ALBERT

Description: The vacuum integrity of the discharge tube of a copper vapor laser (CVL) is normally protected by Brewster angled windows. In an attempt to increase the operating efficiency of the CVL, flat windows were used to replace the Brewster windows. Experimental data confirm that the overall efficiency of the CVL does increase when such windows are used. The experimental results are discussed in terms of a computer model found in the literature. The cause of the efficiency increase appears due to a double optical cavity set up by the flat windows. However, the variation of the efficiency due to changes in the pulse repetition frequency (PRF) and buffer gas pressure are less well understood.

Description: We present new data on the stability of hornblende in a Martian mantle composition, on CO2 solubility in iron-rich basaltic magmas, and on the solubility of H2O in an alkalic basaltic magma. These new data are combined with a summary of data from the literature to present a summary of the current state of our estimates of solubilities of H2O and CO2 in probable Martian magmas and the stability of hornblende in a slightly hydrous mantle. The new results suggest that hornblende stability is not sensitive to the Mg/(Mg+Fe) ratio (mg#) of the mantle, that is the results for terrestrial mantle compositions are similar to the more iron-rich Martian composition. Likewise, CO2 solubility in iron-rich tholeiitic basaltic magmas is similar to iron-poor terrestrial compositions. The solubility of H2O has been measured in an alkalic basaltic (basanite) composition for the first time, and it is significantly lower than predicted for models of water solubility in magmas. The lack of mg# dependence observed in hornblende stability and on CO2 solubility that in many cases terrestrial results can be applied to Martian compositions. This conclusion does not apply to other phenomena such as primary magma compositions and major mantle mineral mineralogy.

Description: Petrologic analysis of surface samples has been used to deduce pressure and temperature conditions existing in the crust and upper mantle at specific times in the Earth's history, as well as to estimate the chemical and mineralogical composition of the crust and upper mantle. The same techniques can be applied to samples of the Martian surface to provide P, T, time and composition constraints of the Martian interior. Estimates of P and T conditions existing at a given time would, in turn, provide strong constraints on the thermal evolution of Mars. Knowledge of the chemical and mineralogical composition of the Martian interior is of fundamental importance in assessing the early history of the solar system. A general petrological approach is outlined, describing the kinds of sample required, summarizing current understanding of the Martian interior based on experimental petrology, and outlining some of the important experiments needed to allow a full petrologic interpretation of Martian samples.

Description: Isoprene oxidation schemes vary greatly among gas-phase chemical mechanisms, with potentially significant ramifications for air quality modeling and interpretation of satellite observations in biogenic-rich regions. In this study, in situ observations from the 2013 SENEX mission are combined with a constrained O-D photochemical box model to evaluate isoprene chemistry among five commonly used gas-phase chemical mechanisms: CBO5, CB6r2, MCMv3.2, MCMv3.3.1, and a recent version of GEOS-Chem. Mechanisms are evaluated and inter-compared with respect to formaldehyde (HCHO), a high-yield product of isoprene oxidation. Though underestimated by all considered mechanisms, observed HCHO mixing ratios are best reproduced by MCMv3.3.1 (normalized mean bias = -15%), followed by GEOS-Chem (-17%), MCMv3.2 (-25%), CB6r2 (-32%) and CB05 (-33%). Inter-comparison of HCHO production rates reveals that major restructuring of the isoprene oxidation scheme in the Carbon Bond mechanism increases HCHO production by only approx. 5% in CB6r2 relative to CBO5, while further refinement of the complex isoprene scheme in the Master Chemical Mechanism increases HCHO production by approx. 16% in MCMv3.3.1 relative to MCMv3.2. The GEOS-Chem mechanism provides a good approximation of the explicit isoprene chemistry in MCMv3.3.1 and generally reproduces the magnitude and source distribution of HCHO production rates. We analytically derive improvements to the isoprene scheme in CB6r2 and incorporate these changes into a new mechanism called CB6r2-UMD, which is designed to preserve computational efficiency. The CB6r2-UMD mechanism mimics production of HCHO in MCMv3.3.1 and demonstrates good agreement with observed mixing ratios from SENEX (-14%). Improved simulation of HCHO also impacts modeled ozone: at approx. 0.3 ppb NO, the ozone production rate increases approx. 3% between CB6r2 and CB6r2-UMD, and rises another approx. 4% when HCHO is constrained to match observations.

Description: The solubility of CO2-CO fluids in a midocean ridge basalt have been measured at 1200 C, 500-1500 bar, and oxygen fugacities between NNO and NNO-4. In agreement with results of previous studies, the results reported here imply that, at least at low pressures, CO2 dissolves in basaltic melt only in the form of carbonate groups. The dissolution reaction is heterogeneous, with CO2 molecules in the fluid reacting directly with reactive oxygens in the melt to produce CO3(2-). CO, on the other hand, is insoluble, dissolving neither as carbon, molecular CO, nor CO3(2-). It is shown that, for a given pressure and temperature, the concentration of dissolved carbon-bearing species in basaltic melt in equilibrium with a carbon-oxygen fluid is proportional to the mole fraction of CO2 in the fluid, which is a function of fO2. At low pressures CO2 solubility is a linear function of CO2 fugacity at constant temperatures.

Description: Recent studies suggest overestimates in current U.S. emission inventories of nitrogen oxides (NOx=NO+NO2). Here, we expand a previously developed Fuel-based Inventory of motor-Vehicle Emissions (FIVE) to the continental U.S. for the year 2013, and evaluate our estimates of mobile source emissions with the U.S. Environmental Protection Agency's National Emissions Inventory (NEI) interpolated to 2013. We find that mobile source emissions of NOx and carbon monoxide (CO) in the NEI are higher than FIVE by 28% and 90%, respectively. Using a chemical transport model, we model mobile source emissions from FIVE, and find consistent levels of urban NOx and CO as measured during the Southeast Nexus (SENEX) Study in 2013. Lastly, we assess the sensitivity of ozone (O3) over the Eastern U.S. to uncertainties in mobile source NOx emissions and biogenic volatile organic compound (VOC) emissions. The ground-level O3 is sensitive to reductions in mobile source NOx emissions, most notably in the Southeastern U.S. and during O3 exceedance events, under the revised standard proposed in 2015 (〉70 ppb, 8-hr maximum). This suggests that decreasing mobile source NOx emissions could help in meeting more stringent O3 standards in the future.

Description: The minimum melt composition in equilibrium with an iron-rich garnet lherzolite assemblage is ascertained from a study of the liquidus relations of iron-rich basaltic compositions at 23 kb. The experimentally determined primary melt composition and its calculated sodium content reveal that Martian garnet lherzolite minimum melts are picritic alkali olivine basalts. Martian primary melts are found to be more picritic than terrestrial garnet lherzolite primary melts.

Description: A bulk composition for Mars is derived to a pressure-dependent mineralogy. The density distribution of the present model is compared with density distributions derived from the global gravity field. It is argued that the uppermost Martian mantle is likely to be dominated by olivine and orthopyroxene, as is the earth's upper mantle, although the Martian mantle has a lower MgO/(MgO + FeO) ratio (0.74 vs 0.89). The olivine-peridotite layer extends to a depth of 900 to 1100 km where the transition to silicate spinel begins. Calculations of the high-pressure liquidus and solidus temperatures indicate that for the case of a molten core the minimum temperature at the core-mantle boundary is about 2000 K, whereas for the case of a solid core the maximum temperature is about 1800 K. Summation of the masses in the various layers of Mars yields a value of 0.353 for the dimensionless moment of inertia, which is intermediate between the generally accepted value of 0.365 and the value of 0.345 predicated on a nonaxisymmetric distribution of mass about the Tharsis plateau.

Description: Nitric oxide (NO) is emitted in large quantities from coal-burning power plants. During the day, the plumes from these sources are efficiently mixed into the boundary layer, while at night, they may remain concentrated due to limited vertical mixing during which they undergo horizontal fanning. At night, the degree to which NO is converted to HNO3 and therefore unable to participate in next-day ozone (O3) formation depends on the mixing rate of the plume, the composition of power plant emissions, and the composition of the background atmosphere. In this study, we use observed plume intercepts from the Wintertime INvestigation of Transport, Emissions and Reactivity (WINTER) campaign to test sensitivity of overnight NOx removal to the N2O5 loss rate constant, plume mixing rate, background O3, and background levels of volatile organic compounds using a 2-D box model of power plant plume transport and chemistry. The factor that exerted the greatest control over NOx removal was the loss rate constant of N2O5. At the lowest observed N2O5 loss rate constant, no other combination of conditions converts more than 10 percent of the initial NOx to HNO3. The other factors did not influence NOx removal to the same degree.

Description: We report enhancements of glyoxal relative to carbon monoxide and formaldehyde from biomass burning plumes intercepted from the NOAA WP-3D aircraft during the 2013 Southeast Nexus and 2015 Shale Oil and Natural Gas Nexus field campaigns. The intercepted biomass burning plumes were from small agricultural fires. Since the plume ages were not known, these values are normalized excess mixing ratios, instead of the more common emission ratio, which is used only for fresh emissions. Glyoxal was measured using broadband cavity enhanced spectroscopy, which provides a sensitive and highly selective measurement of glyoxal. Emissions of other species such as methane, formaldehyde, and nitrous acid agreed with previous laboratory and field measurements, but the glyoxal emissions relative to CO were on average a factor of 4 lower than previously reported. Several glyoxal loss processes such as aerosol uptake were examined to determine if they could affect the observed glyoxal concentrations, but they were insufficient to explain the lower measured values of glyoxal relative to other biomass burning trace gases, indicating that glyoxal emissions from biomass burning may be significantly overestimated.