Highlights of OH, H2SO4, and methane sulfonic acid measurements made aboard the NASA P-3B during Transport and Chemical Evolution over the Pacific

Measurements of hydroxyl radical (OH), sulfuric acid (H2SO4), and methane sulfonic acid (MSA) were performed aboard the NASA P-3B using the selected ion chemical ionization mass spectrometry technique during the Transport and Chemical Evolution over the Pacific (TRACE-P) study. Photochemical box model calculations of OH concentrations yielded generally good agreement with an overall tendency to overestimate the measured OH by ∼20%. Further analysis reveals that this overestimation is present only at altitudes greater than ∼1.5 km, with the model underestimating OH measurements at lower altitudes. Boundary layer H2SO4 measurements, performed in a volcanic plume off the southern coast of Japan, revealed some of the largest marine boundary layer H2SO4 concentrations ever observed and were accompanied by new particle formation. Nighttime measurements of OH, H2SO4, and MSA in the remote pacific off Midway Island revealed significant boundary layer concentrations of H2SO4 and MSA, indicating evidence of nighttime boundary layer oxidation processes but in the absence of OH. A cursory exploration of the sources of production of the H2SO4 and MSA observed at night is presented

Long-path quantum cascade laser–based sensor for methane measurements

Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Atmospheric and Oceanic Technology 33 (2016): 2373-2384, doi:10.1175/JTECH-D-16-0024.1.A long-path methane (CH4) sensor was developed and field deployed using an 8-μm quantum cascade laser. The high optical power (40 mW) of the laser allowed for path-integrated measurements of ambient CH4 at total pathlengths from 100 to 1200 m with the use of a retroreflector. Wavelength modulation spectroscopy was used to make high-precision measurements of atmospheric pressure–broadened CH4 absorption over these long distances. An in-line reference cell with higher harmonic detection provided metrics of system stability in rapidly changing and harsh environments. The system consumed less than 100 W of power and required no consumables. The measurements intercompared favorably (typically less than 5% difference) with a commercial in situ methane sensor when accounting for the different spatiotemporal scales of the measurements. The sensor was field deployed for 2 weeks at an arctic lake to examine the robustness of the approach in harsh field environments. Short-term precision over a 458-m pathlength was 10 ppbv at 1 Hz, equivalent to a signal from a methane enhancement above background of 5 ppmv in a 1-m length. The sensor performed well in a range of harsh environmental conditions, including snow, rain, wind, and changing temperatures. These field measurements demonstrate the capabilities of the approach for use in detecting large but highly variable emissions in arctic environments.The authors gratefully acknowledge funding for this work by MIRTHE through NSF-ERC Grant EEC-0540832. D. J. Miller acknowledges support by the National Science Foundation Graduate Research Fellowship under Grant DGE-0646086. K. Sun acknowledges support by the NASA Earth and Space Science Fellowship IIP-1263579.2017-05-0

Steady state free radical budgets and ozone photochemistry during TOPSE

A steady state model, constrained by a number of measured quantities, was used to derive peroxy radical levels for the conditions of the Tropospheric Ozone Production about the Spring Equinox (TOPSE) campaign. The analysis is made using data collected aboard the NCAR/NSF C-130 aircraft from February through May 2000 at latitudes from 40° to 85°N, and at altitudes from the surface to 7.6 km. HO2 + RO2 radical concentrations were measured during the experiment, which are compared with model results over the domain of the study showing good agreement on the average. Average measurement/model ratios are 1.04 (σ = 0.73) and 0.96 (σ = 0.52) for the MLB and HLB, respectively. Budgets of total peroxy radical levels as well as of individual free radical members were constructed, which reveal interesting differences compared to studies at lower latitudes. The midlatitude part of the study region is a significant net source of ozone, while the high latitudes constitute a small net sink leading to the hypothesis that transport from the middle latitudes can explain the observed increase in ozone in the high latitudes. Radical reservoir species concentrations are modeled and compared with the observations. For most conditions, the model does a good job of reproducing the formaldehyde observations, but the peroxide observations are significantly less than steady state for this study. Photostationary state (PSS) derived total peroxy radical levels and NO/NO2ratios are compared with the measurements and the model; PSS-derived results are higher than observations or the steady state model at low NO concentrations

Measurements of coal particle shape, mass and temperature histories: Impact of particle irregularity on temperature predictions and measurements

Individual coal and carbon particles were levitated in an electrodynamic balance (EDB) and characterized using high-speed diode array and video based imaging systems to determine particle surface area, volume, drag, mass and density. These same particles were then heated bidirectionally using a long pulsed Nd:YAG laser to simulate combustion level heating fluxes (heating rates on order of 10{sup 4} to 10{sup 5} K/s). Measurements of particle surface temperature, size and laser temporal power variation were made and recorded during each heating experiment. Measured temperature histories were compared with a heat transfer analysis that accounted for variations in particle shape, mass, density, and laser heating power. Results of this study indicate that with well characterized materials of known properties agreement between measurement and model of within 20 K is typical throughout an entire heating and cooling profile. Large particle to particle variations are observed in coal particle temperature histories during rapid heating. These variations can be explained in large part by accounting for particle to particle property (shape, mass and density) variations. Even when accounting for particle to particle shape and density variation, however, model predictions greatly underestimate observed temperature histories. It is concluded that these discrepancies are largely due to uncertainties in the thermal properties (heat capacity and thermal conductivity) typically used to model coal combustion behavior

Impacts of biomass burning in Southeast Asia on ozone and reactive nitrogen over the western Pacific in spring

Aircraft measurements of ozone (O3) and its precursors (reactive nitrogen, CO, nonmethane hydrocarbons) were made over the western Pacific during the Transport and Chemical Evolution Over the Pacific (TRACE-P) campaign, which was conducted during February-April 2001. Biomass burning activity was high over Southeast Asia (SEA) during this period (dry season), and convective activity over SEA frequently transported air from the boundary layer to the free troposphere, followed by eastward transport to the sampling region over the western Pacific south of 30°N. This data set allows for systematic investigations of the chemical and physical processes in the outflow from SEA. Methyl chloride (CH3Cl) and CO are chosen as primary and secondary tracers, respectively, to gauge the degree of the impact of emissions of trace species from biomass burning. Biomass burning is found to be a major source of reactive nitrogen (NO x, PAN, HNO3, and nitrate) and O3 in this region from correlations of these species with the tracers. Changes in the abundance of reactive nitrogen during upward transport are quantified from the altitude change of the slopes of the correlations of these species with CO. NOx decreased with altitude due to its oxidation to HNO3. On the other hand, PAN was conserved during transport from the lower to the middle troposphere, consistent with its low water solubility and chemical stability at low temperatures. Large losses of HNO3 and nitrate, which are highly water soluble, occurred in the free troposphere, most likely due to wet removal by precipitation. This has been shown to be the major pathway of NOy loss in the middle troposphere. Increases in the mixing ratios of O3 and its precursors due to biomass burning in SEA are estimated using the tracers. Enhancements of CO and total reactive nitrogen (NOy), which are directly emitted from biomass burning, were largest at 2-4 km. At this altitude the increases in NOy and O3 were 810 parts per trillion by volume (pptv) and 26 parts per billion by volume (ppbv) above their background values of 240 pptv and 31 ppbv, respectively. The slope of the O3-CO correlation in biomass burning plumes was similar to those observed in fire plumes in northern Australia, Africa, and Canada. The O3 production efficiency (OPE) derived from the O3-CO slope and NOx/CO emission ratio (ER) is shown to be positively correlated with the C2H4 /NOx ER, indicating that the C2H4/NO x ER is a critical parameter in determining the OPE. Comparison of the net O3 flux across the western Pacific region and total O3 production due to biomass burning in SEA suggests that about 70% of O3 produced was transported to the western Pacific. Copyright 2004 by the American Geophysical Union

Clarifying the Dominant Sources and Mechanisms of Cirrus Cloud Formation

Formation of cirrus clouds depends on the availability of ice nuclei to begin condensation of atmospheric water vapor. Although it is known that only a small fraction of atmospheric aerosols are efficient ice nuclei, the critical ingredients that make those aerosols so effective have not been established. We have determined in situ the composition of the residual particles within cirrus crystals after the ice was sublimated. Our results demonstrate that mineral dust and metallic particles are the dominant source of residual particles, whereas sulfate and organic particles are underrepresented, and elemental carbon and biological materials are essentially absent. Further, composition analysis combined with relative humidity measurements suggests that heterogeneous freezing was the dominant formation mechanism of these clouds.National Science Foundation (U.S.) (NSF AGS-0840732)National Science Foundation (U.S.) (NSF grant AGS-1036275)United States. National Aeronautics and Space Administration (NASA Earth and Space Science Graduate Fellowship)United States. National Aeronautics and Space Administration (NASA Radiation Sciences Program award number NNX07AL11G)United States. National Aeronautics and Space Administration (NASA Radiation Sciences Program award number NNX08AH57G)United States. National Aeronautics and Space Administration (NASA Earth Science Division Atmospheric Composition program award number NNH11AQ58UI

Open-path, quantum cascade-laser-based sensor for high-resolution atmospheric ammonia measurements

We demonstrate a compact, open-path, quantum cascade-laser-based atmospheric ammonia sensor operating at 9.06 μm for high-sensitivity, high temporal resolution, ground-based measurements. Atmospheric ammonia (NH3) is a gas-phase precursor to fine particulate matter, with implications for air quality and climate change. Currently, NH3 sensing challenges have led to a lack of widespread in situ measurements. Our open-path sensor configuration minimizes sampling artifacts associated with NH3 surface adsorption onto inlet tubing and reduced pressure sampling cells, as well as condensed-phase partitioning ambiguities. Multi-harmonic wavelength modulation spectroscopy allows for selective and sensitive detection of atmospheric pressure-broadened absorption features. An in-line ethylene reference cell provides real-time calibration (±20% accuracy) and normalization for instrument drift under rapidly changing field conditions. The sensor has a sensitivity and noise-equivalent limit (1σ) of 0.15 ppbv NH3 at 10 Hz, a mass of ~ 5 kg and consumes ~ 50 W of electrical power. The total uncertainty in NH3 measurements is 0.20 ppbv NH3 ± 10%, based on a spectroscopic calibration method. Field performance of this open-path NH3 sensor is demonstrated, with 10 Hz time resolution and a large dynamic response for in situ NH3 measurements. This sensor provides the capabilities for improved in situ gas-phase NH3 sensing relevant for emission source characterization and flux measurements

Export efficiency of black carbon aerosol in continental outflow: Global implications

We use aircraft observations of Asian outflow from the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) mission over the NW Pacific in March–April 2001 to estimate the export efficiency of black carbon (BC) aerosol during lifting to the free troposphere, as limited by scavenging from the wet processes (warm conveyor belts and convection) associated with this lifting. Our estimate is based on the enhancement ratio of BC relative to CO in Asian outflow observed at different altitudes and is normalized to the enhancement ratio observed in boundary layer outflow (0–1 km). We similarly estimate export efficiencies of sulfur oxides (SO x = SO2(g) + fine SO4 2−) and total inorganic nitrate (HNO3 T = HNO3(g) + fine NO3 −) for comparison to BC. Normalized export efficiencies for BC are 0.63–0.74 at 2–4 km altitude and 0.27–0.38 at 4–6 km. Values at 2–4 km altitude are higher than for SO x (0.48–0.66) and HNO3 T (0.29–0.62), implying that BC is scavenged in wet updrafts but not as efficiently as sulfate or nitrate. Simulation of the TRACE-P period with a global three-dimensional model (GEOS-CHEM) indicates that a model timescale of 1 ± 1 days for conversion of fresh hydrophobic to hydrophilic BC provides a successful fit to the export efficiencies observed in TRACE-P. The resulting mean atmospheric lifetime of BC is 5.8 ± 1.8 days, the global burden is 0.11 ± 0.03 Tg C, and the decrease in Arctic snow albedo due to BC deposition is 3.1 ± 2.5%.Earth and Planetary Science

Electronic sculpting of ligand-GPCR subtype selectivity:the case of angiotensin II

GPCR subtypes possess distinct functional and pharmacological profiles, and thus development of subtype-selective ligands has immense therapeutic potential. This is especially the case for the angiotensin receptor subtypes AT1R and AT2R, where a functional negative control has been described and AT2R activation highlighted as an important cancer drug target. We describe a strategy to fine-tune ligand selectivity for the AT2R/AT1R subtypes through electronic control of ligand aromatic-prolyl interactions. Through this strategy an AT2R high affinity (<i>K</i>_i = 3 nM) agonist analogue that exerted 18,000-fold higher selectivity for AT2R versus AT1R was obtained. We show that this compound is a negative regulator of AT1R signaling since it is able to inhibit MCF-7 breast carcinoma cellular proliferation in the low nanomolar range