efficient Removal of Tetracycline from Aqueous Media with a Fe3O4 Nanoparticles@graphene Oxide Nanosheets Assembly

PubMed Central

Hu, Xinjiang; Zhao, Yunlin; Wang, Hui; Tan, Xiaofei; Yang, Yuanxiu; Liu, Yunguo

2017-01-01

A readily separated composite was prepared via direct assembly of Fe3O4 magnetic nanoparticles onto the surface of graphene oxide (GO) (labeled as Fe3O4@GO) and used as an adsorbent for the removal of tetracycline (TC) from wastewater. The effects of external environmental conditions, such as pH, ionic strength, humic acid (HA), TC concentration, and temperature, on the adsorption process were studied. The adsorption data were analyzed by kinetics and isothermal models. The results show that the Fe3O4@GO composite has excellent sorptive properties and can efficiently remove TC. At low pH, the adsorption capacity of Fe3O4@GO toward TC decreases slowly with increasing pH value, while the adsorption capacity decreases rapidly at higher pH values. The ionic strength has insignificant effect on TC adsorption. The presence of HA affects the affinity of Fe3O4@GO to TC. The pseudo-second-order kinetics model and Langmuir model fit the adsorption data well. When the initial concentration of TC is 100 mg/L, a slow adsorption process dominates. Film diffusion is the rate limiting step of the adsorption. Importantly, Fe3O4@GO has good regeneration performance. The above results are of great significance to promote the application of Fe3O4@GO in the treatment of antibiotic wastewater. PMID:29194395

Simulating ozone dry deposition at a boreal forest with a multi-layer canopy deposition model

NASA Astrophysics Data System (ADS)

Zhou, Putian; Ganzeveld, Laurens; Rannik, Üllar; Zhou, Luxi; Gierens, Rosa; Taipale, Ditte; Mammarella, Ivan; Boy, Michael

2017-01-01

A multi-layer ozone (O3) dry deposition model has been implemented into SOSAA (a model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to improve the representation of O3 concentration and flux within and above the forest canopy in the planetary boundary layer. We aim to predict the O3 uptake by a boreal forest canopy under varying environmental conditions and analyse the influence of different factors on total O3 uptake by the canopy as well as the vertical distribution of deposition sinks inside the canopy. The newly implemented dry deposition model was validated by an extensive comparison of simulated and observed O3 turbulent fluxes and concentration profiles within and above the boreal forest canopy at SMEAR II (Station to Measure Ecosystem-Atmosphere Relations II) in Hyytiälä, Finland, in August 2010. In this model, the fraction of wet surface on vegetation leaves was parametrised according to the ambient relative humidity (RH). Model results showed that when RH was larger than 70 % the O3 uptake onto wet skin contributed ˜ 51 % to the total deposition during nighttime and ˜ 19 % during daytime. The overall contribution of soil uptake was estimated about 36 %. The contribution of sub-canopy deposition below 4.2 m was modelled to be ˜ 38 % of the total O3 deposition during daytime, which was similar to the contribution reported in previous studies. The chemical contribution to O3 removal was evaluated directly in the model simulations. According to the simulated averaged diurnal cycle the net chemical production of O3 compensated up to ˜ 4 % of dry deposition loss from about 06:00 to 15:00 LT. During nighttime, the net chemical loss of O3 further enhanced removal by dry deposition by a maximum ˜ 9 %. Thus the results indicated an overall relatively small contribution of airborne chemical processes to O3 removal at this site.

Nanostructured GdxZn1-xO thin films by nebulizer spray pyrolysis technique: Role of doping concentration on the structural and optical properties

NASA Astrophysics Data System (ADS)

Mariappan, R.; Ponnuswamy, V.; Suresh, P.; Suresh, R.; Ragavendar, M.

2013-07-01

Nanostructured GdxZn1-xO thin films with different Gd concentration from 0% to 10% deposited at 400 °C using the NSP technique. The films were characterized by structural, surface and optical properties, respectively. X-ray diffraction analysis shows that the Gd doped ZnO films have lattice parameters a = 3.2497 Å and c = 5.2018 Å with hexagonal structure and preferential orientation along (0 0 2) plane. The estimated values compare well with the standard values. When film thickness increases from 222 to 240 nm a high visible region transmittance (>70%) is observed. The optical band gap energy, optical constants (n and k), complex dielectric constants (ɛr and ɛi) and optical conductivities (σr and σi) were calculated from optical transmittance data. The optical band gap energy is 3.2 eV for pure ZnO film and 3.6 eV for Gd0.1Zn0.9O film. The PL studies confirm the presence of a strong UV emission peak at 399 nm. Besides, the UV emission of ZnO films decreases with the increase of Gd doping concentration correspondingly the ultra-violet emission is replaced by blue and green emissions.

Low Temperature Propane Oxidation over Co 3O 4 based Nano-array Catalysts. Ni Dopant Effect, Reaction Mechanism and Structural Stability

DOE PAGES

Ren, Zheng; Wu, Zili; Gao, Puxian; ...

2015-06-09

Low temperature propane oxidation has been achieved by Co 3O 4-based nano-array catalysts featuring low catalytic materials loading. The Ni doping into the Co 3O 4 lattice has led to enhanced reaction kinetics at low temperature by promoting the surface lattice oxygen activity. In situ DRIFTS investigation in tandem with isotopic oxygen exchange reveals that the propane oxidation proceeds via Mars-van Krevelen mechanism where surface lattice oxygen acts as the active site whereas O 2 in the reaction feed does not directly participate in CO 2 formation. The Ni doping promotes the formation of less stable carbonates on the surfacemore » to facilitate the CO 2 desorption. The thermal stability of Ni doped Co 3O 4 decreases with increased Ni concentration while catalytic activity increases. A balance between enhanced activity and compromised thermal stability shall be considered in the Ni doped Co 3O 4 nano-array catalysts for low temperature hydrocarbon oxidation. This study provides useful and timely guidance for rational catalyst design toward low temperature catalytic oxidation.« less

Effect of dissolved ozone or ferric ions on photodegradation of thiacloprid in presence of different TiO2 catalysts.

PubMed

Cernigoj, Urh; Stangar, Urska Lavrencic; Jirkovský, Jaromír

2010-05-15

Combining TiO(2) photocatalysis with inorganic oxidants (such as O(3) and H(2)O(2)) or transition metal ions (Fe(3+), Cu(2+) and Ag(+)) often leads to a synergic effect. Electron transfer between TiO(2) and the oxidant is usually involved. Accordingly, the degree of synergy could be influenced by TiO(2) surface area. With this in mind, the disappearance of thiacloprid, a neonicotinoid insecticide, was studied applying various photochemical AOPs and different TiO(2) photocatalysts. In photocatalytic ozonation experiments, synergic effect of three different TiO(2) photocatalysts was quantified. Higher surface area resulted in a more pronounced synergic effect but an increasing amount of TiO(2) did not influence the degree of the synergy. This supports the theory that the synergy is a consequence of adsorption of ozone on the TiO(2) surface. No synergy was observed in photocatalytic degradation of thiacloprid in the presence of dissolved iron(III) species performed under varied experimental conditions (concentration, age of iron(III) solution, different TiO(2) films, usage of TiO(2) slurries). This goes against the literature for different organic compounds (i.e., monuron). It indicates different roles of iron(III) in the photodegradation of different organic molecules. Moreover, TiO(2) surface area did not affect photodegradation efficiency in iron(III)-based experiments which could confirm absence of electron transfer between TiO(2) photocatalyst and iron(III). Copyright (c) 2009 Elsevier B.V. All rights reserved.

δ-Doping of oxygen vacancies dictated by thermodynamics in epitaxial SrTiO 3 films

DOE PAGES

Li, Fengmiao; Yang, Fang; Liang, Yan; ...

2017-06-01

Homoepitaxial SrTiO 3(110) film is grown by molecular beam epitaxy in ultra-high vacuum with oxygen diffusing from substrate as the only oxidant. The resulted oxygen vacancies (V Os) are found to be spatially confined within few subsurface layers only, forming a quasi-two-dimensional doped region with a tunable high concentration. Such a δ-function distribution of V Os is essentially determined by the thermodynamics associated with the surface reconstruction, and facilitated by the relatively high growth temperature. Here, our results demonstrate that it is feasible to tune V Os distribution at the atomic scale by controlling the lattice structure of oxide surfaces.more » Transition metal oxide interfaces have exhibited a variety of novel phenomena, including the high-mobility two-dimensional electron gas, superconductivity and unusual magnetism. While these phenomena are inherently related to the artificially designed architecture, oxygen vacancies (V Os) are recognized to be particularly important in determining the exotic behaviors of the oxides systems. As electron donors in oxides, V Os were observed to be one of the major factors for the high carrier density at the LaAlO 3/SrTiO 3 interface. V Os induce ferromagnetism in the epitaxial LaCoO 3 films via the ordering of excess electrons in Co 3d orbit. It was also suggested that the existence of V Os plays an important role in the formation of undesirable insulating phase in ultrathin films of many metallic oxide materials, referred to as the “dead layer” behavior. How V Os are involved in such complex phenomena is still unclear. One essential issue toward the design of emergent properties of oxide films is how to characterize and control V Os at the atomic scale. Recently, quantitative measurements of V O concentration have been realized with high spatial resolution benefited by the development of the state-of-the-art aberration-corrected scanning transmission microscope (STEM) and related spectroscopy techniques. However, tuning the V O density precisely by growth control is still extremely challenging. Different oxidants, i.e., molecular O 2, O 3 and atomic O, have been used with different feeding pressure during the growth. This approach is limited by thermodynamics of the material since the pressure of oxidant has to coordinate with temperature and other parameters in order to ensure the formation of the desired phase. In many cases the optimal condition for oxygen stoichiometry cannot be reached, and residual V Os are inevitably formed. It has been reported that V Os even form inhomogeneous clusters in SrTiO 3 (STO) films. Post annealing is another thermodynamic approach and seems to be effective to reduce the V O density. However, it does not allow the precise control of V Os distribution at the atomic scale either. In the current work, to study the control of V Os at the atomic scale, we grow SrTiO 3 homoepitaxial films along the polar [110] direction. Atomically well-defined (4 × 1) reconstruction is maintained on the surface all through the growth [see Fig. 1 (a) and (b)], which compensates the polarity. More importantly, the energy configuration associated with the surface reconstruction results in the spatial confinement of V Os within only few subsurface layers of the film, while their concentration remains extremely low on the topmost surface and in the bulk of STO substrate. In conclusion, we show that such a quasi-two-dimensional (2D) V O-doped layer, mimicking the δ-doping case in conventional semiconductors, can be precisely controlled.« less

δ-Doping of oxygen vacancies dictated by thermodynamics in epitaxial SrTiO 3 films

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

Li, Fengmiao; Yang, Fang; Liang, Yan

Homoepitaxial SrTiO 3(110) film is grown by molecular beam epitaxy in ultra-high vacuum with oxygen diffusing from substrate as the only oxidant. The resulted oxygen vacancies (V Os) are found to be spatially confined within few subsurface layers only, forming a quasi-two-dimensional doped region with a tunable high concentration. Such a δ-function distribution of V Os is essentially determined by the thermodynamics associated with the surface reconstruction, and facilitated by the relatively high growth temperature. Here, our results demonstrate that it is feasible to tune V Os distribution at the atomic scale by controlling the lattice structure of oxide surfaces.more » Transition metal oxide interfaces have exhibited a variety of novel phenomena, including the high-mobility two-dimensional electron gas, superconductivity and unusual magnetism. While these phenomena are inherently related to the artificially designed architecture, oxygen vacancies (V Os) are recognized to be particularly important in determining the exotic behaviors of the oxides systems. As electron donors in oxides, V Os were observed to be one of the major factors for the high carrier density at the LaAlO 3/SrTiO 3 interface. V Os induce ferromagnetism in the epitaxial LaCoO 3 films via the ordering of excess electrons in Co 3d orbit. It was also suggested that the existence of V Os plays an important role in the formation of undesirable insulating phase in ultrathin films of many metallic oxide materials, referred to as the “dead layer” behavior. How V Os are involved in such complex phenomena is still unclear. One essential issue toward the design of emergent properties of oxide films is how to characterize and control V Os at the atomic scale. Recently, quantitative measurements of V O concentration have been realized with high spatial resolution benefited by the development of the state-of-the-art aberration-corrected scanning transmission microscope (STEM) and related spectroscopy techniques. However, tuning the V O density precisely by growth control is still extremely challenging. Different oxidants, i.e., molecular O 2, O 3 and atomic O, have been used with different feeding pressure during the growth. This approach is limited by thermodynamics of the material since the pressure of oxidant has to coordinate with temperature and other parameters in order to ensure the formation of the desired phase. In many cases the optimal condition for oxygen stoichiometry cannot be reached, and residual V Os are inevitably formed. It has been reported that V Os even form inhomogeneous clusters in SrTiO 3 (STO) films. Post annealing is another thermodynamic approach and seems to be effective to reduce the V O density. However, it does not allow the precise control of V Os distribution at the atomic scale either. In the current work, to study the control of V Os at the atomic scale, we grow SrTiO 3 homoepitaxial films along the polar [110] direction. Atomically well-defined (4 × 1) reconstruction is maintained on the surface all through the growth [see Fig. 1 (a) and (b)], which compensates the polarity. More importantly, the energy configuration associated with the surface reconstruction results in the spatial confinement of V Os within only few subsurface layers of the film, while their concentration remains extremely low on the topmost surface and in the bulk of STO substrate. In conclusion, we show that such a quasi-two-dimensional (2D) V O-doped layer, mimicking the δ-doping case in conventional semiconductors, can be precisely controlled.« less

Numerical investigation of the effects of iron oxidation reactions on the fume formation mechanism in arc welding

NASA Astrophysics Data System (ADS)

Sanibondi, Paolo

2015-09-01

Fume formation during arc welding has been modelled using a stochastic approach taking into account iron oxidation reactions. The model includes the nucleation and condensation of Fe and FeO vapours, the reaction of gaseous O2 and O on the nanoparticle surface, the coagulation of the nanoparticles including a sintering time as a function of temperature and composition, assuming chemical equilibrium for species in the gaseous phase. Results suggest that fumes generated in gas metal arc welding with oxidizing shielding mixtures are composed of aggregates of primary particles that are nucleated from gas-phase FeO and further oxidized to Fe3O4 and Fe2O3 in the liquid and solid phase, respectively. The composition of the fumes at the end of the formation process depends on the relative initial concentration of Fe and O2 species in the gas mixture and on the diameter of the primary particles that compose the aggregates: as the oxidation reactions are driven by deposition of oxygen on nanoparticle surface, the oxidation of larger particles is slower than that of smaller particles because of their lower surface to volume ratio. Solid-state diffusion is limiting the oxidation process at temperatures lower than 1500 K, inducing the formation of not fully oxidized particles composed of Fe3O4.

Further evidence for particle nucleation in clear air adjacent to marine cumulus clouds

NASA Astrophysics Data System (ADS)

Perry, Kevin D.; Hobbs, Peter V.

1994-11-01

Observational evidence is presented for the nucleation of condensation nuclei (CN) in the clear air adjacent to an isolated, marine, cumulus cloud. Two separate regions of particle nucleation are identified: one located above the cloud top, and the second located downwind of the cloud near the level of the anvil outflow. The regions of high CN concentrations were located in extremely clean marine air, with unactivated aerosol surface area (excluding the nucleation mode) less than 2 sq micrometers/cu cm, air temperature -31 C, and higher relative humidities than the undisturbed environment. Vertical profile measurements downwind of the cloud showed that CN concentrations at the level of the anvil outflow (4.9 km) were 8 times greater than at any other level between the surface and 5.3 km. A conceptual model is formulated in which aerosol particles, sulfur dioxide (SO2), sulfuric acid vapor (H2SO4), dimethyl sulfide (DMS), and ozone (O3) from the boundary layer are entrained into the cumulus cloud. Total aerosol number concentrations and unactivated aerosol surface area decrease with height in the cloud due to Brownian diffusion and diffusiophoresis of cloud interstitial aerosol to hydrometeors, coalescence scavenging by cloud droplets, collisional scavenging by ice particles, and subsequent removal by precipitation. The air that is detrained from the cloud raises the relative humidity and vents the clean air, SO2, H2SO4, DMS, and O3 to the near-cloud environment. Hydroxyl radicals then oxidize the SO2 and DMS to H2SO4. Under the conditions of high relative humidity, low total aerosol surface area, low temperatures, and high SO2 concentrations near cloud top, significant concentrations of new particles can be produced by homogeneous-bimolecular nucleation of sulfuric acid solution droplets from H2SO4 and H2O vapor molecules. The concentration of CN as a function of time is calculated for the case described in this paper using a bimodal integral nucleation model. The model results show that significant numbers of CN could have been produced within a few hours by the homogeneous-bimolecular nucleation of sulfuric acid solution droplets under the observed conditions provided the concentration of SO2 near cloud top was enhanced by vertical transport.

Fast response of sprayed vanadium pentoxide (V2O5) nanorods towards nitrogen dioxide (NO2) gas detection

NASA Astrophysics Data System (ADS)

Mane, A. A.; Suryawanshi, M. P.; Kim, J. H.; Moholkar, A. V.

2017-05-01

The V2O5 nanorods have been successfully spray deposited at optimized substrate temperature of 400 °C onto the glass substrates using vanadium trichloride (VCl3) solution of different concentrations. The effect of solution concentration on the physicochemical and NO2 gas sensing properties of sprayed V2O5 nanorods is studied at different operating temperatures and gas concentrations. The XRD study reveals the formation of V2O5 having an orthorhombic symmetry. The FE-SEM micrographs show the nanorods-like morphology of V2O5. The AFM micrographs exhibit a well covered granular surface topography. For direct allowed transition, the band gap energy values are found to be decreased from 2.45 eV to 2.42 eV. The nanorods deposited with 30 mM solution concentration shows the maximum response of 24.2% for 100 ppm NO2 gas concentration at an operating temperature of 200 °C with response and recovery times of 13 s and 140 s, respectively. Finally, the chemisorption mechanism of NO2 gas on the V2O5 nanorods is discussed.

Composite WO 3/TiO 2 nanostructures for high electrochromic activity

DOE PAGES

Reyes-Gil, Karla R.; Stephens, Zachary D.; Stavila, Vitalie; ...

2015-01-06

A composite material consisting of TiO 2 nanotubes (NT) with WO 3 electrodeposited on its surface has been fabricated, detached from its Ti substrate, and attached to a fluorine-doped tin oxide (FTO) film on glass for application to electrochromic (EC) reactions. Several adhesion layers were tested, finding that a paste of TiO 2 made from commercially available TiO 2 nanoparticles creates an interface for the TiO 2 NT film to attach to the FTO glass, which is conductive and does not cause solution-phase ions in an electrolyte to bind irreversibly with the material. The effect of NT length and WOmore » 3 concentration on the EC performance were studied. As a result, the composite WO 3/TiO 2 nanostructures showed higher ion storage capacity, better stability, enhanced EC contrast, and longer memory time compared with the pure WO 3 and TiO 2 materials« less

Electrospinning Hetero-Nanofibers In2O3/SnO2 of Homotype Heterojunction with High Gas Sensing Activity

PubMed Central

Du, Haiying; Yao, PengJun; Sun, Yanhui; Wang, Jing; Wang, Huisheng; Yu, Naisen

2017-01-01

In2O3/SnO2 composite hetero-nanofibers were synthesized by an electrospinning technique for detecting indoor volatile organic gases. The physical and chemical properties of In2O3/SnO2 hetero-nanofibers were characterized and analyzed by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), Energy Dispersive X-Ray Spectroscopy (EDX), specific surface Brunauer–Emmett–Teller (BET) and X-ray photoelectron spectroscopy (XPS). Gas sensing properties of In2O3/SnO2 composite hetero-nanofibers were measured with six kinds of indoor volatile organic gases in concentration range of 0.5~50 ppm at the operating temperature of 275 °C. The In2O3/SnO2 composite hetero-nanofibers sensor exhibited good formaldehyde sensing properties, which would be attributed to the formation of n-n homotype heterojunction in the In2O3/SnO2 composite hetero-nanofibers. Finally, the sensing mechanism of the In2O3/SnO2 composite hetero-nanofibers was analyzed based on the energy-band principle. PMID:28792433

Assessing the impacts of current and future concentrations of surface ozone on crop yield with meta-analysis

NASA Astrophysics Data System (ADS)

Feng, Zhaozhong; Kobayashi, Kazuhiko

Meta-analysis was conducted to quantitatively assess the effects of rising ozone concentrations ([O 3]) on yield and yield components of major food crops: potato, barley, wheat, rice, bean and soybean in 406 experimental observations. Yield loss of the crops under current and future [O 3] was expressed relative to the yield under base [O 3] (≤26 ppb). With potato, current [O 3] (31-50 ppb) reduced the yield by 5.3%, and it reduced the yield of barley, wheat and rice by 8.9%, 9.7% and 17.5%, respectively. In bean and soybean, the yield losses were 19.0% and 7.7%, respectively. Compared with yield loss at current [O 3], future [O 3] (51-75 ppb) drove a further 10% loss in yield of soybean, wheat and rice, and 20% loss in bean. Mass of individual grain, seed, or tuber was often the major cause of the yield loss at current and future [O 3], whereas other yield components also contributed to the yield loss in some cases. No significant difference was found between the responses in crops grown in pots and those in the ground for any yield parameters. The ameliorating effect of elevated [CO 2] was significant in the yields of wheat and potato, and the individual grain weight in wheat exposed to future [O 3]. These findings confirm the rising [O 3] as a threat to food security for the growing global population in this century.

Oxidative coupling of methane over supported La{sub 2}O{sub 3} and La-promoted MgO catalysts: Influence of catalyst-support interactions

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

Choudhary, V.R.; Mulla, S.A.R.; Uphade, B.S.

1997-06-01

Methane-to-C{sub 2}-hydrocarbon conversion activity and selectivity (or yield) of MgO and La-promoted MgO catalysts in the oxidative coupling of methane and strong basicity of the catalysts are decreased appreciably when these catalysts are deposited on commonly used commercial low surface area porous catalyst carriers containing Al{sub 2}O{sub 3}, SiO{sub 2}, SiC, or ZrO{sub 2} + HfO{sub 2} as the main components. The decrease in the strong basicity and catalytic activity/selectivity or yield is mostly due to strong chemical interactions between the active catalyst component (viz., MgO and La{sub 2}O{sub 3}) and the reactive components of the catalyst support (viz., Al{submore » 2}O{sub 3} and SiO{sub 2}), resulting in the formation of catalytically inactive binary metal oxides on the support surface. However, the influence of support on the activity/selectivity of La{sub 2}O{sub 3} is relatively very small, and also the chemical interactions of La{sub 2}O{sub 3} with the supports (except that containing a high concentration of SiO{sub 2}) are almost absent. The catalyst-support interactions are thus found to be strongly dependent upon the nature (chemical composition) of both catalyst and support. For developing better supported catalysts for the oxidative coupling of methane, supported La{sub 2}O{sub 3} with some promoters shows high promise.« less

Synthesis and enhanced acetone gas-sensing performance of ZnSnO3/SnO2 hollow urchin nanostructures

NASA Astrophysics Data System (ADS)

Lian, Dandan; Shi, Bing; Dai, Rongrong; Jia, Xiaohua; Wu, Xiangyang

2017-12-01

A kind of novel ZnSnO3/SnO2 hollow urchin nanostructure was synthesized by a facile, eco-friendly two-step liquid-phase process. The structure, morphology, and composition of samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption techniques. The results revealed that many tiny needle-like SnO2 nanowires with the average diameter of 5 nm uniformly grew on the surface of the ZnSnO3 hollow microspheres and the ZnSnO3/SnO2 hollow urchin nanostructures with different SnO2 content also were successfully prepared. In order to comprehend the evolution process of the ZnSnO3/SnO2 hollow urchin nanostructures, the possible growth mechanism of samples was illustrated via several experiments in different reaction conditions. Moreover, the gas-sensing performance of as-prepared samples was investigated. The results showed that ZnSnO3/SnO2 hollow urchin nanostructures with high response to various concentration levels of acetone enhanced selectivity, satisfying repeatability, and good long-term stability for acetone detection. Specially, the 10 wt% ZnSnO3/SnO2 hollow urchin nanostructure exhibited the best gas sensitivity (17.03 for 50 ppm acetone) may be a reliable biomarker for the diabetes patients, which could be ascribed to its large specific surface area, complete pore permeability, and increase of chemisorbed oxygen due to the doping of SnO2.

Sorption of chromium with struvite during phosphorus recovery.

PubMed

Rouff, Ashaki A

2012-11-20

Struvite (MgNH(4)PO(4)·6H(2)O; MAP) precipitation is a viable means of phosphorus (P) recovery from animal and human wastes. The behavior of metal contaminants such as chromium (Cr) during struvite precipitation, however, requires consideration. Here the influence of both Cr concentration and oxidation state on sorption is assessed. The Cr content of struvite precipitated in the presence of 1-100 μM Cr as Cr(III) (22.3-3030.1 mg/kg) was higher than that of solids from Cr(VI) (4.5-5.1 mg/kg) solutions. For 1-20 μM Cr(III) solids, scanning electron microscopy (SEM) revealed etch pit formation on struvite crystal surfaces, indicative of a surface interaction. The formation of an adsorbate was confirmed by X-ray absorption fine structure spectroscopy (XAFS). At initial concentrations ≥20 μM Cr(III), XAFS confirmed the formation of a Cr(OH)(3)·nH(2)O(am) precipitate. Fourier transform infrared (FT-IR) spectroscopy revealed that both Cr(III) and Cr(VI) sorption resulted in distortion of the PO(4)(3-) tetrahedra in the mineral structure. This, combined with SEM results revealed that even at low sorbed concentrations, the Cr impurity can affect the mineral surface and structure. Thus, the initial Cr concentration and oxidation state in wastes targeted for P recovery will dictate the final Cr content, the mechanism of sorption, and impact on the struvite structure.

Melamine-based dendrimer amine-modified magnetic nanoparticles as an efficient Pb(II) adsorbent for wastewater treatment: Adsorption optimization by response surface methodology.

PubMed

Jiryaei Sharahi, Fatemeh; Shahbazi, Afsaneh

2017-12-01

Magnetic Fe 3 O 4 nanoparticles with an average diameter of 64 nm was synthesized solvothermically and subsequently modified with melamine-based dendrimer amine (MDA-Fe 3 O 4 ) via grafting method. The synthesized materials were characterized using DLS, SEM, XRD, FTIR, VSM, TGA and elemental analysis techniques. The MDA-Fe 3 O 4 was employed for the efficient removal of Pb(II) ions from an aqueous solution. The adsorption efficiency was investigated in relation to the independent variables of Pb(II) concentration (80-250 mg L -1 ), pH of the solution (3-7), adsorbent dosage (0.1-0.5 g L -1 ) and temperature (10-40 °C) via a central composite design (CCD) using response surface methodology (RSM). The significance of independent variables and their interactions was tested using ANOVA at a 95% confidence limit (α = 0.05). A second-order quadratic model was established to predict the adsorption efficiency. Under the optimum condition (initial Pb(II) concentration = 110 mg L -1 , MDA-Fe 3 O 4 dosage = 0.49 g L -1 , pH = 5 and temperature = 30 °C) a removal percentage of 85.6% was obtained. The isotherm data fitted well to the Freundlich model within the concentration range of the experimental study. A maximum adsorption capacity of 333.3 mg g -1 was predicted by the Langmuir model. The adsorption rate of Pb(II) ions onto MDA-Fe 3 O 4 was in good agreement with the pseudo-second-order model (R 2  = 0.999; k 2  = 4.7 × 10 -4  g mg -1 min -1 ). Thermodynamically, adsorption was spontaneous and endothermic. The MDA-Fe 3 O 4 was successfully regenerated using 0.3 M HCl with little loss of adsorption capacity (≈7%) for five successive adsorption cycles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of copper oxide concentration on the formation and persistency of environmentally persistent free radicals (EPFRs) in particulates.

PubMed

Kiruri, Lucy W; Khachatryan, Lavrent; Dellinger, Barry; Lomnicki, Slawo

2014-02-18

Environmentally persistent free radicals (EPFRs) are formed by the chemisorption of substituted aromatics on metal oxide surfaces in both combustion sources and superfund sites. The current study reports the dependency of EPFR yields and their persistency on metal loading in particles (0.25, 0.5, 0.75, 1, 2, and 5% CuO/silica). The EPFRs were generated through exposure of particles to three adsorbate vapors at 230 °C: phenol, 2-monochlorophenol (2-MCP), and dichlorobenzene (DCBz). Adsorption resulted in the formation of surface-bound phenoxyl- and semiquinoine-type radicals with characteristic EPR spectra displaying a g value ranging from ∼ 2.0037 to 2.006. The highest EPFR yield was observed for CuO concentrations between 1 and 3% in relation to MCP and phenol adsorption. However, radical density, which is expressed as the number of radicals per copper atom, was highest at 0.75-1% CuO loading. For 1,2-dichlorobenzene adsorption, radical concentration increased linearly with decreasing copper content. At the same time, a qualitative change in the radicals formed was observed--from semiquinone to chlorophenoxyl radicals. The two longest lifetimes, 25 and 23 h, were observed for phenoxyl-type radicals on 0.5% CuO and chlorophenoxyl-type radicals on 0.75% CuO, respectively.

Consequences of plasma oxidation and vacuum annealing on the chemical properties and electron accumulation of In2O3 surfaces

NASA Astrophysics Data System (ADS)

Berthold, Theresa; Rombach, Julius; Stauden, Thomas; Polyakov, Vladimir; Cimalla, Volker; Krischok, Stefan; Bierwagen, Oliver; Himmerlich, Marcel

2016-12-01

The influence of oxygen plasma treatments on the surface chemistry and electronic properties of unintentionally doped and Mg-doped In2O3(111) films grown by plasma-assisted molecular beam epitaxy or metal-organic chemical vapor deposition is studied by photoelectron spectroscopy. We evaluate the impact of semiconductor processing technology relevant treatments by an inductively coupled oxygen plasma on the electronic surface properties. In order to determine the underlying reaction processes and chemical changes during film surface-oxygen plasma interaction and to identify reasons for the induced electron depletion, in situ characterization was performed implementing a dielectric barrier discharge oxygen plasma as well as vacuum annealing. The strong depletion of the initial surface electron accumulation layer is identified to be caused by adsorption of reactive oxygen species, which induce an electron transfer from the semiconductor to localized adsorbate states. The chemical modification is found to be restricted to the topmost surface and adsorbate layers. The change in band bending mainly depends on the amount of attached oxygen adatoms and the film bulk electron concentration as confirmed by calculations of the influence of surface state density on the electron concentration and band edge profile using coupled Schrödinger-Poisson calculations. During plasma oxidation, hydrocarbon surface impurities are effectively removed and surface defect states, attributed to oxygen vacancies, vanish. The recurring surface electron accumulation after subsequent vacuum annealing can be consequently explained by surface oxygen vacancies.

Modification of polystyrene-based activated carbon spheres to improve adsorption of dibenzothiophene

NASA Astrophysics Data System (ADS)

Wang, Qin; Liang, Xiaoyi; Qiao, Wenming; Liu, Chaojun; Liu, Xiaojun; Zhang, Rui; Ling, Licheng

2009-01-01

Polystyrene-based activated carbon spheres (PACS) were modified with either air, HNO 3, (NH 4) 2S 2O 8, H 2O 2 or H 2 to improve their adsorption properties of dibenzothiophene (DBT). The texture and surface chemistry of PACS were characterized by N 2 adsorption, scanning electron microscopy (SEM), temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), acid-base titration and elemental analysis. The results showed that HNO 3 and (NH 4) 2S 2O 8 treatments introduced large amount of acidic groups such as carboxylic, lactones and anhydride groups, while air and H 2O 2 had relatively mild effects and introduced a small quantity of phenol, carbonyl and ether groups. In the HNO 3 treatment, the acidic groups might be fixed on the internal and external surface of PACS, which may act as active sites of adsorption, resulting in increase of the adsorption amount by 45%. Whereas H 2O 2 and (NH 4) 2S 2O 8 treatments might fix more oxygen-containing groups on the external surface, which may hinder DBT molecule enter into micropores, leading to rather lower adsorption capacity with the extent of oxidation. So, the concentration, distribution and types of the acidic functional groups are responsible for the removal of DBT.

Effect of Er{sup 3+} ions on the phase formation and properties of In{sub 2}O{sub 3}nanostructures crystallized upon microwave heating

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

Lemos, Samantha C.S.; Romeiro, Fernanda C.; Paula, Leonardo F. de

Regular sized nanostructures of indium oxide (In{sub 2}O{sub 3}) were homogeneously grown using a facile route, i.e. a microwave-hydrothermal method combined with rapid thermal treatment in a microwave oven. The presence of Er{sup 3+} doping plays an important role in controlling the formation of cubic (bcc) and rhombohedral (rh) In{sub 2}O{sub 3} phases. The samples presented broad photoluminescent emission bands in the green-orange region, which were attributed to the recombination of electrons at oxygen vacancies. The photocatalytic activities of pure bcc-In{sub 2}O{sub 3} and a bcc-rh-In{sub 2}O{sub 3} mixture towards the UVA degradation of methylene blue (MB) were also evaluated.more » The results showed that Er{sup +3} doped In{sub 2}O{sub 3} exhibited the highest photocatalytic activity with a photonic efficiency three times higher than the pure oxide. The improved performance was attributed to the higher surface area, the greater concentration of electron traps due the presence of the dopant and the possible formation of heterojunctions between the cubic and rhombohedral phases. - Graphical abstract: Photodegradation curves as a function of irradiation time of the samples obtained upon rapid microwave heating. - Highlights: • Efficient and rapid microwave heating to obtain Er{sup 3+} doped In{sub 2}O{sub 3} nanostructures. • Er{sup 3+} ions doping is fundamental to stabilizing the crystalline rhombohedral phase. • Symmetry breaking induced by vacancies in the lattice leads to photoluminescence. • Surface area of doped sample was two times higher than the surface of pure oxide. • The presence of defects in the lattice structure favors photocatalytic activity.« less

Identification of chemical fingerprints in long-range transport of burning induced upper tropospheric ozone from Colorado to the North Atlantic Ocean.

PubMed

Jeon, Wonbae; Choi, Yunsoo; Souri, Amir Hossein; Roy, Anirban; Diao, Lijun; Pan, Shuai; Lee, Hwa Woon; Lee, Soon-Hwan

2018-02-01

This study investigates a significant biomass burning (BB) event occurred in Colorado of the United States in 2012 using the Community Multi-scale Air Quality (CMAQ) model. The simulation reasonably reproduced the significantly high upper tropospheric O 3 concentrations (up to 145ppb) caused by BB emissions. We find the BB-induced O 3 was primarily affected by chemical reactions and dispersion during its transport. In the early period of transport, high NO x and VOCs emissions caused O 3 production due to reactions with the peroxide and hydroxyl radicals, HO 2 and OH. Here, NO x played a key role in O 3 formation in the BB plume. The results indicated that HO 2 in the BB plume primarily came from formaldehyde (HCHO+hv=2HO 2 +CO), a secondary alkoxy radical (ROR=HO 2 ). CO played an important role in the production of recycled HO 2 (OH+CO=HO 2 ) because of its abundance in the BB plume. The chemically produced HO 2 was largely converted to OH by the reactions with NO (HO 2 +NO=OH+NO 2 ) from BB emissions. This is in contrast to the surface, where HO 2 and OH are strongly affected by VOC and HONO, respectively. In the late stages of transport, the O 3 concentration was primarily controlled by dispersion. It stayed longer in the upper troposphere compared to the surface due to sustained depletion of NO x . Sensitivity analysis results support that O 3 in the BB plume is significantly more sensitive to NO x than VOCs. Copyright © 2017 Elsevier B.V. All rights reserved.

Combined impacts of nitrous acid and nitryl chloride on lower-tropospheric ozone: new module development in WRF-Chem and application to China

NASA Astrophysics Data System (ADS)

Zhang, Li; Li, Qinyi; Wang, Tao; Ahmadov, Ravan; Zhang, Qiang; Li, Meng; Lv, Mengyao

2017-08-01

Nitrous acid (HONO) and nitryl chloride (ClNO2) - through their photolysis - can have profound effects on the nitrogen cycle and oxidation capacity of the lower troposphere. Previous numerical studies have separately considered and investigated the sources/processes of these compounds and their roles in the fate of reactive nitrogen and the production of ozone (O3), but their combined impact on the chemistry of the lower part of the troposphere has not been addressed yet. In this study, we updated the WRF-Chem model with the currently known sources and chemistry of HONO and chlorine in a new chemical mechanism (CBMZ_ReNOM), and applied it to a study of the combined effects of HONO and ClNO2 on summertime O3 in the boundary layer over China. We simulated the spatial distributions of HONO, ClNO2, and related compounds at the surface and within the lower troposphere. The results showed that the modeled HONO levels reached up to 800-1800 ppt at the surface (0-30 m) over the North China Plain (NCP), the Yangtze River Delta (YRD), and the Pearl River Delta (PRD) regions and that HONO was concentrated within a 0-200 m layer. In comparison, the simulated surface ClNO2 mixing ratio was around 800-1500 ppt over the NCP, YRD, and central China regions and was predominantly present in a 0-600 m layer. HONO enhanced daytime ROx (OH + HO2 + RO2) and O3 at the surface (0-30 m) by 2.8-4.6 ppt (28-37 %) and 2.9-6.2 ppb (6-13 %), respectively, over the three most developed regions, whereas ClNO2 increased surface O3 in the NCP and YRD regions by 2.4-3.3 ppb (or 5-6 %) and it also had a significant impact (3-6 %) on above-surface O3 within 200-500 m. The combined effects increased surface O3 by 11.5, 13.5, and 13.3 % in the NCP, YRD, and PRD regions, respectively. Over the boundary layer (0-1000 m), the HONO and ClNO2 enhanced O3 by up to 5.1 and 3.2 %, respectively, and their combined effect increased O3 by 7.1-8.9 % in the three regions. The new module noticeably improved O3 predictions at ˜ 900 monitoring stations throughout China by reducing the mean bias from -4.3 to 0.1 ppb. Our study suggests the importance of considering these reactive nitrogen species simultaneously into chemical transport models to better simulate the formation of summertime O3 in polluted regions.

Influence of Y doping concentration on the properties of nanostructured MxZn1-xO (M=Y) thin film deposited by nebulizer spray pyrolysis technique

NASA Astrophysics Data System (ADS)

Mariappan, R.; Ponnuswamy, V.; Chandra Bose, A.; Suresh, R.; Ragavendar, M.

2014-09-01

Yttrium doped Zinc Oxide (YxZn1-xO) thin films deposited at a substrate temperature 400 °C. The effect of substrate temperature on the structural, surface morphology, compositional, optical and electrical properties of YxZn1-xO thin films was studied. X-ray diffraction studies show that all films are polycrystalline in nature with hexagonal crystal structure having highly textured (002) plane parallel to the surface of the substrate. The structural parameters, such as lattice constants (a and c), crystallite size (D), dislocation density (δ), microstrain (σ) and texture coefficient were calculated for different yttrium doping concentrations (x). High resolution scanning electron microscopy measurements reveal that the surface morphology of the films change from platelet like grains to hexagonal structure with grain size increase due to the yttrium doping. Energy dispersive spectroscopy confirms the presence of Y, Zn and O elements in the films prepared. Optical studies showed that all samples have a strong optical transmittance higher than 70% in the visible range. A slight shift of the absorption edge towards the large wavelengths was observed as the Y doping concentration increased. This result shows that the band gap is slightly decreased from 3.10 to 2.05 eV with increase of the yttrium doping concentrations (up to 7.5%) and then slightly increased. Room temperature PL measurements were done and the band-to-band emission energies of films were determined and reported. The complex impedance of the 10%Y doped ZnO film shows two distinguished semicircles and the diameter of the arcs got decreased in diameter as the temperature increases from 70 to 175 °C.

In Situ Fabrication of 3D Ag@ZnO Nanostructures for Microfluidic Surface-Enhanced Raman Scattering Systems

PubMed Central

2015-01-01

In this work, we develop an in situ method to grow highly controllable, sensitive, three-dimensional (3D) surface-enhanced Raman scattering (SERS) substrates via an optothermal effect within microfluidic devices. Implementing this approach, we fabricate SERS substrates composed of Ag@ZnO structures at prescribed locations inside microfluidic channels, sites within which current fabrication of SERS structures has been arduous. Conveniently, properties of the 3D Ag@ZnO nanostructures such as length, packing density, and coverage can also be adjusted by tuning laser irradiation parameters. After exploring the fabrication of the 3D nanostructures, we demonstrate a SERS enhancement factor of up to ∼2 × 106 and investigate the optical properties of the 3D Ag@ZnO structures through finite-difference time-domain simulations. To illustrate the potential value of our technique, low concentrations of biomolecules in the liquid state are detected. Moreover, an integrated cell-trapping function of the 3D Ag@ZnO structures records the surface chemical fingerprint of a living cell. Overall, our optothermal-effect-based fabrication technique offers an effective combination of microfluidics with SERS, resolving problems associated with the fabrication of SERS substrates in microfluidic channels. With its advantages in functionality, simplicity, and sensitivity, the microfluidic-SERS platform presented should be valuable in many biological, biochemical, and biomedical applications. PMID:25402207

Sediment toxicity and bioaccumulation of nano and micron-sized aluminum oxide.

PubMed

Stanley, Jacob K; Coleman, Jessica G; Weiss, Charles A; Steevens, Jeffery A

2010-02-01

Nano-aluminum oxide (Al(2)O(3)) is used commercially in coatings and abrasives. Nano-Al(2)O(3) can also be generated through the oxidation of nano-aluminum in military propellants and energetics. The purpose of the present study was to assess toxicity and bioaccumulation of nano-Al(2)O(3) to a variety of sediment organisms (Tubifex tubifex, Hyalella azteca, Lumbriculus variegatus, and Corbicula fluminea). The bioaccumulation and toxicity of nano-Al(2)O(3) was compared with that of micron-sized Al(2)O(3) to investigate potential size-related effects. Results of the present study show species-specific differences in relative bioaccumulation of nano and micron-sized Al(2)O(3). Significant toxic effects (survival and growth) were observed in H. azteca testing, but only at high concentrations unlikely to be found in the environment. Nano-Al(2)O(3) was found to be more toxic than micron-sized Al(2)O(3) to H. azteca survival in a 14-d study in which organisms were in direct contact with a thin layer of 625 or 2,500 mg of Al(2)O(3) dispersed on the surface of either sediment or sand. A significant growth effect was also observed for nano but not micron-sized Al(2)O(3) at the highest treatment level tested (100 g/kg Al(2)O(3)) in a 10-d H. azteca bioassay in which Al(2)O(3) was homogenized with sediment. However, differences in measured sediment Al concentrations (micron-sized = 55.1 [+/-0.6] g/kg Al; nano-sized = 66.2 [+/-0.6] g/kg Al) in the nano and micron-sized Al(2)O(3) preclude direct comparison of the toxicity of these two treatments based on particle size. Copyright 2009 SETAC.

Surface tension of evaporating nanofluid droplets

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

Chen, Ruey-Hung; Phuoc, Tran X.; Martello, Donald

2011-05-01

Measurements of nanofluid surface tension were made using the pendant droplet method. Three different types of nanoparticles were used - laponite, silver and Fe 2O 3 - with de-ionized water (DW) as the base fluid. The reported results focus on the following categories; (1) because some nanoparticles require surfactants to form stable colloids, the individual effects of the surfactant and the particles were investigated; (2) due to evaporation of the pendant droplet, the particle concentration increases, affecting the apparent surface tension; (3) because of the evaporation process, a hysteresis was found where the evaporating droplet can only achieve lower valuesmore » of surface tension than that of nanofluids at the same prepared concentrations: and (4) the Stefan equation relating the apparent surface tension and heat of evaporation was found to be inapplicable for nanofluids investigated. Comparisons with findings for sessile droplets are also discussed, pointing to additional effects of nanoparticles other than the non-equilibrium evaporation process.« less

Cr2O3-modified ZnO thick film resistors as LPG sensors.

PubMed

Patil, D R; Patil, L A

2009-02-15

Thick films of pure ZnO were obtained by screen-printing technique. Surface functionalized ZnO thick films by Cr(2)O(3) were obtained by dipping pure ZnO thick films into 0.01M aqueous solution of chromium trioxide (CrO(3)). The dipped films were fired at 500 degrees C for 30 min. Upon firing, the CrO(3) would reduce to Cr(2)O(3). Cr(2)O(3)-activated (0.47 mass%) ZnO thick films resulted in LPG sensor. Upon exposure to 100 ppm LPG, the barrier height between Cr(2)O(3) and ZnO grains decreases markedly, leading to a drastic decrease in resistance. The sensor was found to sense LPG at 350 degrees C and no cross sensitivity was observed to other hazardous, polluting and inflammable gases. The quick response ( approximately 18s) and fast recovery ( approximately 42s) are the main features of this sensor. The effects of microstructures and dopant concentrations on the gas sensing performance of the sensor were studied and discussed.

Dynamic investigation of the role of the surface sulfates in NO{sub x} reduction and SO{sub 2} oxidation over V{sub 2}O{sub 5}-WO{sub 3}/TiO{sub 2} catalysts

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

Orsenigo, C.; Lietti, L.; Tronconi, E.

1998-06-01

Transient experiments performed over synthesized and commercial V{sub 2}O{sub 5}-WO{sub 3}/TiO{sub 2} catalysts during catalyst conditioning and during step changes of the operating variables (SO{sub 2} inlet concentration and temperature) show that conditioning of the catalyst is required to attain significant and reproducible steady-state data in both the reduction of NO{sub x} and the oxidation of SO{sub 2}. The response time of conditioning for NO{sub x} reduction is of a few hours and that for SO{sub 2} oxidation is of several hours. Fourier transform infrared spectroscopy temperature programmed decomposition, and thermogravimetric measurements showed that catalyst conditioning is associated with amore » slow process of buildup of sulfates: the different characteristic conditioning times observed in the reduction of NO{sub x} and in the oxidation of SO{sub 2} suggest that the buildup of sulfates occurs first at the vanadyl sites and later on at the exposed titania surface. Formation of sulfates at or near the vanadyl sites increases the reactivity in the de-NO{sub x} reaction, possibly due to the increase in the Broensted and Lewis acidity of the catalyst, whereas the titania surface acts as SO{sub 3} acceptor and affects the outlet SO{sub 3} concentration during catalyst conditioning for the SO{sub 2} oxidation reaction. The response time to step changes in SO{sub 2} concentration and temperature is of a few hours in the case of SO{sub 2} oxidation and much shorter in the case of NO{sub x} reduction. The different time responses associated with conditioning and with step changes in the settings of the operating variables have been rationalized in terms of the different extent of perturbation of the sulfate coverage experienced by the catalyst.« less

Inactivation and UV Disinfection of Murine Norovirus with TiO2 under Various Environmental Conditions▿

PubMed Central

Lee, JungEun; Zoh, KyungDuk; Ko, GwangPyo

2008-01-01

We studied inactivation and UV disinfection of murine norovirus (MNV) as a surrogate for human norovirus. We investigated the effects of different surface characteristics, temperatures, and NaCl concentrations on MNV survival using both a plaque assay and a real-time TaqMan reverse transcription (RT)-PCR assay. MNV survived more than 40 days on diaper material, on gauze, and in a stool suspension. Compared to inactivation at lower temperatures (−20 and 4°C), inactivation of MNV was greater at higher temperatures (18 and 30°C). On the surface of both gauze and diaper material, there was a <2-log10 reduction in the amount of infectious MNV in 40 days after incubation at both −20 and 4°C, compared to a >5-log10 reduction after incubation at 30°C in 24 days. MNV survived better in a stool suspension than on the surface of gauze or diaper material. A higher salt concentration increased the rate of inactivation of MNV. In 72 h, <0.3-, 1.5-, and 2.5-log10 reductions in the amount of infectious MNV occurred in distilled water and 0.5 and 1 M NaCl, respectively. We observed only minor reductions in the numbers of viral RNA copies as quantified by real-time TaqMan RT-PCR regardless of the temperature, the salt concentration, or the suspending medium. We also evaluated UV disinfection of infectious MNV with and without TiO2. The amount of MNV was significantly reduced by 254-nm UV with and without TiO2. When 25 mJ/cm2 UV was used, 3.3- and 3.6-log10 reductions in the amounts of infectious MNV occurred with and without TiO2, respectively. Our results demonstrate that MNV can persist in various environmental conditions and can be efficiently controlled by UV disinfection. PMID:18245239

Impacts of ultramafic outcrops in Peninsular Malaysia and Sabah on soil and water quality.

PubMed

Tashakor, Mahsa; Modabberi, Soroush; van der Ent, Antony; Echevarria, Guillaume

2018-05-08

This study focused on the influence of ultramafic terrains on soil and surface water environmental chemistry in Peninsular Malaysia and in the State of Sabah also in Malaysia. The sampling included 27 soils from four isolated outcrops at Cheroh, Bentong, Bukit Rokan, and Petasih from Peninsular Malaysia and sites near Ranau in Sabah. Water samples were also collected from rivers and subsurface waters interacting with the ultramafic bodies in these study sites. Physico-chemical parameters (including pH, EC, CEC) as well as the concentration of major and trace elements were measured in these soils and waters. Geochemical indices (geoaccumulation index, enrichment factor, and concentration factor) were calculated. Al 2 O 3 and Fe 2 O 3 had relatively high concentrations in the samples. A depletion in MgO, CaO, and Na 2 O was observed as a result of leaching in tropical climate, and in relation to weathering and pedogenesis processes. Chromium, Ni, and Co were enriched and confirmed by the significant values obtained for Igeo, EF, and CF, which correspond to the extreme levels of contamination for Cr and high to moderate levels of contamination for Ni and Co. The concentrations of Cr, Ni, and Co in surface waters did not reflect the local geochemistry and were within the permissible ranges according to WHO and INWQS standards. Subsurface waters were strongly enriched by these elements and exceeded these standards. The association between Cr and Ni was confirmed by factor analysis. The unexpected enrichment of Cu in an isolated component can be explained by localized mineralization in Sabah.

Comparison and mechanism of photocatalytic activities of N-ZnO and N-ZrO2 for the degradation of rhodamine 6G.

PubMed

Sudrajat, Hanggara; Babel, Sandhya

2016-05-01

N-doped ZnO (N-ZnO) and N-doped ZrO2 (N-ZrO2) are synthesized by novel, simple thermal decomposition methods. The catalysts are evaluated for the degradation of rhodamine 6G (R6G) under visible and UV light. N-ZnO exhibits higher dye degradation under both visible and UV light compared to N-ZrO2 due to possessing higher specific surface area, lower crystalline size, and lower band gap. However, it is less reusable than N-ZrO2 and its photocatalytic activity is also deteriorated at low pH. At the same intensity of 3.5 W/m(2), UVC light is shown to be a better UV source for N-ZnO, while UVA light is more suitable for N-ZrO2. At pH 7 with initial dye concentration of 10 mg/L, catalyst concentration of 1 g/L, and UVC light, 94.3 % of R6G is degraded by N-ZnO within 2 h. Using UVA light under identical experimental conditions, 93.5 % degradation of R6G is obtained by N-ZrO2. Moreover, the type of light source is found to determine the reactive species produced in the R6G degradation by N-ZnO and N-ZrO2. Less oxidative reactive species such as superoxide radical and singlet oxygen play a major role in the degradation of R6G under visible light. On the contrary, highly oxidative hydroxyl radicals are predominant under UVC light. Based on the kinetic study, the adsorption of R6G on the catalyst surface is found to be the controlling step.

Reduction Mechanisms of Cu2+-Doped Na2O-Al2O3-SiO2 Glasses during Heating in H2 Gas.

PubMed

Nogami, Masayuki; Quang, Vu Xuan; Ohki, Shinobu; Deguchi, Kenzo; Shimizu, Tadashi

2018-01-25

Controlling valence state of metal ions that are doped in materials has been widely applied for turning optical properties. Even though hydrogen has been proven effective to reduce metal ions because of its strong reducing capability, few comprehensive studies focus on practical applications because of the low diffusion rate of hydrogen in solids and the limited reaction near sample surfaces. Here, we investigated the reactions of hydrogen with Cu 2+ -doped Na 2 O-Al 2 O 3 -SiO 2 glass and found that a completely different reduction from results reported so far occurs, which is dominated by the Al/Na concentration ratio. For Al/Na < 1, Cu 2+ ions were reduced via hydrogen to metallic Cu, distributing in glass body. For Al/Na > 1, on the other hand, the reduction of Cu 2+ ions occurred simultaneously with the formation of OH bonds, whereas the reduced Cu metal moved outward and formed a metallic film on glass surface. The NMR and Fourier transform infrared results indicated that the Cu 2+ ions were surrounded by Al 3+ ions that formed AlO 4 , distorted AlO 4 , and AlO 5 units. The diffused H 2 gas reacted with the Al-O - ···Cu + units, forming Al-OH and metallic Cu, the latter of which moved freely toward glass surface and in return enhanced H 2 diffusion.

Influence of B doping on the carrier transport mechanism and barrier height of graphene/ZnO Schottky contact

NASA Astrophysics Data System (ADS)

Li, Yapeng; Li, Yingfeng; Zhang, Jianhua; Tong, Ting; Ye, Wei

2018-03-01

The ZnO films were fabricated on the surface of n-Si(1 1 1) substrate using the sol-gel method, and the graphene was then transferred to its surface for the fabrication of the graphene/ZnO Schottky contact. The results showed that ZnO films presented a strong (0 0 2) preferred direction, and that the particle sizes on the surface decreased as the doping concentration of B ions increased. The electrical properties of the graphene/ZnO Schottky contact were measured by using current-voltage measurements. It was found that the graphene/ZnO Schottky contact showed a fine rectification behavior when the doping concentration of B ions was increased. However, when the doping concentration of the B ions increased to 0.15 mol l-1, the leakage current increased and rectification behavior weakened. This was due to the Fermi level pinning caused by the presence of the O vacancy at the interface of the graphene/ZnO Schottky contact.

The characterization, mobility, and persistence of roaster-derived arsenic in soils at Giant Mine, NWT

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

Bromstad, Mackenzie J.; Wrye, Lori A.; Jamieson, Heather E.

Approximately 20,000 tonnes of arsenic (As)-bearing emissions from roasting gold (Au)-bearing arsenopyrite ore were aerially released from 1949 to 1999 at Giant Mine, near Yellowknife, Canada. Soil samples collected within 4 km of the former roaster from sites undisturbed by mining or other human activity contain up to 7700 mg/kg total As. Total As concentrations are highest within a few cm of the surface, and particularly enriched in soil pockets on rock outcrops. Scanning electron microscopy and synchrotron microanalysis show that roaster-derived arsenic trioxide (As2O3) has persisted in shallow soils in the area. Roaster-generated maghemite and hematite are also present.more » These anthropogenic forms of As are much more common in near-surface soils than natural As-bearing minerals. Comparison of the proportions of As, Sb, and Au concentrations in outcrop soil samples and historic As2O3-rich dust captured by emission controls suggest most of the roaster-derived As in soils at Giant was likely deposited before 1964. Topographic restriction by rock outcrops and a dry, cold climate likely contribute to the persistence of As2O3 in outcrop soils.« less

Effect of AlCl3 concentration on nanoparticle removal by coagulation.

PubMed

Zhang, Lizhu; Mao, Jingchun; Zhao, Qing; He, Shaobo; Ma, Jun

2015-12-01

In recent years, engineered nanoparticles, as a new group of contaminants emerging in natural water, have been given more attention. In order to understand the behavior of nanoparticles in the conventional water treatment process, three kinds of nanoparticle suspensions, namely multi-walled carbon nanotube-humic acid (MWCNT-HA), multi-walled carbon nanotube-N,N-dimethylformamide (MWCNT-DMF) and nanoTiO2-humic acid (TiO2-HA) were employed to investigate their coagulation removal efficiencies with varying aluminum chloride (AlCl3) concentrations. Results showed that nanoparticle removal rate curves had a reverse "U" shape with increasing concentration of aluminum ion (Al(3+)). More than 90% of nanoparticles could be effectively removed by an appropriate Al(3+) concentration. At higher Al(3+) concentration, nanoparticles would be restabilized. The hydrodynamic particle size of nanoparticles was found to be the crucial factor influencing the effective concentration range (ECR) of Al(3+) for nanoparticle removal. The ECR of Al(3+) followed the order MWCNT-DMF>MWCNT-HA>TiO2-HA, which is the reverse of the nanoparticle size trend. At a given concentration, smaller nanoparticles carry more surface charges, and thus consume more coagulants for neutralization. Therefore, over-saturation occurred at relatively higher Al(3+) concentration and a wider ECR was obtained. The ECR became broader with increasing pH because of the smaller hydrodynamic particle size of nanoparticles at higher pH values. A high ionic strength of NaCl can also widen the ECR due to its strong potential to compress the electric double layer. It was concluded that it is important to adjust the dose of Al(3+) in the ECR for nanoparticle removal in water treatment. Copyright © 2015. Published by Elsevier B.V.

The effect of oxygen vacancies on the binding interactions of NH3 with rutile TiO2(110) -1×1

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

Kim, Boseong; Li, Zhenjun; Kay, Bruce D.

2012-11-21

A series of NH3 temperature-programmed desorption (TPD) spectra was taken after the NH3 dose at 70 K on rutile TiO2(110)-1×1 surfaces with the oxygen vacancy (VO) concentrations of ~0% (p-TiO2) and 5% (r-TiO2), respectively, to study the effect of VO’s on the desorption energy of NH3 as a function of the coverage, θ. Our results show that at zero coverage limit, the desorption energy of NH3 on r-TiO2 is 115 kJ/mol, which is 10 kJ/mol less than that on p-TiO2. The desorption energy from the Ti4+ sites decreases with increasing θ due to the repulsive NH3 - NH3 interactions andmore » approaches ~ 55 kJ/mol upon the saturation of Ti4+ sites (θ = 1 monolayer, ML) on both p- and r-TiO2. The absolute saturation coverage is determined to be about 10% smaller on r-TiO2 than that on p-TiO2. Further, the trailing edges of the NH3 TPD spectra on the hydroxylated TiO2(110) (h-TiO2) appear to be the same as that on r-TiO2 while those on oxidized TiO2(110) (o-TiO2) shift to higher temperatures. We present the detailed analysis of the results and reconcile the observed differences based on the repulsive adsorbate-adsorbate interactions between neighboring NH3 molecules and the surface charge associated with the presence of VO’s. Besides NH3, no other reaction products are observed in the TPD spectra.« less

Adsorption mechanisms of selenium oxyanions at the aluminum oxide/water interface

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

Peak, Derek

2008-06-09

Sorption processes at the mineral/water interface typically control the mobility and bioaccessibility of many inorganic contaminants such as oxyanions. Selenium is an important micronutrient for human and animal health, but at elevated concentrations selenium toxicity is a concern. The objective of this study was to determine the bonding mechanisms of selenate (SeO{sub 4}{sup 2-}) and selenite (SeO{sub 3}{sup 2-}) on hydrous aluminum oxide (HAO) over a wide range of reaction pH using extended X-ray absorption fine structure (EXAFS) spectroscopy. Additionally, selenate adsorption on corundum ({alpha}-Al{sub 2}O{sub 3}) was studied to determine if adsorption mechanisms change as the aluminum oxide surfacemore » structure changes. The overall findings were that selenite forms a mixture of outer-sphere and inner-sphere bidentate-binuclear (corner-sharing) surface complexes on HAO, selenate forms primarily outer-sphere surface complexes on HAO, and on corundum selenate forms outer-sphere surface complexes at pH 3.5 but inner-sphere monodentate surface complexes at pH 4.5 and above. It is possible that the lack of inner-sphere complex formation at pH 3.5 is caused by changes in the corundum surface at low pH or secondary precipitate formation. The results are consistent with a structure-based reactivity for metal oxides, wherein hydrous metal oxides form outer-sphere complexes with sulfate and selenate, but inner-sphere monodentate surface complexes are formed between sulfate and selenate and {alpha}-Me{sub 2}O{sub 3}.« less

Robust Hydrophobic Surfaces from Suspension HVOF Thermal Sprayed Rare-Earth Oxide Ceramics Coatings.

PubMed

Bai, M; Kazi, H; Zhang, X; Liu, J; Hussain, T

2018-05-03

This study has presented an efficient coating method, namely suspension high velocity oxy-fuel (SHVOF) thermal spraying, to produce large super-hydrophobic ceramic surfaces with a unique micro- and nano-scale hierarchical structures to mimic natural super-hydrophobic surfaces. CeO 2 was selected as coatings material, one of a group of rare-earth oxide (REO) ceramics that have recently been found to exhibit intrinsic hydrophobicity, even after exposure to high temperatures and abrasive wear. Robust hydrophobic REO ceramic surfaces were obtained from the deposition of thin CeO 2 coatings (3-5 μm) using an aqueous suspension with a solid concentration of 30 wt.% sub-micron CeO 2 particles (50-200 nm) on a selection of metallic substrates. It was found that the coatings' hydrophobicity, microstructure, surface morphology, and deposition efficiency were all determined by the metallic substrates underneath. More importantly, it was demonstrated that the near super-hydrophobicity of SHVOF sprayed CeO 2 coatings was achieved not only by the intrinsic hydrophobicity of REO but also their unique hierarchically structure. In addition, the coatings' surface hydrophobicity was sensitive to the O/Ce ratio, which could explain the 'delayed' hydrophobicity of REO coatings.

Multidimensional Co3O4 nano sponge for the highly sensitive SERS applications

NASA Astrophysics Data System (ADS)

Zhao, Miao-miao; Liu, Wen-yao; Du, Jian-gong; Guo, Xu-dong; Wang, Lei; Xia, Mei-jing; Tang, Jun

2017-01-01

In this work, surface enhanced Raman spectroscopy (SERS) substrates with Ag nanoparticles (NPs) decorated Co3O4 nanowires (NWs) grafted on the three-dimensional (3D) network architecture of Ni foam (denoted as Ag-NP@Co3O4-NW/Ni-foam) arrays are manufactured. In the experiment, the hierarchical Ag-NP@Co3O4-NW/Ni-foam arrays exhibit strong SERS activity due to the higher density of the "hot spots" created from the large quantities of neighboring Ag NPs. Using this hierarchical 3D SERS substrates, the crystal violet (a banned drug of aquaculture) with concentration down to 10-14 mol/L can be detected, which shows potential application in SERS-based rapid trace-level detection of harmful food additives.

Identification and significance of sulphonamides (p-TSA, o-TSA, BSA) in an urban water cycle (Berlin, Germany).

PubMed

Richter, Doreen; Massmann, Gudrun; Dünnbier, Uwe

2008-03-01

Because of the nature of the water cycle in Berlin, a number of persistent wastewater residues are present in the surface water and may potentially reach the groundwater via bank filtration and artificial recharge. The occurrence and behaviour of the wastewater residues para-toluenesulphonamide (p-TSA), ortho-toluenesulphonamide (o-TSA) and benzenesulphonamide (BSA) through wastewater treatment, surface water, bank filtration and drinking water treatment was studied. In addition, groundwater below a former sewage farm was investigated. All three compounds are ubiquitous in the aquatic environment of Berlin. p-TSA concentrations are much higher than those of o-TSA and BSA. p-TSA was found in high concentrations in the wastewater influent (2 to 15microg/L), in the wastewater effluent (<0.15 to 2.34microg/L) and in sewage farm groundwater (<0.05 to 20microg/L) and in lower concentrations in the surface water (<0.05 to 1.15microg/L), bank filtrate (<0.05 to 0.30microg/L) and drinking water (<0.05 to 0.54microg/L). p-TSA is considerably depleted during waste- and drinking water treatment ( approximately 90% reduction each). The concentration ranges for o-TSA and BSA in wastewater influents were 0.11 to 8microg/L and <0.05 to 0.64microg/L, respectively, while the values for wastewater effluents were 0.14 to 4microg/L for o-TSA and 0.25 to 0.49microg/L for BSA. Wastewater treatment and drinking water treatment do not reduce the concentrations of o-TSA and BSA. The behaviour of o-TSA during wastewater treatment varies largely between different wastewater treatment plants where concentrations increase, remain constant or decrease. BSA forms during treatment. The concentrations measured in surface water, sewage farm groundwater, bank filtrate and drinking water were <0.05 to 1.74microg/L for o-TSA and <0.05 to 0.53microg/L for BSA.

Photochemical decoration of magnetic composites with silver nanostructures for determination of creatinine in urine by surface-enhanced Raman spectroscopy.

PubMed

Alula, Melisew Tadele; Yang, Jyisy

2014-12-01

In this study, silver nanostructures decorated magnetic nanoparticles for surface-enhanced Raman scattering (SERS) measurements were prepared via photoreduction utilizing the catalytic activity of ZnO nanostructure. The ZnO/Fe3O4 composite was first prepared by dispersing pre-formed magnetic nanoparticles into alkaline zinc nitrate solutions. After annealing of the precipitates, the formed ZnO/Fe3O4 composites were successfully decorated with silver nanostructures by soaking the composites into silver nitrate/ethylene glycol solution following UV irradiations. To find the optimal condition when preparing Ag@ZnO/Fe3O4 composites for SERS measurements, factors such as the reaction conditions, photoreduction time, concentration of zinc nitrate and silver nitrate were studied. Results indicated that the photoreduction efficiency was significantly improved with the assistance of ZnO but the amount of ZnO in the composite is not critical. The concentration of silver nitrate and UV irradiation time affected the morphologies of the formed composites and optimal condition in preparation of the composites for SERS measurement was found using 20mM of silver nitrate with an irradiation time of 90 min. Under the optimized condition, the obtained SERS intensities were highly reproducible with a SERS enhancement factor in the order of 7. Quantitative analyses showed that a linear range up to 1 µM with a detection limit lower than 0.1 µM in the detection of creatinine in aqueous solution could be obtained. Successful applying of these prepared composites to determine creatinine in urine sample was obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Bi-template assisted synthesis of mesoporous manganese oxide nanostructures: Tuning properties for efficient CO oxidation.

PubMed

Roy, Mouni; Basak, Somjyoti; Naskar, Milan Kanti

2016-02-21

A simple soft bi-templating process was used for the synthesis of mesoporous manganese oxide nanostructures using KMnO4 as a precursor and polyethylene glycol and cetyltrimethylammonium bromide as templates in the presence of benzaldehyde as an organic additive in alkaline media, followed by calcination at 400 °C. X-ray diffraction and Raman spectroscopic analysis of the calcined products confirmed the existence of stoichiometric (MnO2 and Mn5O8) and non-stoichiometric mixed phases (MnO2 + Mn5O8) of Mn oxides obtained by tuning the concentration of the additive and the synthesis time. The surface properties of the prepared Mn oxides were determined by X-ray photoelectron spectroscopy. The mesoporosity of the samples was confirmed by N2 adsorption-desorption. Different synthetic conditions resulted in the formation of different morphologies of the Mn oxides (α-MnO2, Mn5O8, and α-MnO2 + Mn5O8), such as nanoparticles, nanorods, and nanowires. The synthesized mesoporous Mn oxide nanostructures were used for the catalytic oxidation of the harmful air pollutant carbon monoxide. The Mn5O8 nanoparticles with the highest Brunauer-Emmett-Teller surface area and the non-stoichiometric manganese oxide (α-MnO2 + Mn5O8) nanorods with a higher Mn(3+) concentration had the best catalytic efficiency.

Nuclear Microprobe using Elastic Recoil Detection (ERD) for Hydrogen Profiling in High Temperature Protonic Conductors

NASA Technical Reports Server (NTRS)

Berger, Pascal; Sayir, Ali; Berger, Marie-Helene

2004-01-01

The interaction between hydrogen and various high temperature protonic conductors (HTPC) has not been clearly understood due to poor densification and unreacted secondary phases. the melt-processing technique is used in producing fully dense simple SrCe(0.9)Y (0.10) O(3-delta) and complex Sr3Ca(1+x)Nb(2+x)O(9-delta) perovskites that can not be achieved by solid-state sintering. the possibilities of ion beam analysis have been investigated to quantify hydrogen distribution in HTPC perovskites subjected to water heat treatment. Nuclear microprobe technique is based on the interactions of a focused ion beam of MeV light ions (H-1, H-2, He-3, He-4,.) with the sample to be analyzed to determine local elemental concentrations at the cubic micrometer scale, the elastic recoil detection analysis technique (ERDA) has been carried out using He-4(+) microbeams and detecting the resulting recoil protons. Mappings of longitudinal sections of water treated SrCeO3 and Sr(Ca(1/3)Nb(2/3))O3 perovskites have been achieved, the water treatment strongly alters the surface of simple SrCe(0.9)Y(0.10)O(3-delta) perovskite. From Rutherford Back Scattering measurements (RBS), both Ce depletion and surface re-deposition is evidenced. the ERDA investigations on water treated Sr3Ca(1+x)Nb(2+x)O(9-delta) perovskite did not exhibit any spatial difference for the hydrogen incorporation from the surface to the centre. the amount of hydrogen incorporation for Sr3Ca(1+x)Nb(2+x)O(9-delta) was low and required further development of two less conventional techniques, ERDA in forward geometry and forward elastic diffusion H-1(p,p) H-1 with coincidence detection.

Self-Limiting Oxides on WSe2 as Controlled Surface Acceptors and Low-Resistance Hole Contacts.

PubMed

Yamamoto, Mahito; Nakaharai, Shu; Ueno, Keiji; Tsukagoshi, Kazuhito

2016-04-13

Transition metal oxides show much promise as effective p-type contacts and dopants in electronics based on transition metal dichalcogenides. Here we report that atomically thin films of under-stoichiometric tungsten oxides (WOx with x < 3) grown on tungsten diselenide (WSe2) can be used as both controlled charge transfer dopants and low-barrier contacts for p-type WSe2 transistors. Exposure of atomically thin WSe2 transistors to ozone (O3) at 100 °C results in self-limiting oxidation of the WSe2 surfaces to conducting WOx films. WOx-covered WSe2 is highly hole-doped due to surface electron transfer from the underlying WSe2 to the high electron affinity WOx. The dopant concentration can be reduced by suppressing the electron affinity of WOx by air exposure, but exposure to O3 at room temperature leads to the recovery of the electron affinity. Hence, surface transfer doping with WOx is virtually controllable. Transistors based on WSe2 covered with WOx show only p-type conductions with orders of magnitude better on-current, on/off current ratio, and carrier mobility than without WOx, suggesting that the surface WOx serves as a p-type contact with a low hole Schottky barrier. Our findings point to a simple and effective strategy for creating p-type devices based on two-dimensional transition metal dichalcogenides with controlled dopant concentrations.

Sorption of Th (IV) to silica as a function of pH, humic/fulvic acid, ionic strength, electrolyte type.

PubMed

Chen, Changlun; Wang, Xiangke

2007-02-01

The removal behavior of thorium (Th(IV)) has been investigated in multicomponent systems containing silica (SiO2) as the model of inorganic particles because of its widespread presence in the earth's crust and soil humic acid (HA)/fulvic acid (FA) by batch experiments. The influence of pH from 2 to 12, ionic strength from 0.02 to 0.2 M KNO3, soil HA/FA concentration from 8.3 to 22.5 mg/L, and foreign cations (Li+, Na+, K+) and anions (NO3(-), Cl-) on the sorption of Th(IV) onto SiO2 was also tested. The sorption isotherms of Th(IV) at approximately constant pH (3.50+/-0.02) were determined and analyzed regressively with three kinds of sorption isotherm models, i.e., linear, Langmuir, and Freundlich models. The results demonstrated that the sorption of Th(IV) onto SiO2 increased steeply with increasing pH from 2 to 4. Generally, humic substances (HSs) were shown to enhance Th(IV) sorption at low pH, but to reduce Th(IV) sorption at intermediate and high pH. It was a hypothesis that the significantly positive influence of HA/FA at pH from 2 to 4 on the sorption of Th(IV) onto SiO2 was attributed to strong surface binding of HA/FA on SiO2 and subsequently the formation of ternary surface complexes such as [triple bond]MO-O-HA-Th or [triple bond]MO-O-FA-Th. The results also demonstrated that the sorption was strongly dependent on the concentration of HA/FA, and independent of ionic strength and foreign ions under our experimental conditions.

Effect of Doping on Surface Reactivity and Conduction Mechanism in Sm-doped CeO2 Thin Films

DOE PAGES

Yang, Nan; Belianinov, Alex; Strelcov, Evgheni; ...

2014-11-21

Scanning probe microscopy measurements show irreversible surface electrochemistry in Sm-doped CeO2 thin films, which depends on humidity, temperature and doping concentration. A systematic study by electrochemical strain microscopy (ESM) in samples with two different Sm content and in several working conditions allows disclosing the microscopic mechanism underlying the difference in water adsorption and splitting with subsequent proton liberation. We measure the behavior of the hysteresis loops by changing temperature and humidity, both in standard ESM configuration and using the first order reversal curve (FORC) method. Complementing our study with spectroscopic measurements by hard x-ray photoemission spectroscopy we find that watermore » incorporation is favored until the doping with Sm is too high to allow the presence of Ce3+. The influence of doping on the surface reactivity and conduction mechanism clearly emerges from all of our experimental results. We find that at lower Sm concentration proton conduction is prevalent, featured by lower activation energy and higher mobility. Defect concentrations determine the type of the prevalent charge carrier in a doping dependent manner.« less

Surface greenhouse gas fluxes downwind of a penguin colony in the maritime sub-Antarctic

NASA Astrophysics Data System (ADS)

Drewer, Julia; Braban, Christine F.; Tang, Y. Sim; Anderson, Margaret; Skiba, Ute M.; Dragosits, Ulrike; Trathan, Phil

2015-12-01

The relationship between ammonia (NH3) concentrations downwind from a penguin colony and local surface greenhouse gas (GHG) fluxes was investigated on the remote sub-Antarctic Bird Island (54°00‧S, 38°03‧W) during summer 2010 (November and December). A Macaroni penguin (Eudyptes chrysolophus) colony (40,000 pairs) at Goldcrest Point is a large point source of NH3 on the island and a measurement transect of 23 m, 36 m, 70 m, 143 m and 338 m was set up downwind from the colony. Atmospheric NH3 concentrations measured by passive diffusion samplers declined from 23 μg m-3 close to the colony to less than 1 μg m-3 338 m downwind. As increased nitrogen (N) deposition can affect soil carbon (C) and N cycling, it can therefore potentially influence GHG and nitric oxide (NO) emission rates. However, in this study, a clear correlation between surface GHG fluxes and atmospheric NH3 concentrations could not be established. Average fluxes for nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) over the entire transect and the eight week study period ranged from 7 to 23 μg N2O-N m-2 h-1, -5.5-245 μg CH4 m-2 h-1, and CO2 respiration rates averaged 2.2 μmol m-2 s-1. Laboratory studies using intact soil cores from the transect also did not show any significant correlation between atmospheric NH3 concentrations and N2O, NO, CH4 emissions or CO2 respiration rates. Overall, fluxes measured in the laboratory study reflected the high variability measured in the field. Large changes in soil depth along the transect, due to the topography of the island, possibly influenced fluxes more than NH3 concentration and seabirds appeared to have a more localised input (e.g. ground nesting birds). However, warmer temperatures might have a large potential to increase GHG fluxes in this ecosystem. This study confirms that GHG fluxes do occur in these ornithogenic ecosystems, however, the scale of the impact remains largely unquantified due to high uncertainties and high spatial variability.

Incorporation of Fe3O4/CNTs nanocomposite in an epoxy coating for corrosion protection of carbon steel

NASA Astrophysics Data System (ADS)

Pham, Gia Vu; Truc Trinh, Anh; To, Thi Xuan Hang; Duong Nguyen, Thuy; Trang Nguyen, Thu; Hoan Nguyen, Xuan

2014-09-01

In this study Fe3O4/CNTs composite with magnetic property was prepared by attaching magnetic nanoparticles (Fe3O4) to carbon nanotubes (CNTs) by hydrothermal method. The obtained Fe3O4/CNTs composite was characterized by Fourier transform infrared (FTIR) spectroscopy, powder x-ray diffraction and transmission electron microscopy. The Fe3O4/CNTs composite was then incorporated into an epoxy coating at concentration of 3 wt%. Corrosion protection of epoxy coating containing Fe3O4/CNTs composite was evaluated by electrochemical impedance spectroscopy and adhesion measurement. The impedance measurements show that Fe3O4/CNTs composite enhanced the corrosion protection of epoxy coating. The corrosion resistance of the carbon steel coated by epoxy coating containing Fe3O4/CNTs composite was significantly higher than that of carbon steel coated by clear epoxy coating and epoxy coating containing CNTs. FE-SEM photographs of fracture surface of coatings showed good dispersion of Fe3O4/CNTs composite in the epoxy matrix.

Investigating the electronic properties of Al2O3/Cu(In,Ga)Se2 interface

NASA Astrophysics Data System (ADS)

Kotipalli, R.; Vermang, B.; Joel, J.; Rajkumar, R.; Edoff, M.; Flandre, D.

2015-10-01

Atomic layer deposited (ALD) Al2O3 films on Cu(In,Ga)Se2 (CIGS) surfaces have been demonstrated to exhibit excellent surface passivation properties, which is advantageous in reducing recombination losses at the rear metal contact of CIGS thin-film solar cells. Here, we report, for the first time, experimentally extracted electronic parameters, i.e. fixed charge density (Qf) and interface-trap charge density (Dit), for as-deposited (AD) and post-deposition annealed (PDA) ALD Al2O3 films on CIGS surfaces using capacitance-voltage (C-V) and conductance-frequency (G-f) measurements. These results indicate that the AD films exhibit positive fixed charges Qf (approximately 1012 cm-2), whereas the PDA films exhibit a very high density of negative fixed charges Qf (approximately 1013 cm-2). The extracted Dit values, which reflect the extent of chemical passivation, were found to be in a similar range of order (approximately 1012 cm-2 eV-1) for both AD and PDA samples. The high density of negative Qf in the bulk of the PDA Al2O3 film exerts a strong Coulomb repulsive force on the underlying CIGS minority carriers (ns), preventing them to recombine at the CIGS/Al2O3 interface. Using experimentally extracted Qf and Dit values, SCAPS simulation results showed that the surface concentration of minority carriers (ns) in the PDA films was approximately eight-orders of magnitude lower than in the AD films. The electrical characterization and estimations presented in this letter construct a comprehensive picture of the interfacial physics involved at the Al2O3/CIGS interface.

Surface tension of Nanofluid-type fuels containing suspended nanomaterials

PubMed Central

2012-01-01

The surface tension of ethanol and n-decane based nanofluid fuels containing suspended aluminum (Al), aluminum oxide (Al2O3), and boron (B) nanoparticles as well as dispersible multi-wall carbon nanotubes (MWCNTs) were measured using the pendant drop method by solving the Young-Laplace equation. The effects of nanoparticle concentration, size and the presence of a dispersing agent (surfactant) on surface tension were determined. The results show that surface tension increases both with particle concentration (above a critical concentration) and particle size for all cases. This is because the Van der Waals force between particles at the liquid/gas interface increases surface free energy and thus increases surface tension. At low particle concentrations, however, addition of particles has little influence on surface tension because of the large distance between particles. An exception is when a surfactant was used or when (MWCNTs) was involved. For such cases, the surface tension decreases compared to the pure base fluid. The hypothesis is the polymer groups attached to (MWCNTs) and the surfactant layer between a particle and the surround fluid increases the electrostatic force between particles and thus reduce surface energy and surface tension. PMID:22513039

Role of surface defects on the formation of the 2-dimensional electron gas at polar interfaces

NASA Astrophysics Data System (ADS)

Artacho, Emilio; Aguado-Puente, Pablo

2014-03-01

The discovery of a 2-dimensional electron gas (2DEG) at the interface between two insulators, LaAlO3 and SrTiO3, has fuelled a great research activity on this and similar systems in the last years. The electronic reconstruction model, typically invoked to explain the formation of the 2DEG, while being intuitive and successful on predicting fundamental aspects of this phenomenon like the critical thickness of LaAlO3, fails to explain many other experimental observations. Oxygen vacancies, on the other hand, are known to dramatically affect the physical behaviour of this system, but their role at the atomic level is far from well understood. Here we perform ab initio simulations in order to assess whether the formation of oxygen vacancies at the surface of the polar material can account for various recent experimental results that defy the current theoretical understanding of these interfaces. We simulate SrTiO3/LaAlO3 slabs with various concentrations of surface oxygen vacancies and analyze the role of the defects on the formation of the metallic interface, their electrostatic coupling with the 2DEG and the interplay with the different instabilities of the materials involved. Financial support from Spanish MINECO under grant FIS2012-37549-C05-01. Computational resources provided by the Red Espñola de Supercomputación and DIPC.

Hydrothermal synthesis of graphene oxide/multiwalled carbon nanotube/Fe3O4 ternary nanocomposite for removal of Cu (II) and methylene blue

NASA Astrophysics Data System (ADS)

Long, Zhihang; Zhan, Yingqing; Li, Fei; Wan, Xinyi; He, Yi; Hou, Chunyan; Hu, Hai

2017-09-01

In this work, highly activated graphene oxide/multiwalled carbon nanotube/Fe3O4 ternary nanocomposite adsorbent was prepared from a simple hydrothermal route by using ferrous sulfate as precursor. For this purpose, the graphene oxide/multiwalled carbon nanotube architectures were formed through the π-π attractions between them, followed by attaching Fe3O4 nanoparticles onto their surface. The structure and composition of as-prepared ternary nanocomposite were characterized by XRD, FTIR, XPS, SEM, TEM, Raman, TGA, and BET. It was found that the resultant porous graphene oxide/multiwalled carbon nanotube/Fe3O4 ternary nanocomposite with large surface area could effectively prevent the π-π stacking interactions between graphene oxide nanosheets and greatly improve sorption sites on the surfaces. Thus, owing to the unique ternary nanocomposite architecture and synergistic effect among various components, as-prepared ternary nanocomposite exhibited high separation efficiency when they were used to remove the Cu (II) and methylene blue from aqueous solutions. Furthermore, the adsorption isotherms of ternary nanocomposite structures for Cu (II) and methylene blue removal fitted the Langmuir isotherm model. This work demonstrated that the graphene oxide/multiwalled carbon nanotube/Fe3O4 ternary nanocomposite was promising as an efficient adsorbent for heavy metal ions and organic dye removal from wastewater in low concentration.

High-Thermal- and Air-Stability Cathode Material with Concentration-Gradient Buffer for Li-Ion Batteries.

PubMed

Shi, Ji-Lei; Qi, Ran; Zhang, Xu-Dong; Wang, Peng-Fei; Fu, Wei-Gui; Yin, Ya-Xia; Xu, Jian; Wan, Li-Jun; Guo, Yu-Guo

2017-12-13

Delivery of high capacity with high thermal and air stability is a great challenge in the development of Ni-rich layered cathodes for commercialized Li-ion batteries (LIBs). Herein we present a surface concentration-gradient spherical particle with varying elemental composition from the outer end LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM) to the inner end LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA). This cathode material with the merit of NCM concentration-gradient protective buffer and the inner NCA core shows high capacity retention of 99.8% after 200 cycles at 0.5 C. Furthermore, this cathode material exhibits much improved thermal and air stability compared with bare NCA. These results provide new insights into the structural design of high-performance cathodes with high energy density, long life span, and storage stability materials for LIBs in the future.

Optimization of Acid Orange 7 Degradation in Heterogeneous Fenton-like Reaction Using Fe3-xCoxO4 Catalyst

NASA Astrophysics Data System (ADS)

Ibrahim, M. Z.; Alrozi, R.; Zubir, N. A.; Bashah, N. A.; Ali, S. A. Md; Ibrahim, N.

2018-05-01

The oxidation process such as heterogeneous Fenton and/or Fenton-like reactions is considered as an effective and efficient method for treatment of dye degradation. In this study, the degradation of Acid Orange 7 (AO7) was investigated by using Fe3-xCoxO4 as a heterogeneous Fenton-like catalyst. Response surface methodology (RSM) was used to optimize the operational parameters condition and the interaction of two or more parameters. The parameter studies were catalyst dosage (X1 ), pH (X2 ) and H2O2 concentration (X3 ) towards AO7 degradation. Based on analysis of variance (ANOVA), the derived quadratic polynomial model was significant whereby the predicted values matched the experimental values with regression coefficient of R2 = 0.9399. The optimum condition for AO7 degradation was obtained at catalyst dosage of 0.84 g/L, pH of 3 and H2O2 concentration of 46.70 mM which resulted in 86.30% removal of AO7 dye. These findings present new insights into the influence of operational parameters in the heterogeneous Fenton-like oxidation of AO7 using Fe3-xCoxO4 catalyst.

Analysis of Ozone Transportation in Tlaxcala-Puebla Mexico Air Basin

NASA Astrophysics Data System (ADS)

Barrera-Huertas, H.; Torres, R.; Ruiz-Suárez, L. G.; Garcia, J.; Gutierrez, W.; Torres, A.

2014-12-01

Preliminary results of an investigation conducted between March and April 2012 on the influence of air pollutants transport in the Puebla-Tlaxcala Valley airshed are presented. The campaign included ozone (O3), nitrogen dioxide (NO2) and meteorological variables monitoring at surface in Huaquechula, Chipilo and Amozoc rural sites, and measurements of O3 vertical profile O3 and meteorology in Chipilo. The synoptic conditions during the campaign showed dominance of "Norte" conditions favoring air masses circulation from Pacific Ocean crossing southern Mexican Plateau to the Gulf of Mexico that influences the establishment of evening southeasterly winds in the Puebla-Tlaxcala Valley. Wind roses and contaminants analysis in surface for O3 during entire campaign indicates that before noon the movement of air masses was dominated by runoff of Malinche toward the southeast and south of the valley; and in the afternoon a regional pattern of winds from southwest Valley prevails coming from Cuautla Valley and south of Morelos State. The analysis of three representative days of atmospheric circulation in the valley as well as anthropogenic diurnal activity, a rate of morning increase in O3 concentrations similar at all three sites was observed, even in the absence of precursors such as NO2 during some weekends. By analyzing and engage data from O3 vertical profile and surface meteorology data, we could infer that there are minimal ozone contributions from local sources, but important from regional origin, and even O3 entrainment in height brought to the surface when mixing layer is growing. The back trajectory analysis from Chipilo at noon indicates that could be additional contributions of O3 from both Cuautla Valley and other areas of pollutants emission such as Tula, (in the north of Mexico City), and that weekend effect with the occurrence of high O3 levels observed there extends to this region. Although interbasin exchange of pollutants between the Puebla-Tlaxcala Valley and Cuautla is confirmed, also was identified that O3 contribution in the free troposphere is important to sustaining high O3 values during the afternoon in Puebla. This implies that establishment of control strategies at regional level should be based on detailed studies of the influence of O3 seasonality in the free troposphere.

Effect of hydrolysis of N2O5 on nitrate and ammonium formation in Beijing China: WRF-Chem model simulation.

PubMed

Su, Xing; Tie, Xuexi; Li, Guohui; Cao, Junji; Huang, Rujin; Feng, Tian; Long, Xin; Xu, Ruiguang

2017-02-01

Beijing, the capital of China, is a mega city with a population of >20 million. In recent years, the city has experienced heavy air pollution, with particulate matter (PM) being one of its top pollutants. In the last decade, extensive efforts have been made to characterize the sources, properties, and processes of PM in Beijing. Despite progress made by previous studies, there are still some important questions to be answered and addressed. The focus of this research is to study the impact of the heterogeneous hydrolysis of N 2 O 5 on the formation of nitrate (NO 3 - ) and ammonium (NH 4 + ) in Beijing. The results show that during heavy pollution days (e.g., during 14-17 September 2015, with PM 2.5 concentration over 100μg/m 3 ), the concentrations of NO 2 and O 3 were high, with maxima of 90 and 240μg/m 3 , respectively, providing high precursors for the formation of N 2 O 5 . In addition, the aerosol and sulfate concentrations were also high, with maxima of 201μg/m 3 and 23μg/m 3 respectively, providing reacting surface for the heterogeneous reaction. As a result, the hydrolysis of N 2 O 5 led to 21.0% enhancement of nitrate (NO 3 - ) and 7.5% enhancement of ammonium (NH 4 + ). It is worth to note that this important effect only occurred in high pollution days (PM 2.5 concentration over 100μg/m 3 ). During low-pollution periods (PM 2.5 concentration <100μg/m 3 ), the effect of hydrolysis of N 2 O 5 on the formation of nitrate and ammonium was insignificant (variation rate <5%). This study suggests that during heavy pollution periods, the hydrolysis of N 2 O 5 enhances the level of aerosol pollution in Beijing, and needs to be further studied in order to perform efficient air pollution control and mitigation strategies. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluating the influences of biomass burning during 2006 BASE-ASIA: a regional chemical transport modeling

NASA Astrophysics Data System (ADS)

Fu, J. S.; Hsu, N. C.; Gao, Y.; Huang, K.; Li, C.; Lin, N.-H.; Tsay, S.-C.

2011-12-01

To evaluate the impact of biomass burning from Southeast Asia to East Asia, this study conducted numerical simulations during NASA's 2006 Biomass-burning Aerosols in South-East Asia: Smoke Impact Assessment (BASE-ASIA). Two typical episode periods (27-28 March and 13-14 April) were examined. Two emission inventories, FLAMBE and GFED, were used in the simulations. The influences during two episodes in the source region (Southeast Asia) contributed to the surface CO, O3 and PM2.5 concentrations as high as 400 ppbv, 20 ppbv and 80 μg m-3, respectively. The perturbations with and without biomass burning of the above three species during the intense episodes were in the range of 10 to 60%, 10 to 20% and 30 to 70%, respectively. The impact due to long-range transport could spread over the southeastern parts of East Asia and could reach about 160 to 360 ppbv, 8 to 18 ppbv and 8 to 64 μg m-3 on CO, O3 and PM2.5, respectively; the percentage impact could reach 20 to 50% on CO, 10 to 30% on O3, and as high as 70% on PM2.5. In March, the impact of biomass burning was mainly concentrated in Southeast Asia and Southern China, while in April the impact becomes slightly broader, potentially including the Yangtze River Delta region. Two cross-sections at 15° N and 20° N were used to compare the vertical flux of biomass burning. In the source region (Southeast Asia), CO, O3 and PM2.5 concentrations had a strong upward transport from surface to high altitudes. The eastward transport becomes strong from 2 to 8 km in the free troposphere. The subsidence process during the long-range transport contributed 60 to 70%, 20 to 50%, and 80% to CO, O3 and PM2.5, respectively to surface in the downwind area. The study reveals the significant impact of Southeastern Asia biomass burning on the air quality in both local and downwind areas, particularly during biomass burning episodes. This modeling study might provide lower limit constraints. An additional study is underway for an active biomass burning year to obtain an upper limit and climate effects.

Evaluating the influences of biomass burning during 2006 BASE-ASIA: a regional chemical transport modeling

NASA Astrophysics Data System (ADS)

Fu, J. S.; Hsu, N. C.; Gao, Y.; Huang, K.; Li, C.; Lin, N.-H.; Tsay, S.-C.

2012-05-01

To evaluate the impact of biomass burning from Southeast Asia to East Asia, this study conducted numerical simulations during NASA's 2006 Biomass-burning Aerosols in South-East Asia: Smoke Impact Assessment (BASE-ASIA). Two typical episode periods (27-28 March and 13-14 April) were examined. Two emission inventories, FLAMBE and GFED, were used in the simulations. The influences during two episodes in the source region (Southeast Asia) contributed to the surface CO, O3 and PM2.5 concentrations as high as 400 ppbv, 20 ppbv and 80 μg m-3, respectively. The perturbations with and without biomass burning of the above three species during the intense episodes were in the range of 10 to 60%, 10 to 20% and 30 to 70%, respectively. The impact due to long-range transport could spread over the southeastern parts of East Asia and could reach about 160 to 360 ppbv, 8 to 18 ppbv and 8 to 64 μg m-3 on CO, O3 and PM2.5, respectively; the percentage impact could reach 20 to 50% on CO, 10 to 30% on O3, and as high as 70% on PM2.5. In March, the impact of biomass burning mainly concentrated in Southeast Asia and southern China, while in April the impact becomes slightly broader and even could go up to the Yangtze River Delta region. Two cross-sections at 15° N and 20° N were used to compare the vertical flux of biomass burning. In the source region (Southeast Asia), CO, O3 and PM2.5 concentrations had a strong upward transport from surface to high altitudes. The eastward transport becomes strong from 2 to 8 km in the free troposphere. The subsidence process during the long-range transport contributed 60 to 70%, 20 to 50%, and 80% on CO, O3 and PM2.5, respectively to surface in the downwind area. The study reveals the significant impact of Southeastern Asia biomass burning on the air quality in both local and downwind areas, particularly during biomass burning episodes. This modeling study might provide constraints of lower limit. An additional study is underway for an active biomass burning year to obtain an upper limit and climate effects.

Hydroquinone-ZnO nano-laminate deposited by molecular-atomic layer deposition

NASA Astrophysics Data System (ADS)

Huang, Jie; Lucero, Antonio T.; Cheng, Lanxia; Hwang, Hyeon Jun; Ha, Min-Woo; Kim, Jiyoung

2015-03-01

In this study, we have deposited organic-inorganic hybrid semiconducting hydroquinone (HQ)/zinc oxide (ZnO) superlattices using molecular-atomic layer deposition, which enables accurate control of film thickness, excellent uniformity, and sharp interfaces at a low deposition temperature (150 °C). Self-limiting growth of organic layers is observed for the HQ precursor on ZnO surface. Nano-laminates were prepared by varying the number of HQ to ZnO cycles in order to investigate the physical and electrical effects of different HQ to ZnO ratios. It is indicated that the addition of HQ layer results in enhanced mobility and reduced carrier concentration. The highest Hall mobility of approximately 2.3 cm2/V.s and the lowest n-type carrier concentration of approximately 1.0 × 1018/cm3 were achieved with the organic-inorganic superlattice deposited with a ratio of 10 ZnO cycles to 1 HQ cycle. This study offers an approach to tune the electrical transport characteristics of ALD ZnO matrix thin films using an organic dopant. Moreover, with organic embedment, this nano-laminate material may be useful for flexible electronics.

Selective adsorption of bovine hemoglobin on functional TiO2 nano-adsorbents: surface physic-chemical properties determined adsorption activity

NASA Astrophysics Data System (ADS)

Guo, Shiguang; Zhang, Jianghua; Shao, Mingxue; Zhang, Xia; Liu, Yufeng; Xu, Junli; Meng, Hao; Han, Yide

2015-04-01

Surface functionalized nanoparticles are efficient adsorbents which have shown good potential for protein separation. In this work, we chose two different types of organic molecules, oleic acid (OA) and 3-glycidoxypropyltrimethoxy silane (GPTMS), to functionalize the surface of TiO2 nanoparticles, and we studied the effects of this modification on their surface physicochemical properties in correlation with their selective adsorption of proteins. The results showed that the surface zeta potential and the surface water wettability of the modified TiO2 were significantly changed in comparison with the original TiO2 nanoparticles. The adsorption activities of bovine hemoglobin (BHb) and bovine serum albumin (BSA) on these functionalized TiO2 samples were investigated under different conditions, including pH values, contact time, ion strength, and initial protein concentration. In comparison with the non-specific adsorption of original TiO2, however, both the OA-TiO2 and GPTMS-TiO2 exhibited increased BHb adsorption and decreased BSA adsorption at the same time. Using a binary protein mixture as the adsorption object, a higher separation factor (SF) was obtained for OA-TiO2 under optimum conditions. The different adsorption activities of BHb and BSA on the modified TiO2 were correlated with different interactions at the protein/solid interface, and the chemical force as well as the electrostatic force played an important role in the selective adsorption process.

Magnetic separation of heavy metal ions and evaluation based on surface-enhanced Raman spectroscopy: copper(II) ions as a case study.

PubMed

Yan, Xue; Zhang, Xue-Jiao; Yuan, Ya-Xian; Han, San-Yang; Xu, Min-Min; Gu, Ren'ao; Yao, Jian-Lin

2013-11-01

A new approach was developed for the magnetic separation of copper(II) ions with easy operation and high efficiency. p-Mercaptobenzoic acid served as the modified tag of Fe2O3@Au nanoparticles both for the chelation ligand and Raman reporter. Through the chelation between the copper(II) ions and carboxyl groups on the gold shell, the Fe2O3@Au nanoparticles aggregated to form networks that were enriched and separated from the solution by a magnet. A significant decrease in the concentration of copper(II) ions in the supernatant solution was observed. An extremely sensitive method based on surface-enhanced Raman spectroscopy was employed to detect free copper(II) ions that remained after the magnetic separation, and thus to evaluate the separation efficiency. The results indicated the intensities of the surface-enhanced Raman spectroscopy bands from p-mercaptobenzoic acid were dependent on the concentration of copper(II) ions, and the concentration was decreased by several orders of magnitude after the magnetic separation. The present protocol effectively decreased the total amount of heavy metal ions in the solution. This approach opens a potential application in the magnetic separation and highly sensitive detection of heavy metal ions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rational Design and Synthesis of Carboxylate Gemini Surfactants with an Excellent Aggregate Behavior for Nano-La2O3 Morphology-Controllable Preparation.

PubMed

Liao, Xueming; Gao, Zhinong; Xia, Yan; Niu, Fei; Zhai, Wenzhong

2017-04-04

A series of carboxylate gemini surfactants (CGS, C n -Φ-C n , n = 12, 14, 16, 18) with diphenyl ketone as a spacer group were prepared using a simple and feasible synthetic method. These CGS exhibited an excellent surface activity with extremely low critical micelle concentration (CMC) value (approximately 10 -5 mol/L), good performance in reducing surface tension (nearly 30 mN/m), and the ability of molecular self-assembly into different aggregate morphologies via adjusting the concentrations, which is attributed to the introduction of diphenyl ketone and carboxylic acid ammonium salt in the molecular structure. Moreover, the surface activity and self-assembly ability of CGS were further optimized by tuning the length of the tail chain. These excellent properties imply that CGS can be a soft template to prepare nanomaterials, especially in morphology-controllable synthesis. By adjusting the concentration of one of CGS (C 12 -Φ-C 12 ), nano-La 2 O 3 particles with diverse morphologies were obtained, including spherical shape, bead-chain shape, rod shape, velvet-antler shape, cedar shape, and bowknot shape. This work offers a vital insight into the rational design of template agents for the development of morphology-controllable nanomaterials.

Surface gas pollutants in Lhasa, a highland city of Tibet: current levels and pollution implications

NASA Astrophysics Data System (ADS)

Ran, L.; Lin, W. L.; Deji, Y. Z.; La, B.; Tsering, P. M.; Xu, X. B.; Wang, W.

2014-05-01

Through several years of development, the city of Lhasa has become one of the most populated and urbanized areas on the highest plateau in the world. In the process of urbanization, current and potential air quality issues have been gradually concerned. To investigate the current status of air pollution in Lhasa, various gas pollutants including NOx, CO, SO2 and O3 were continuously measured from June 2012 to May 2013 at an urban site (29.40° N, 91.08° E, 3650 m a.s.l.). The seasonal variations of primary gas pollutants exhibited a peak from November to January with a large variability. High concentrations of primary trace gases almost exclusively occurred under low wind speed and showed no distinct dependence on wind direction, implying local urban emissions to be predominant. A comparison of NO2, CO and SO2 concentrations in summer between 1998 and 2012 indicated a significant increase in emissions of these gas pollutants and a change in their intercorrelations, as a result of a substantial growth in the demand of energy consumption using fossil fuels instead of previously widely used biofuels. The pronounced diurnal double peaks of primary trace gases in all seasons suggested automobile exhaust to be a major emission source in Lhasa. The secondary gas pollutant O3 displayed an average diurnal cycle of a shallow flat peak for about 4-5 h in the afternoon and a minimum in the early morning. Nighttime O3 was sometimes completely consumed by the high level of NOx. Seasonally, the variations of O3 concentrations displayed a low valley in winter and a peak in spring. In autumn and winter, transport largely contributed to the observed O3 concentrations, given its dependence on wind speed and wind direction, while in spring and summer photochemistry played an important role. A more efficient buildup of O3 concentrations in the morning and a higher peak in the afternoon was found in summer 2012 than in 1998. An enhancement in O3 concentrations would be expected in the future and more attention should be given to O3 photochemistry in response to increasing precursor emissions in this area.

Efficient dechlorination of chlorinated solvent pollutants under UV irradiation by using the synthesized TiO2 nano-sheets in aqueous phase.

PubMed

Ndong, Landry Biyoghe Bi; Ibondou, Murielle Primaelle; Miao, Zhouwei; Gu, Xiaogang; Lu, Shuguang; Qiu, Zhaofu; Sui, Qian; Mbadinga, Serge Maurice

2014-05-01

Titanium dioxide (TiO2), which is the widely used photo-catalyst, has been synthesized by simple hydrothermal solution containing tetrabutyl titanate and hydrofluoric acid. The synthesized product has been applied to photo-degradation in aqueous phase of chlorinated solvents, namely tetrachloroethene (PCE), trichloroethene (TCE) and 1,1,1-trichloroethane (TCA). The photo-degradation results revealed that the degradation of these harmful chemicals was better in UV/synthesized TiO2 system compared to UV/commercial P25 system and UV only system. The photo-catalytic efficiency of the synthesized TiO2 was 1.4, 1.8 and 3.0 folds higher compared to the commercial P25 for TCA, TCE and PCE degradation, respectively. Moreover, using nitrobenzene (NB) as a probe of hydroxyl radical (·OH), the degradation rate was better over UV/synthesized TiO2, suggesting the high concentration of ·OH generated in UV/synthesized TiO2 system. In addition, ·OH concentration was confirmed by the strong peak displayed in EPR analysis over UV/synthesized TiO2 system. The characterization result using XRD and TEM showed that the synthesized TiO2 was in anatase form and consisted of well-defined sheet-shaped structures having a rectangular outline with a thickness of 4 nm, side length of 50 nm and width of 33 nm and a surface 90.3 m(2)/g. XPS analysis revealed that ≡Ti-F bond was formed on the surface of the synthesized TiO2. The above results on both photocatalytic activity and the surface analysis demonstrated the good applicability of the synthesized TiO2 nano-sheets for the remediation of chlorinated solvent contaminated groundwater. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Sterilization of Bacillus pumilus spores using supercritical fluid carbon dioxide containing various modifier solutions.

PubMed

Shieh, Edison; Paszczynski, Andrzej; Wai, Chien M; Lang, Qingyong; Crawford, Ronald L

2009-03-01

Supercritical fluid carbon dioxide (SF-CO(2)) with small amounts of chemical modifier(s) provides a very effective sterilization technique that should be useful for destroying microorganism on heat-sensitive devices such as instruments flown on planetary-bound spacecraft. Under a moderate temperature (50 degrees C) and pressure (100 atm), spores of Bacillus pumilus strains ATCC 7061 and SAFR 032 can be effectively inactivated/eliminated from metal surfaces and small electronic devices in only 45 min using optimized modifier concentrations. Modifiers explored in this study included hydrogen peroxide (H(2)O(2)), tert-butyl hydroperoxide, formic acid, and Triton X-100. During sterilization procedure the modifiers were continuously added to SF-CO(2) in either methanol or water at controlled concentrations. The lowest effective concentrations were established for each modifier. Complete elimination of both types of B. pumilus endospores occurred with an optimal modifier addition of either or 10% methanol containing 12% H(2)O(2) or 12% tert-butyl hydroperoxide in SF-CO(2), or a mixture of 6% H(2)O(2) and 6% tert-butyl hydroperoxide. Using water as the carrier of SF-CO(2) modifier, the complete elimination of spores viability of both B. pumilus strains occurred with an addition of either 3.3% water containing 3% H(2)O(2), or 3.3% water containing 10% methanol and 0.5% formic acid, or 3.3% water containing 10% methanol, 1% formic acid and 2% H(2)O(2).

Amplified Peroxidase-Like Activity in Iron Oxide Nanoparticles Using Adenosine Monophosphate: Application to Urinary Protein Sensing.

PubMed

Yang, Ya-Chun; Wang, Yen-Ting; Tseng, Wei-Lung

2017-03-22

Numerous compounds such as protein and double-stranded DNA have been shown to efficiently inhibit intrinsic peroxidase-mimic activity in Fe 3 O 4 nanoparticles (NP) and other related nanomaterials. However, only a few studies have focused on finding new compounds for enhancing the catalytic activity of Fe 3 O 4 NP-related nanomaterials. Herein, phosphate containing adenosine analogs are reported to enhance the oxidation reaction of hydrogen peroxide (H 2 O 2 ) and amplex ultrared (AU) for improving the peroxidase-like activity in Fe 3 O 4 NPs. This enhancement is suggested to be a result of the binding of adenosine analogs to Fe 2+ /Fe 3+ sites on the NP surface and from adenosine 5'-monophosphate (AMP) acting as the distal histidine residue of horseradish peroxidase for activating H 2 O 2 . Phosphate containing adenosine analogs revealed the following trend for the enhanced activity of Fe 3 O 4 NPs: AMP > adenosine 5'-diphosphate > adenosine 5'-triphosphate. The peroxidase-like activity in the Fe 3 O 4 NPs progressively increased with increasing AMP concentration and polyadenosine length. The Michaelis constant for AMP attached Fe 3 O 4 NPs is 5.3-fold lower and the maximum velocity is 2.7-fold higher than those of the bare Fe 3 O 4 NPs. Furthermore, on the basis of AMP promoted peroxidase mimicking activity in the Fe 3 O 4 NPs and the adsorption of protein on the NP surface, a selective fluorescent turn-off system for the detection of urinary protein is developed.

Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars

USGS Publications Warehouse

Marion, G.M.; Catling, D.C.; Kargel, J.S.

2003-01-01

Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 ??C to 25 ??C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars. Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl2??4H2O, FeCl2??6H2O, FeSO4??H2O, FeSO4??7H2O, FeCO3, and Fe(OH)3] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO4, Fe-HCO3, H-Fe-Cl, and H-Fe-SO4. We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO3), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification. What began as a dilute Mg-Fe-HCO3 dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO4-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O2(g)], but later caused oxidation of iron [high O2(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses. ?? 2003 Elsevier Ltd.

Liquefied petroleum gas sensor based on manganese (III) oxide and zinc manganese (III) oxide nanoparticles

NASA Astrophysics Data System (ADS)

Sharma, Shiva; Chauhan, Pratima; Husain, Shahid

2018-01-01

In this paper, {{{Mn}}}2{{{O}}}3 and {{{ZnMn}}}2{{{O}}}4 nanoparticles (NPs) are successfully synthesized using chemical co-precipitation method at room temperature and further annealed at 450 °C. The structure, crystallite size, morphology, specific surface area (SSA) and band gap energy have been determined by x-ray diffraction, transmission electron microscopy, Brunauer-Emmett-Teller surface area analysis, scanning electron microscopy (SEM-EDS) and UV-visible spectrophotometer. The sensor films of the {{{Mn}}}2{{{O}}}3 NPs and {{{ZnMn}}}2{{{O}}}4 NPs have been fabricated onto glass substrate using spin coater system separately. These sensor films are investigated for different concentrations (200-1200 ppm) of liquefied petroleum gas (LPG) at different operating temperatures ranging from 100 °C to 400 °C. A comparative study of gas sensing properties shows that spinel {{{ZnMn}}}2{{{O}}}4 sensor film exhibit excellent response (≈ 80 % ) towards 1000 ppm LPG at 300 °C in comparison to {{{Mn}}}2{{{O}}}3 sensor films. The enhancement in the gas sensing characteristics of {{{ZnMn}}}2{{{O}}}4 sensor film is attributed to the reduced crystallite size, greater SSA, and modification in structure as well as morphology.

Dissolution behavior of MgO based inert matrix fuel for the transmutation of minor actinides

NASA Astrophysics Data System (ADS)

Mühr-Ebert, E. L.; Lichte, E.; Bukaemskiy, A.; Finkeldei, S.; Klinkenberg, M.; Brandt, F.; Bosbach, D.; Modolo, G.

2018-07-01

This study explores the dissolution properties of magnesia-based inert matrix nuclear fuel (IMF) containing transuranium elements (TRU). Pure MgO pellets as well as MgO pellets containing CeO2, as surrogate for TRU oxides, and are considered as model systems for genuine magnesia based inert matrix fuel were fabricated. The aim of this study is to identify conditions at which the matrix material can be selectively dissolved during the head-end reprocessing step, allowing a separation of MgO from the actinides, whereas the actinides remain undissolved. The dissolution behavior was studied in macroscopic batch experiments as a function of nitric acid concentration, dissolution medium volume, temperature, stirring velocity, and pellet density (85, 90, 96, and 99%TD). To mimic pellets with various burn-ups the density of the here fabricated pellets was varied. MgO is soluble even under mild conditions (RT, 2.5 mol/L HNO3). The dissolution rates of MgO at different acid concentrations are rather similar, whereas the dissolution rate is strongly dependent on the temperature. Via a microscopic approach, a model was developed to describe the evolution of the pellet surface area during dissolution and determine a surface normalized dissolution rate. Moreover, dissolution rates of the inert matrix fuel containing CeO2 were determined as a function of the acid concentration and temperature. During the dissolution of MgO/CeO2 pellets the MgO dissolves completely, while CeO2 (>99%) remains undissolved. This study intends to provide a profound understanding of the chemical performance of magnesia based IMF containing fissile material. The feasibility of the dissolution of magnesia based IMF with nitric acid is discussed.

Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides

USGS Publications Warehouse

White, A.F.; Peterson, M.L.

1996-01-01

Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25??C. For an aqueous transition metal m, such reactions are 3[Fe2+Fe3+2]O4(magnetite) + 2/nmz ??? 4[Fe3+2]O3(maghemite) + Fe2+ + 2/nmz-n and 3[Fe2+Ti]O3(ilmenite) + 2/nmz ??? Fe3+2Ti3O9(pseudorutile) + Fe2+ + 2/nmz-n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] ??? [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 ?? 10-10 mol m-2 s-1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe2+ is oxidized homogeneously in solution to Fe3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental solution. In contrast, magnetite weathered under oxidizing vadose conditions show minimum reactivity toward chromate ions. The ability of Fe(II) oxides to reduce transition metals in soils and groundwaters will be strongly dependent on the redox environment.

Investigation of the High Mobility IGZO Thin Films by Using Co-Sputtering Method

PubMed Central

Hsu, Chao-Ming; Tzou, Wen-Cheng; Yang, Cheng-Fu; Liou, Yu-Jhen

2015-01-01

High transmittance ratio in visible range, low resistivity, and high mobility of IGZO thin films were prepared at room temperature for 30 min by co-sputtering of Zn2Ga2O5 (Ga2O3 + 2 ZnO, GZO) ceramic and In2O3 ceramic at the same time. The deposition power of pure In2O3 ceramic target was fixed at 100 W and the deposition power of GZO ceramic target was changed from 80 W to 140 W. We chose to investigate the deposition power of GZO ceramic target on the properties of IGZO thin films. From the SEM observations, all of the deposited IGZO thin films showed a very smooth and featureless surface. From the measurements of XRD patterns, only the amorphous structure was observed. We aimed to show that the deposition power of GZO ceramic target had large effect on the Eg values, Hall mobility, carrier concentration, and resistivity of IGZO thin films. Secondary ion mass spectrometry (SIMS) analysis in the thicknesses’ profile of IGZO thin films found that In and Ga elements were uniform distribution and Zn element were non-uniform distribution. The SIMS analysis results also showed the concentrations of Ga and Zn elements increased and the concentrations of In element was almost unchanged with increasing deposition power.

Synthesis of a colloid solution of silica-coated gold nanoparticles for X-ray imaging applications

NASA Astrophysics Data System (ADS)

Kobayashi, Yoshio; Nagasu, Ryoko; Shibuya, Kyosuke; Nakagawa, Tomohiko; Kubota, Yohsuke; Gonda, Kohsuke; Ohuchi, Noriaki

2014-08-01

This work proposes a method for fabricating silica-coated gold (Au) nanoparticles, surface modified with poly(ethylene glycol) (PEG) (Au/SiO2/PEG), with a particle size of 54.8 nm. X-ray imaging of a mouse is performed with the colloid solution. A colloid solution of 17.9 nm Au nanoparticles was prepared by reducing Au ions (III) with sodium citrate in water at 80 °C. The method used for silica-coating the Au nanoparticles was composed of surface-modification of the Au nanoparticles with (3-aminopropyl)-trimethoxysilane (APMS) and a sol-gel process. The sol-gel process was performed in the presence of the surface-modified Au nanoparticles using tetraethylorthosilicate, APMS, water, and sodium hydroxide, in which the formation of silica shells and the introduction of amino groups to the silica-coated particles took place simultaneously (Au/SiO2-NH2). Surface modification of the Au/SiO2-NH2 particles with PEG, or PEGylation of the particle surface, was performed by adding PEG with a functional group that reacted with an amino group in the Au/SiO2-NH2 particle colloid solution. A computed tomography (CT) value of the aqueous colloid solution of Au/SiO2/PEG particles with an actual Au concentration of 0.112 M was as high as 922 ± 12 Hounsfield units, which was higher than that of a commercial X-ray contrast agent with the same iodine concentration. Injecting the aqueous colloid solution of Au/SiO2/PEG particles into a mouse increased the light contrast of tissues. A CT value of the heart rose immediately after the injection, and this rise was confirmed for up to 6 h.

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.

TiO2 nanoparticles aggregation and disaggregation in presence of alginate and Suwannee River humic acids. pH and concentration effects on nanoparticle stability.

PubMed

Loosli, Frédéric; Le Coustumer, Philippe; Stoll, Serge

2013-10-15

The behavior of manufactured TiO2 nanoparticles is studied in a systematic way in presence of alginate and Suwannee River humic acids at variable concentrations. TiO2 nanoparticles aggregation, disaggregation and stabilization are investigated using dynamic light scattering and electrophoretic experiments allowing the measurement of z-average hydrodynamic diameters and zeta potential values. Stability of the TiO2 nanoparticles is discussed by considering three pH-dependent electrostatic scenarios. In the first scenario, when pH is below the TiO2 nanoparticle point of zero charge, nanoparticles exhibit a positively charged surface whereas alginate and Suwannee River humic acids are negatively charged. Fast adsorption at the TiO2 nanoparticles occurs, promotes surface charge neutralization and aggregation. By increasing further alginate and Suwannee River humic acids concentrations charge inversion and stabilization of TiO2 nanoparticles are obtained. In the second electrostatic scenario, at the surface charge neutralization pH, TiO2 nanoparticles are rapidly forming aggregates. Adsorption of alginate and Suwannee River humic acids on aggregates leads to their partial fragmentation. In the third electrostatic scenario, when nanoparticles, alginate and Suwannee River humic acids are negatively charged, only a small amount of Suwannee River humic acids is adsorbed on TiO2 nanoparticles surface. It is found that the fate and behavior of individual and aggregated TiO2 nanoparticles in presence of environmental compounds are mainly driven by the complex interplay between electrostatic attractive and repulsive interactions, steric and van der Waals interactions, as well as concentration ratio. Results also suggest that environmental aquatic concentration ranges of humic acids and biopolymers largely modify the stability of aggregated or dispersed TiO2 nanoparticles. Copyright © 2013 Elsevier Ltd. All rights reserved.

Photocatalytic growth of Ag nanocrystals on hydrothermally synthesized multiphasic TiO2/reduced graphene oxide (rGO) nanocomposites and their SERS performance

NASA Astrophysics Data System (ADS)

Guo, Tian-Long; Li, Ji-Guang; Sun, Xudong; Sakka, Yoshio

2017-11-01

TiO2/reduced graphene oxide (rGO) nanocomposites were prepared via a facile one-step hydrothermal method using TiCl3 as the TiO2 precursor. Cetyltrimethyl ammonium bromide (CTAB) was introduced as a stabilizer for GO in solution. The effects of GO content, Ti3+ concentration and urea additive on phase constituent and morphology of the TiO2 crystallites in the nanocomposites were systematically investigated. UV-vis absorption ability of the as-made composites was further tested and discussed. Ag nanocrystals (NCs) were photocatalytically grown on the surfaces of biphasic (anatase + brookite) and triphasic (anatase + brookite + rutile) TiO2/rGO nanocomposites to evaluate their surface-enhanced Raman scattering (SERS) performances. Morphology evolution of the Ag NCs in response to different photocatalytic ability of the TiO2/rGO nanocomposite was also investigated in detail. The nanocomposite with triphasic TiO2 of proper phase constituents was confirmed to favor the growth of Ag particles of two distinctly different sizes and to produce SERS substrates of substantially better performance.

Electrical DNA biosensor using aluminium interdigitated electrode for E.Coli O157:H7 detection

NASA Astrophysics Data System (ADS)

Natasha, N. Z.; Rajapaksha, R. D. A. A.; Uda, M. N. A.; Hashim, U.

2017-09-01

Escherichia Coli (E.Coli) O157:H7 is the one of the most dangerous foodborne pathogens based diseases that presence in our daily life that causes illness and death increase every year. Aluminum Interdigitated Electrode (Al IDE) biosensor was introduced to detect E.Coli O157:H7 in earlier stage. In this paper we investigated ssDNA of E.Coli O157:H7 bacteria detection through electrical behavior of Al IDE sensor. The physical properties of Al IDE biosensor has been characterized using Low Power Microscope (LPM), High Power Microscope (HPM), Scanning Electron Microscope (SEM) and 3D Nano Profiler. The bare Al IDE was electrical characterized by using I-V measurement. The surface modification was accomplished by salinization using APTES and immobilization using Carboxylic Probe E.Coli which was the first step in preparing Al IDE biosensor. Geared up prepared biosensor was hybridized with complementary, non-complementary and single based mismatch ssDNA to confirmed specificity detection of E Coli O157:H7 ssDNA target. The Current - Voltage was performed for each step such as bare Al IDE, surface modification, immobilization and hybridization. Sensitivity measurement was accomplished using different concentration of complementary ssDNA target from 1 fM - 10 µM. Selectivity measurements was achieved using same concentration which was 10 µM concentration for complement, non-complement and mismatch E.Coli O157:H7 ssDNA target. It's totally proved that the Al IDE able to detect specific and small current down to Femtomolar concentration.

Monodisperse magnetite (Fe3O4) nanoparticles modified with water soluble polymers for the diagnosis of breast cancer by MRI method

NASA Astrophysics Data System (ADS)

Rezayan, Ali Hossein; Mousavi, Majid; Kheirjou, Somayyeh; Amoabediny, Ghasem; Ardestani, Mehdi Shafiee; Mohammadnejad, Javad

2016-12-01

In this study, magnetic nanoparticles (MNPs) were synthesized via co-precipitation method. To enhance the biocompatibility and colloidal stability of the synthesized nanoparticles, they were modified with carboxyl functionalized PEG via dopamine (DPA) linker. Both modified and unmodified Fe3O4 nanoparticles exhibited super paramagnetic behavior (particle size below 20 nm). The saturation magnetization (Ms) of PEGdiacid-modified Fe3O4 was 45 emu/g, which was less than the unmodified Fe3O4 nanoparticles (70 emu/g). This difference indicated that PEGdiacid polymer was immobilized on the surface of Fe3O4 nanoparticles successfully. To evaluate the efficiency of the resulting nanoparticles as contrast agents for magnetic resonance imaging (MRI), different concentration of MNPs and different value of echo time TE were investigated. The results showed that by increasing the concentration of the nanoparticles, transverse relaxation time (T2) decreased, which subsequently resulted in MR signal enhancement. T2-weighted MR images of the different concentration of MNPs in different value of echo time TE indicated that MR signal intensity increased with increase in TE value up to 66 and then remained constant. The cytotoxicity effect of the modified and unmodified nanoparticles was evaluated in three different concentrations (12, 60 and 312 mg l-1) on MDA-MB-231 cancer cells for 24 and 48 h. In both tested time (24 and 48 h) for all three samples, the modified nanoparticles had long life time than unmodified nanoparticles. Cellular uptake of modified MNPs was 80% and reduced to 9% by the unmodified MNPs.

Source apportionment of surface ozone in the Yangtze River Delta, China in the summer of 2013

NASA Astrophysics Data System (ADS)

Li, L.; An, J. Y.; Shi, Y. Y.; Zhou, M.; Yan, R. S.; Huang, C.; Wang, H. L.; Lou, S. R.; Wang, Q.; Lu, Q.; Wu, J.

2016-11-01

We applied ozone source apportionment technology (OSAT) with tagged tracers coupled within the Comprehensive Air Quality Model with Extensions (CAMx) to study the region and source category contribution to surface ozone in the Yangtze River Delta area in summer of 2013. Results indicate that the daytime ozone concentrations in the YRD region are influenced by emissions both locally, regionally and super-regionally. At urban Shanghai, Hangzhou and Suzhou receptors, the ozone formation is mainly VOC-limited, precursor emissions form Zhejiang province dominate their O3 concentrations. At the junction area among two provinces and Shanghai city, the ozone is usually influenced by all the three areas. The daily max O3 at the Dianshan Lake in July are contributed by Zhejiang (48.5%), Jiangsu (11.7%), Anhui (11.6%) and Shanghai (7.4%), long-range transport constitutes around 20.9%. At Chongming site, the BVOC emissions rate is higher than urban region. Regional contribution results show that Shanghai constitutes 15.6%, Jiangsu contributes 16.2% and Zhejiang accounts for 25.5% of the daily max O3. The analysis of the source category contribution to high ozone in the Yangtze River Delta region indicates that the most significant anthropogenic emission source sectors contributing to O3 pollution include industry, vehicle exhaust, although the effects vary with source sector and selected pollution episodes. Emissions of NOx and VOCs emitted from the fuel combustion of industrial boilers and kilns, together with VOCs emissions from industrial process contribute a lot to the high concentrations in urban Hangzhou, Suzhou and Shanghai. The contribution from regional elevated power plants cannot be neglected, especially to Dianshan Lake. Fugitive emissions of volatile pollution sources also have certain contribution to regional O3. These results indicate that the regional collaboration is of most importance to reduce ambient ozone pollution, particularly during high ozone episodes.

Glass-ceramic nuclear waste forms obtained by crystallization of SiO 2-Al 2O 3-CaO-ZrO 2-TiO 2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th): Study of the crystallization from the surface

NASA Astrophysics Data System (ADS)

Loiseau, P.; Caurant, D.

2010-07-01

Glass-ceramic materials containing zirconolite (nominally CaZrTi 2O 7) crystals in their bulk can be envisaged as potential waste forms for minor actinides (Np, Am, Cm) and Pu immobilization. In this study such matrices are synthesized by crystallization of SiO 2-Al 2O 3-CaO-ZrO 2-TiO 2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th) as surrogates. A thin partially crystallized layer containing titanite and anorthite (nominally CaTiSiO 5 and CaAl 2Si 2O 8, respectively) growing from glass surface is also observed. The effect of the nature and concentration of surrogates on the structure, the microstructure and the composition of the crystals formed in the surface layer is presented in this paper. Titanite is the only crystalline phase able to significantly incorporate trivalent lanthanides whereas ThO 2 precipitates in the layer. The crystal growth thermal treatment duration (2-300 h) at high temperature (1050-1200 °C) is shown to strongly affect glass-ceramics microstructure. For the system studied in this paper, it appears that zirconolite is not thermodynamically stable in comparison with titanite growing form glass surface. Nevertheless, for kinetic reasons, such transformation (i.e. zirconolite disappearance to the benefit of titanite) is not expected to occur during interim storage and disposal of the glass-ceramic waste forms because their temperature will never exceed a few hundred degrees.

Adsorption Assisted Photocatalytic Removal of Methyl Orange by MgAl2O4-Sb2S3 Composite Material.

PubMed

Muneeb, Muhammad; Ismail, Bushra; Fazal, Tanzeela; Khan, Abdur Rehman; Afzia, Mehwish

2016-01-01

The current article is about the water treatment in which colored water contaminated by methyl orange has been used for adsorption assisted photocatalysis. Coupling of photocatalysis with the traditional water treatment processes has been in practice since last couple of years for the improvement of degradation efficiencies, for example, photocatalysis coupled with ultrafilteration, adsorption, flocculation, biological methods, photolysis, membrane distillation, etc. Among all these coupling approaches, adsorption assisted photocatalysis being a very simple and highly efficient approach is suffering from few drawbacks on the account of high cost, low stability and surface area of the adsorbent support. The present study is a contribution towards improvement in this coupling approach. A low cost, highly stable spinel magnesium aluminate (MgAl2O4) material synthesized at nanoscale is used for composite formation with antimony sulphide (Sb2S3) material having high absorption coefficient in the visible light of solar spectrum. A review of recent patents shows that the field of photoctalysis is dominated by the traditional TiO2 catalyst. The modification of TiO2 by either composite formation or by doping is the main focus. Coprecipitation method is used for the synthesis of spinel in which the desired precursors in the respective molar ratios were mixed and annealing of the resulting precipitates was carried out at 800oC for 8 h. Sb2S3 was synthesized by the hydrothermal method in which the required molar solution of precursors was mixed with urea solution and the whole mixture was maintained at 105oC for 6 hrs in a Teflon lined autoclave. The resulting suspension was then annealed at 37oC for 3 hours. The composite of Sb2S3 and MgAl2O4 has been synthesized by mixing both the materials in 1:1 and heat treated in an oven at a temperature of 200oC. Peaks in X-ray diffraction pattern correspond to both the Sb2S3 and spinel phase. All the peaks corresponding to the Sb2S3 and spinel phase were found to be shifted to higher d-spacing values. This indicates the expansion of unit cells of the Sb2S3 and MgAl2O4 phases. Thermal studies show that only 3% weight loss is observed at a temperature of 200-1000oC which may be due to the loss of surface water from the sample. Surface area, pore volume and pore size obtained from N2 adsorption were 143m2/g, 0.21cc/g and 23.26Å, respectively. The removal efficiency of 0.1g catalyst for methyl orange solution of 5mg/L concentration after reaction in dark conditions for the time of one hour was calculated to be 24% owing to the adsorption. The visible light degradation efficiency of the 0.1g catalyst for 1, 5, 19, 25 and 50 mg/L concentrations of MO solutions were 97, 93, 75, 72 and 62% respectively. The dosage of the catalyst was found to have a direct relationship with the degradation efficiency. Lower pH was found suitable for the degradation owing to better interaction of catalyst surface and the adsorbed dye. Percent degradation increased with the increase in the time and temperature of reaction. The degradation kinetics followed pseudo first order rate equation; the calculated value of rate constant was 0.0102 min-1. The mechanism involves the excitation of electrons in the valence band of Sb2S3 to the conduction band by the absorption of visible and UV light. The electrons and holes participate in the surface reactions resulting in the formation of superoxide and hydroxyl radicals which degrade the targeted polluted. Lower concentration of MO solutions, acidic pH, higher catalyst dosage and greater reaction times were found suitable for the degradation efficiency.

Quantifying the Impact of Tropospheric Ozone on Crops Productivity at regional scale using JULES-crop

NASA Astrophysics Data System (ADS)

Leung, F.

2016-12-01

Tropospheric ozone (O3) is the third most important anthropogenic greenhouse gas. It is causing significant crop production losses. Currently, O3 concentrations are projected to increase globally, which could have a significant impact on food security. The Joint UK Land Environment Simulator modified to include crops (JULES-crop) is used here to quantify the impacts of tropospheric O3 on crop production at the regional scale until 2100. We evaluate JULES-crop against the Soybean Free-Air-Concentration-Enrichment (SoyFACE) experiment in Illinois, USA. Experimental data from SoyFACE and various literature sources is used to calibrate the parameters for soybean and ozone damage parameters in soybean in JULES-crop. The calibrated model is then applied for a transient factorial set of JULES-crop simulations over 1960-2005. Simulated yield changes are attributed to individual environmental drivers, CO2, O3 and climate change, across regions and for different crops. A mixed scenario of RCP 2.6 and RCP 8.5 climatology and ozone are simulated to explore the implication of policy. The overall findings are that regions with high ozone concentration such as China and India suffer the most from ozone damage, soybean is more sensitive to O3 than other crops. JULES-crop predicts CO2 fertilisation would increase the productivity of vegetation. This effect, however, is masked by the negative impacts of tropospheric O3. Using data from FAO and JULES-crop estimated that ozone damage cost around 55.4 Billion USD per year on soybean. Irrigation improves the simulation of rice only, and it increases the relative ozone damage because drought can reduce the ozone from entering the plant stomata. RCP 8.5 scenario results in a high yield for all crops mainly due to the CO2 fertilisation effect. Mixed climate scenarios simulations suggest that RCP 8.5 CO2 concentration and RCP 2.6 O3 concentration result in the highest yield. Further works such as more crop FACE-O3 experiments and more Crop functional types in JULES are necessary. The model will thus contribute to a complete understanding of the impacts of climate change on food production. JULES will be later coupled with the Unified Model to quantify the impact of tropospheric O3 on crops productivity including feedbacks between the land-surface, atmospheric chemistry and climate change.

Development of a fully integrated falling film microreactor for gas-liquid-solid biotransformation with surface immobilized O2 -dependent enzyme.

PubMed

Bolivar, Juan M; Krämer, Christina E M; Ungerböck, Birgit; Mayr, Torsten; Nidetzky, Bernd

2016-09-01

Microstructured flow reactors are powerful tools for the development of multiphase biocatalytic transformations. To expand their current application also to O2 -dependent enzymatic conversions, we have implemented a fully integrated falling film microreactor that provides controllable countercurrent gas-liquid phase contacting in a multi-channel microstructured reaction plate. Advanced non-invasive optical sensing is applied to measure liquid-phase oxygen concentrations in both in- and out-flow as well as directly in the microchannels (width: 600 μm; depth: 200 μm). Protein-surface interactions are designed for direct immobilization of catalyst on microchannel walls. Target enzyme (here: d-amino acid oxidase) is fused to the positively charged mini-protein Zbasic2 and the channel surface contains a negatively charged γ-Al2 O3 wash-coat layer. Non-covalent wall attachment of the chimeric Zbasic2 _oxidase resulted in fully reversible enzyme immobilization with fairly uniform surface coverage and near complete retention of biological activity. The falling film at different gas and liquid flow rates as well as reactor inclination angles was shown to be mostly wavy laminar. The calculated film thickness was in the range 0.5-1.3 × 10(-4)  m. Direct O2 concentration measurements at the channel surface demonstrated that the liquid side mass transfer coefficient (KL ) for O2 governed the overall gas/liquid/solid mass transfer and that the O2 transfer rate (≥0.75 mM · s(-1) ) vastly exceeded the maximum enzymatic reaction rate in a wide range of conditions. A value of 7.5 (±0.5) s(-1) was determined for the overall mass transfer coefficient KL a, comprising a KL of about 7 × 10(-5)  m · s(-1) and a specific surface area of up to 10(5)  m(-1) . Biotechnol. Bioeng. 2016;113: 1862-1872. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Direct conversion from Jerusalem artichoke to hydroxymethylfurfural (HMF) using the Fenton reaction.

PubMed

Seo, Yeong Hwan; Han, Jong-In

2014-05-15

A simple method for hydroxymethylfurfural (HMF) production from non-crop biomass of the Jerusalem artichoke was developed using the Fenton reaction, in a mixture of 2-butanol and water. Four parameters (temperature, reaction time, Fe(2+) concentration, and H2O2 concentration) were identified as experimental factors, and HMF yield was selected as the response parameter. The experimental factors were optimised by employing Response Surface Methodology (RSM). The maximum HMF yield, of 46%, was obtained with a reaction time of 90 min, Fe(2+) concentration of 1.3 mM, and 0.47 M of H2O2 at 180 °C. Copyright © 2014. Published by Elsevier Ltd.

Preparation of porous magnesium oxide foam and study on its enrichment of uranium

NASA Astrophysics Data System (ADS)

Wang, Yunsheng; Chen, Yuantao; Liu, Chen; Yu, Fang

2018-06-01

Herein, we prepared porous magnesium oxide (MP-MgO) by in situ carbonization and using Mg(NO3)2 as precursor along with P123 as soft template. The BET surface area, and total pore volume of MP-MgO were found to be 14.76 m2 g, 0.15 cm3 g-1, respectively. The adsorption behavior of U (Ⅵ) by the porous MgO was studied by static adsorption experiments, and also the effects of adsorption time, pH of wastewater and U (Ⅵ) concentration were discussed. The results indicated that the optimum pH for MP-MgO was 3.0-4.5, the removal of uranium in this case was mainly due to surface complexation. Through the study, we found that the adsorption capacity of MP-MgO for uranium was more than 2500 mg g-1, the adsorption equilibrium time was about 150 min. Moreover, the kinetic study showed that the process followed the pseudo-first-order model, and the adsorption process was spontaneous and endothermic.

Synthesis of Cu/SiO2 Core-Shell Particles Using Hyperbranched Polyester as Template and Dispersant

NASA Astrophysics Data System (ADS)

Han, Wensong

2017-07-01

Third-generation hyperbranched polyester (HBPE3) was synthesized by stepwise polymerization with N, N-diethylol-3-amine methylpropionate as AB2 monomer and pentaerythritol as core molecule. Then, Cu particles were prepared by reduction of copper nitrate with ascorbic acid in aqueous solution using HBPE3 as template. Finally, Cu/SiO2 particles were prepared by coating silica on the surface of Cu particles. The structure and morphology of the samples were characterized by Fourier-transform infrared (FT-IR) spectrometry, x-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results confirmed the formation of the silica coating on the surface of Cu and that the Cu/SiO2 particles had spherical shape with particle size in the range of 0.8 μm to 2 μm. Compared with pure Cu, the synthesized Cu/SiO2 core-shell particles exhibited better oxidation resistance at high temperature. Moreover, the oxidation resistance of the Cu/SiO2 particles increased significantly with increasing tetraethyl orthosilicate (TEOS) concentration.

The influence of photoelectron processes in a semiconductor substrate on the adsorption of polycationic and polyanionic molecules

NASA Astrophysics Data System (ADS)

Stetsyura, S. V.; Kozlowski, A. V.

2017-03-01

White-light illumination during the adsorption of polyanionic molecules of glucose oxidase (GO x ) enzyme on the surface of p-Si/SiO2/polyethylenimine structure leads to a threefold decrease in the surface concentration of GO x molecules. Same illumination during the GO x adsorption on the n-Si/SiO2/PEI structure leads to a sevenfold increase in the surface concentration of enzyme molecules. Changes in the amount of adsorbed GO x molecules depending on the intensity of irradiation are explained by electron transfer processes and recharging of electronic states at the Si/SiO2 interface and within SiO2 layer.

Mg-containing hydroxyapatite coatings on Ti-6Al-4V alloy for dental materials

NASA Astrophysics Data System (ADS)

Yu, Ji-Min; Choe, Han-Cheol

2018-02-01

In this study, Mg-containing hydroxyapatite coatings on Ti-6A1-4 V alloy for dental materials were researched using various experimental instruments. Plasma electrolytic oxidation (PEO) was performed in electrolytes containing Mg (symbols of specimens: CaP, 5M%, 10M%, and 20M%) at 280 V for 3 min. The electrolyte used for PEO was produced by mixing Ca(CH3COO)2·H2O, C3H7NaCaO6P, and MgCl2·6H2O. The phases and composition of the oxide films were evaluated by X-ray diffraction and field-emission scanning electron microscopy with energy dispersive X-ray spectrometry. The irregularity of the surface, pore size, and number of pores decreased as the Mg concentration increased. The ratio of the areas occupied and not occupied by pores decreased as the Mg concentration increased, with the numbers of both large and small pores decreasing with increasing Mg concentration. The number of particles on the internal surfaces of pores was increased as the Mg content increased. Mg content of all samples containing Mg ions showed higher in the pore outside than that of pore inside, whereas the Ca content was higher inside the pores. The P content of samples with the addition of Mg ions showed higher values inside the pores than outside. The Ca/P and [Mg + Ca]/P molar ratios in the PEO films decreased with Mg content. The crystallite size of anatase was increased with increasing Mg concentration in the solution.

Enhanced performance of inverted organic photovoltaic cells using CNTs-TiO(X) nanocomposites as electron injection layer.

PubMed

Zhang, Hong; Xu, Meifeng; Cui, Rongli; Guo, Xihong; Yang, Shangyuan; Liao, Liangsheng; Jia, Quanjie; Chen, Yu; Dong, Jinquan; Sun, Baoyun

2013-09-06

In this study, we fabricated inverted organic photovoltaic cells with the structure ITO/carbon nanotubes (CNTs)-TiO(X)/P3HT:PCBM/MoO₃/Al by spin casting CNTs-TiO(X) nanocomposite (CNTs-TiO(X)) as the electron injection layer onto ITO/glass substrates. The power conversion efficiency (PCE) of the 0.1 wt% single-walled nanotubes (SWNTs)-TiO(X) nanocomposite device was almost doubled compared with the TiO(X) device, but with increasing concentration of the incorporated SWNTs in the TiO(X) film, the performance of the devices appeared to decrease rapidly. Devices with multi-walled NTs in the TiO(X) film have a similar trend. This phenomenon mainly depends on the inherent physical and chemical characteristics of CNTs such as their high surface area, their electron-accepting properties and their excellent carrier mobility. However, with increasing concentration of CNTs, CNTs-TiO(X) current leakage pathways emerged and also a recombination of charges at the interfaces. In addition, there was a significant discovery. The incorporated CNTs were highly conducive to enhancing the degree of crystallinity and the ordered arrangement of the P3HT in the active layers, due to the intermolecular π-π stacking interactions between CNTs and P3HT.

Optimization of photocatalytic degradation of palm oil mill effluent in UV/ZnO system based on response surface methodology.

PubMed

Ng, Kim Hoong; Cheng, Yoke Wang; Khan, Maksudur R; Cheng, Chin Kui

2016-12-15

This paper reports on the optimization of palm oil mill effluent (POME) degradation in a UV-activated-ZnO system based on central composite design (CCD) in response surface methodology (RSM). Three potential factors, viz. O 2 flowrate (A), ZnO loading (B) and initial concentration of POME (C) were evaluated for the significance analysis using a 2 3 full factorial design before the optimization process. It is found that all the three main factors were significant, with contributions of 58.27% (A), 15.96% (B) and 13.85% (C), respectively, to the POME degradation. In addition, the interactions between the factors AB, AC and BC also have contributed 4.02%, 3.12% and 1.01% to the POME degradation. Subsequently, all the three factors were subjected to statistical central composite design (CCD) analysis. Quadratic models were developed and rigorously checked. A 3D-response surface was subsequently generated. Two successive validation experiments were carried out and the degradation achieved were 55.25 and 55.33%, contrasted with 52.45% for predicted degradation value. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development of surface functionalized ZnO-doped LiFePO4/C composites as alternative cathode material for lithium ion batteries

NASA Astrophysics Data System (ADS)

Saroha, Rakesh; Panwar, Amrish K.; Sharma, Yogesh; Tyagi, Pawan K.; Ghosh, Sudipto

2017-02-01

Surface modified olivine-type LiFePO4/C-ZnO doped samples were synthesized using sol-gel assisted ball-milling route. In this work, the influence of ZnO-doping on the physiochemical, electrochemical and surface properties such as charge separation at solid-liquid interphase, surface force gradient, surface/ionic conductivity of pristine LiFePO4/C (LFP) has been investigated thoroughly. Synthesized samples were characterized using X-ray diffraction, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. All the synthesized samples were indexed to the orthorhombic phase with Pnma space group. Pristine LiFePO4 retain its structure for higher ZnO concentrations (i.e. 2.5 and 5.0 wt.% of LFP). Surface topography and surface force gradient measurements by EFM revealed that the kinetics of charge carriers, e-/Li+ is more in ZnO-doped LFP samples, which may be attributed to diffusion or conduction process of the charges present at the surface. Among all the synthesized samples LFP/C with 2.5 wt.% of ZnO (LFPZ2.5) displays the highest discharge capacity at all C-rates and exhibit excellent rate performance. LFPZ2.5 delivers a specific discharge capacity of 164 (±3) mAh g-1 at 0.1C rate. LFPZ2.5 shows best cycling performance as it provides a discharge capacity of 135 (±3) mAh g-1 at 1C rate and shows almost 95% capacity retention after 50 charge/discharge cycles. Energy density plot shows that LFPZ2.5 offers high energy and power density measured at high discharge rates (5C), proving its usability for hybrid vehicles application.

Solid frustrated-Lewis-pair catalysts constructed by regulations on surface defects of porous nanorods of CeO2

PubMed Central

Zhang, Sai; Huang, Zheng-Qing; Ma, Yuanyuan; Gao, Wei; Li, Jing; Cao, Fangxian; Li, Lin; Chang, Chun-Ran; Qu, Yongquan

2017-01-01

Identification on catalytic sites of heterogeneous catalysts at atomic level is important to understand catalytic mechanism. Surface engineering on defects of metal oxides can construct new active sites and regulate catalytic activity and selectivity. Here we outline the strategy by controlling surface defects of nanoceria to create the solid frustrated Lewis pair (FLP) metal oxide for efficient hydrogenation of alkenes and alkynes. Porous nanorods of ceria (PN-CeO2) with a high concentration of surface defects construct new Lewis acidic sites by two adjacent surface Ce3+. The neighbouring surface lattice oxygen as Lewis base and constructed Lewis acid create solid FLP site due to the rigid lattice of ceria, which can easily dissociate H–H bond with low activation energy of 0.17 eV. PMID:28516952

Optical, electrochemical and hydrophilic properties of Y2O3 doped TiO2 nanocomposite films.

PubMed

Zhang, Xiangchao; Yang, Huaming; Tang, Aidong

2008-12-25

The 5% Y2O3 doped TiO2 nanocomposite film (YTF) deposited on ITO glass substrate has been synthesized by the sol-gel dip-coating method. The as-synthesized samples were characterized using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), voltage-current (V-I), electrochemical impedance spectroscopy (EIS) and ultraviolet-visible (UV-vis) analysis technologies. The crystalline structure, surface morphology and surface chemical composition of YTF sample have been primarily investigated. The results demonstrate that YTF is anatase crystalline phase with thickness of 480 nm and consists of spherical shape particles with a grain size of about 15.8 nm. The binding energy appears as a chemical shift, and relatively more Y and Ti species are present on the surface, indicating that active surfaces of the nanocomposite film have been enhanced with more oxygen vacancies Vö due to doping Y2O3 to TiO2. The absorption edge of YTF has a red shift, and the optical properties of YTF in visible light region have been obviously improved. The water contact angle is about 8 degrees after daylight lamp irradiation 60 min. An equivalent circuit model provided a reliable description for the electrochemical systems. Based on the Mott-Schottky equation, the donor concentration (ND) for YTF is 1.05 x 10(20) cm(-3), which enhances 1 order of magnitude than that for pure TiO2 film (TF), the flat-band potential (V(fb)) and the space charge layer (d(sc)) obviously decreased. With the incorporation of Y2O3 into TiO2, the optical, electrochemical and photoinduced hydrophilic properties of YTF in visible light region have obviously improved, indicating that YTF shows promising applications in solar energy conversion, self-cleaning and other potential fields.

Direct detection of cysteine using functionalized BaTiO3 nanoparticles film based self-powered biosensor.

PubMed

Selvarajan, Sophia; Alluri, Nagamalleswara Rao; Chandrasekhar, Arunkumar; Kim, Sang-Jae

2017-05-15

Simple, novel, and direct detection of clinically important biomolecules have continuous demand among scientific community as well as in market. Here, we report the first direct detection and facile fabrication of a cysteine-responsive, film-based, self-powered device. NH 2 functionalized BaTiO 3 nanoparticles (BT-NH 2 NPs) suspended in a three-dimensional matrix of an agarose (Ag) film, were used for cysteine detection. BaTiO 3 nanoparticles (BT NPs) semiconducting as well as piezoelectric properties were harnessed in this study. The changes in surface charge properties of the film with respect to cysteine concentrations were determined using a current-voltage (I-V) technique. The current response increased with cysteine concentration (linear concentration range=10µM-1mM). Based on the properties of the composite (BT/Ag), we created a self-powered cysteine sensor in which the output voltage from a piezoelectric nanogenerator was used to drive the sensor. The potential drop across the sensor was measured as a function of cysteine concentrations. Real-time analysis of sensor performance was carried out on urine samples by non-invasive method. This novel sensor demonstrated good selectivity, linear concentration range and detection limit of 10µM; acceptable for routine analysis. Copyright © 2016 Elsevier B.V. All rights reserved.