The mercury sensitized oxidation of carbon monoxide
Mercury photosensitized oxidation of CO at 275 C
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Mercury photosensitized oxidation of CO at 275 C
Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10degN to 40degS), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (approx.3.4 pptv at 13.5 km), and are 2-4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5-6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.
The research projects and new technological developments that have occured in Russia are highlighted in this document. Some of the research discussed includes: x-ray structure analysis of YBCO superconducting single crystals and accompanying phase transformations; the role of electron-electron interaction in High Temperature Superconductors (HTSC); the formation of Cooper pairs in crystals; the synthesis and research on a new family of superconductors based on complex copper and mercury oxides (HgBa2CuO4 + alpha and HgBa2CaCu2O6 + alpha); methods for the extraction of higher (up to C200) fullerenes and metalfullerenides has been developed; and process of production of Josephson junctions and development of SQUID's.
Tropospheric chemistry of halogens and organic carbon over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically resolved measurements of bromine monoxide (BrO), iodine monoxide (IO) and small oxygenated hydrocarbons like glyoxal (CHOCHO) in the tropical troposphere. BrO, IO, glyoxal, nitrogen dioxide (NO2), water vapor (H2O) and O2-O2 collision complexes (O4/ were measured by the University of Colorado Airborne Multi-AXis Differential Optical Absorption Spectroscopy (CU AMAXDOAS) instrument, aerosol extinction by high spectral resolution lidar (HSRL), in situ aerosol size distributions by an ultra high sensitivity aerosol spectrometer (UHSAS) and in situ H2O by vertical-cavity surface-emitting laser (VCSEL) hygrometer. Data are presented from two research flights (RF12, RF17) aboard the National Science Foundation/ National Center for Atmospheric Research Gulfstream V aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project (January/February 2012). We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols. Our O4-inferred aerosol extinction profiles at 477 nm agree within 6% with HSRL in the boundary layer and closely resemble the renormalized profile shape of Mie calculations constrained by UHSAS at low (sub-Rayleigh) aerosol extinction in the free troposphere. CU AMAX-DOAS provides a flexible choice of geometry, which we exploit to minimize the SCD in the reference spectrum (SCDREF, maximize signal-to-noise ratio) and to test the robustness of BrO, IO and glyoxal differential SCDs. The RF12 case study was conducted in pristine marine and free tropospheric air. The RF17 case study was conducted above the NOAA RV Ka'imimoana (TORERO cruise, KA-12-01) and provides independent validation data from ship-based in situ cavity-enhanced DOAS and MAX-DOAS. Inside the marine boundary layer (MBL) no BrO was detected (smaller than 0.5 pptv), and 0.2-0.55 pptv IO and 32-36 pptv glyoxal were observed. The near-surface concentrations agree within 30% (IO) and 10% (glyoxal) between ship and air-craft. The BrO concentration strongly increased with altitude to 3.0 pptv at 14.5 km (RF12, 9.1 to 8.6 deg N; 101.2 to 97.4 deg W). At 14.5 km, 5-10 pptv NO2 agree with model predictions and demonstrate good control over separating tropospheric from stratospheric absorbers (NO2 and BrO). Our profile retrievals have 12-20 degrees of freedom (DoF) and up to 500m vertical resolution. The tropospheric BrO vertical column density (VCD) was 1.5 x 10(exp 13) molec cm(exp -2) (RF12) and at least 0.5 x 10(exp 13) molec cm(exp -2) (RF17, 0- 10 km, lower limit). Tropospheric IO VCDs correspond to 2.1 x 10(exp 12) molec cm(exp -2) (RF12) and 2.5 x 10(exp 12) molec cm(exp -2) (RF17) and glyoxal VCDs of 2.6 x 10(exp 14) molec cm(exp -2) (RF12) and 2.7 x 10(exp 14) molec cm(exp -2) (RF17). Surprisingly, essentially all BrO as well as the dominant IO and glyoxal VCD fraction was located above 2 km (IO: 58 plus or minus 5 %, 0.1-0.2 pptv; glyoxal: 52 plus or minus 5 %, 3-20 pptv). To our knowledge there are no previous vertically resolved measurements of BrO and glyoxal from aircraft in the tropical free troposphere. The atmospheric implications are briefly discussed. Future studies are necessary to better understand the sources and impacts of free tropospheric halogens and oxygenated hydrocarbons on tropospheric ozone, aerosols, mercury oxidation and the oxidation capacity of the atmosphere.
Oxide cathode durability in mercury electron bombardment ion thrustor
Design, fabrication, and life test of ion engine system using oxide cathode mercury electron bombardment thrustor
Redox variations of terrestrial and lunar basalts and the redox variations in single cooling units (e.g., lava flows and lava lakes) are reviewed. Estimates for the redox states of inner solar system planetary basalts are presented; these estimates are based on consideration of a number of cosmogenic properties, models for planetary interiors, and the sequence of condensation with heliocentric distance from the protosun. It is suggested that basalts on Mercury and the Moon crystallized below the iron-wustite buffer curve; Venusian basalts are more oxidized than those on Mercury, less oxidized than those on earth, and crystallization within the field of wustite stability is thought likely; basalts on earth are dominantly in the field of magnetite stability; Martian basalts are estimated to crystallize in the upper regions of magnetite stability and well into the hematite field of stability expressed in terms of temperature and oxygen fugacity.
Mercury is the least oxidized terrestrial planet of the solar system and is enriched in sulfur, which may be saturated in its mantle, possibly forming Ca- and Mg-rich sulfides. Using literature experimental data, we developed a thermodynamic model for calcium and magnesium partitioning between sulfide and silicate melts to enhance our understanding of the chemical equilibria involved in Mercury’s mantle-crust differentiation. Our models show that temperature and carbon abundance in sulfide have a positive effect on Ca partitioning into sulfides, while pressure decreases it. In addition, carbon abundance and sulfur concentration in the silicate melt are the primary controls on Mg partitioning, both favoring Mg partitioning into sulfides. Our results will be used to better understand the abundance as well as presence of calcium and magnesium sulfides within Mercury’s mantle and crust.
Evacuated apparatus determines the alkali oxide content of an alkali metal by separating the metal from the oxide by amalgamation with mercury. The apparatus prevents oxygen and moisture from inadvertently entering the system during the sampling and analytical procedure.
We present a new model for the global tropospheric chemistry of inorganic bromine (Bry) coupled to oxidant-aerosol chemistry in the GEOS-Chem chemical transport model (CTM). Sources of tropospheric Bry include debromination of sea-salt aerosol, photolysis and oxidation of short-lived bromocarbons, and transport from the stratosphere. Comparison to a GOME-2 satellite climatology of tropospheric BrO columns shows that the model can reproduce the observed increase of BrO with latitude, the northern mid-latitudes maximum in winter, and the Arctic maximum in spring. This successful simulation is contingent on the HOBr + HBr reaction taking place in aqueous aerosols and ice clouds. Bromine chemistry in the model decreases tropospheric ozone mixing ratios by <1-8 nmol/mol (6.5% globally), with the largest effects in the northern extratropics in spring. The global mean tropospheric OH concentration decreases by 4 %. Inclusion of bromine chemistry improves the ability of global models (GEOS-Chem and p-TOMCAT) to simulate observed 19th-century ozone and its seasonality. Bromine effects on tropospheric ozone are comparable in the present-day and pre-industrial atmospheres so that estimates of anthropogenic radiative forcing are minimally affected. Br atom concentrations are 40% higher in the pre-industrial atmosphere due to lower ozone, which would decrease by a factor of 2 the atmospheric lifetime of elemental mercury against oxidation by Br. This suggests that historical anthropogenic mercury emissions may have mostly deposited to northern mid-latitudes, enriching the corresponding surface reservoirs. The persistent rise in background surface ozone at northern mid-latitudes during the past decades could possibly contribute to the observations of elevated mercury in subsurface waters of the North Atlantic.
A study on the field-induced surface-charge region in 3C silicon carbide (SiC) using 1 MHz capacitance-voltage (C-V) measurements at room temperature is here reported. A double column mercury probe was used on oxidized SiC substrates to form metal-oxide-semiconductor (MOS) structures. These structures were characterized in terms of the substrate doping profile, effective fixed oxide charge, and interface trap density. A distinctive feature of the MOS C-V curves from accumulation to inversion is that after going into deep depletion the capacitance rises to its equilibrium inversion level during the voltage sweep. Capacitance transient measurements indicate that the minority-carrier generation occurs at the SiO2/SiC interface.
Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3) is photolyzed at 254 nm to produce O(1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO+NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D)+N2O->2NO, followed by the reaction NO+O3->NO2+O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D)+N2O reactions can be used to systematically vary the relative branching ratio of RO2 +NO reactions relative to RO2 +HO2 and/or RO2+RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO-3 ) reagent ion to detect gas-phase oxidation products of isoprene and -pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.
Analyses of Mars spectra reveal that primary minerals may be more iron rich than average basalts on Earth, and the oxidation state of iron in the pyroxines suggests equally high or higher oxygen fugacities on Mars than Earth. Analysis of Mercury spectra reveal that silicate iron contents are substantially lower than those on Mars. Mercury, however, probably has a substantial iron core. This is consistent with a lower oxidation state of iron on Mercury than on Mars. These findings are consistent with predictions of models of equilibrium condensation and homogeneous accretion. Those models predict that Mercury would have negligible Fe(2+) in silicates (Fe/Fe+Mg approx. 0.5). For Mercury iron should be virtually all metallic, while for Mars the iron would be all oxidized as FeS and silicate. Surface measurements of Fe/Fe+Mg on Venus, Earth, and Mars further support the predicted relative increase in Fe/Fe+Mg ratio (increased oxidation state) with distance from the Sun. The implied high oxygen fugacities on Mars (Fe(3+) in silicates) provide additional consistence with the model predictions.
We present new optical (0.4-0.65 micron) spectra of Mercury and lunar pure anorthosite locations, obtained quasi-simultaneously with the Nordic Optical Telescope (NOT) in 2002. A comparative study is performed with the model of Lucey et al. between iron-poor, mature, pure anorthosite (less than 90% plagioclase feldspar) Clementine spectra from the lunar farside and a combined 0.4-1.0 micron mercurian spectrum, obtained with the NOT, calculated for standard photometric geometry. Mercury is located at more extreme locations in the Lucey ratio-reflectance diagrams than any known lunar soil, specifically with respect to the extremely iron-poor mature anorthosites. Though quantitative prediction of FeO and TiO2 abundances cannot be made without a more generally applicable model, we find qualitatively that the abundances of both these oxides must be near zero for Mercury. We utilize the theory of Hapke, with realistic photometric parameters, to model laboratory spectra of matured mineral powders and lunar soils, and remotely sensed spectra of lunar anorthosites and Mercury. An important difference between fabricated and natural powders is the high value for the internal scattering parameter necessary to interpret the spectra for the former, and the requirement of rough and non-isotropically scattering surfaces in the modelling of the latter. The mature lunar anorthosite spectra were well modelled with binary mixtures of calcic feldspars and olivines, grain sizes of 25-30 micron and a concentration of submicroscopic metallic iron (SMFe) of 0.12-0.15% in grain coatings. The mercurian spectrum is not possible to interpret from terrestrial mineral powder spectra without introducing an average particle scattering function for the bulk soil that increases in backscattering efficiency with wavelength. The observed spectrum is somewhat better predicted with binary mixture models of feldspars and pyroxenes, that single-component regoliths consisting of either albite or diopside. Correct spectral reflectance values were predicted with a concentration of 0.1 wt% SMFe in coatings of 15-30 micron sized grains. Since reasonable cosmogonical formation scenarios for Mercury, or meteoritic infall, predict iron concentrations at least this high, we draw the conclusion that the average grain size of Mercury is about a factor of two smaller than for average returned lunar soil samples. The 0.6-2.5 micron spectrum of McCord and Clark is used to further limit the possible range of mineralogical composition of Mercury. It is found that an intimately mixed and matured 3 : 1 labradorite-to-enstatite regolith composition best matches both the optical and near-infrared spectra, yielding an abundance of approx. 1.2 wt% FeO and -approx. 0 wt% TiO2.
We investigate the possible pathways to produce the extreme energy observed in the calcium exosphere of Mercury. Any mechanism must explain the facts that Ca in Mercury's exosphere is extremely hot, that it is seen almost exclusively on the dawnside of the planet, and that its content varies seasonally, not sporadically. Simple diatomic molecules or their clusters are considered, focusing on calcium oxides while acknowledging that Ca sulfides may also be the precursor molecules. We first discuss impact vaporization to justify the assumption that CaO and Ca-oxide clusters are expected from impacts on Mercury. Then we discuss processes by which the atomic Ca is energized to a 70,000 K gas. The processes considered are (1) electron-impact dissociation of CaO molecules, (2) spontaneous dissociation of Ca-bearing molecules following impact vaporization, (3) shock-induced dissociative ionization, (4) photodissociation and (5) sputtering. We conclude that electron-impact dissociation cannot produce the required abundance of Ca, and sputtering cannot reproduce the observed spatial and temporal variation that is measured. Spontaneous dissociation is unlikely to result in the high energy that is seen. Of the two remaining processes, shock induced dissociative ionization produces the required energy and comes close to producing the required abundance, but rates are highly dependent on the incoming velocity distribution of the impactors. Photodissociation probably can produce the required abundance of Ca, but simulations show that photodissociation cannot reproduce the observed spatial distribution.
Analysis of oxygen in liquid alkali metals
Interactions of ions and protons with material surfaces - surface density, velocity spectrum, mercury ion sputtering, aluminum-aluminum oxide sputtering, and ion implantation
Optical spectra of discharge chambers of electron bombardment mercury ion thrustors with hollow and oxide cathodes