A versatile vacuum ultraviolet ion source for reduced pressure bipolar chemical ionization mass spectrometry

We present the development of a chemical ionization mass spectrometer ion source specifically designed for in situ measurements of trace gases in the upper troposphere and lower stratosphere. The ion source utilizes a commercially available photoionization krypton lamp, primarily emitting photons in the vacuum ultraviolet (VUV) region at wavelengths of 124 and 117&thinsp;nm (corresponding to energies of 10 and 10.6&thinsp;eV, respectively), coupled to a commercially available Vocus proton transfer reaction mass spectrometer. The VUV ion source can produce both negative and positive reagent ions; however, here we primarily focus on generating iodide anions (I&minus;). The instrument's drift tube (also known as ion&ndash;molecule reactor) operates at pressures between 2 and 10&thinsp;mbar, which facilitates ambient sampling at atmospheric pressures as low as 50&thinsp;mbar. The low operating pressure reduces secondary ion chemistry that can occur in iodide chemical ionization mass spectrometry (CIMS). It also allows the addition of water vapor to the drift tube to exceed typical ambient humidity by more than 1 order of magnitude, significantly reducing ambient humidity dependence of sensitivities. An additional benefit of this ion source and drift tube is a 10- to 100-fold reduction in nitrogen consumed during operation relative to standard I&minus; ion sources, resulting in significantly reduced instrument weight and operational costs. In iodide mode, sensitivities of 76&thinsp;cps&thinsp;ppt&minus;1 for nitric acid, 35&thinsp;cps&thinsp;ppt&minus;1 for Br2 and 8.9&thinsp;cps&thinsp;ppt&minus;1 for Cl2 were achieved. Lastly, we demonstrate that this ion source can generate benzene () and ammonium () reagent ions to expand the number of detected atmospheric trace gases.</p

Modelling the Inorganic Bromine Partitioning in the Tropical Tropopause over the Pacific Ocean

The stratospheric inorganic bromine burden (Bry) arising from the degradation of brominated very short-lived organic substances (VSL org ), and its partitioning between reactive and reservoir species, is needed for a comprehensive assessment of the ozone depletion potential of brominated trace gases. Here we present modelled inorganic bromine abundances over the Pacific tropical tropopause based on aircraft observations of VSL org of two campaigns of the Airborne Tropical TRopopause EXperiment (ATTREX 2013 carried out over eastern Pacific and ATTREX 2014 carried out over the western Pacific) and chemistry-climate simulations (along ATTREX flight tracks) using the specific meteorology prevailing. Using the Community Atmosphere Model with Chemistry (CAM-Chem), we model that BrO and Br are the daytime dominant species. Integrated across all ATTREX flights BrO represents ~ 43 % and 48 % of daytime Bry abundance at 17 km over the Western and Eastern Pacific, respectively. The results also show zones where Br/BrO >1 depending on the solar zenith angle (SZA), ozone concentration and temperature. On the other hand, BrCl and BrONO 2 were found to be the dominant night-time species with ~ 61% and 56 % of abundance at 17 km over the Western and Eastern Pacific, respectively. The western-to-eastern differences in the partitioning of inorganic bromine are explained by different abundances of ozone (O3), nitrogen dioxide (NO2) , and total inorganic chlorine (Cly).Fil: Navarro, María A.. University of Miami; Estados UnidosFil: Saiz-lopez, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Cuevas, Carlos Alberto. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Fernandez, Rafael Pedro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; Argentina. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Universidad Tecnologica Nacional. Facultad Regional Mendoza. Secretaría de Ciencia, Tecnología y Postgrado; ArgentinaFil: Atlas, Elliot. University of Miami; Estados UnidosFil: Rodriguez Lloeveras, Xavier. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Kinnison, Douglas E.. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Lamarque, Jean Francois. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Tilmes, Simone. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Thornberry, Troy. State University of Colorado at Boulder; Estados Unidos. Earth System Research Laboratory; Estados UnidosFil: Rollins, Andrew. State University of Colorado at Boulder; Estados Unidos. Earth System Research Laboratory; Estados UnidosFil: Elkins, James W.. Earth System Research Laboratory; Estados UnidosFil: Hintsa, Eric J.. State University of Colorado at Boulder; Estados Unidos. Earth System Research Laboratory; Estados UnidosFil: Moore, Fred L.. State University of Colorado at Boulder; Estados Unidos. Earth System Research Laboratory; Estados Unido

Improvements to a laser-induced fluorescence instrument for measuring SO2 - impact on accuracy and precision

This work describes key improvements made to the in situ laser-induced fluorescence instrument for measuring sulfur dioxide (SO2) that was originally described by Rollins et al.&nbsp;(2016). Here, we report measurements of the SO2 fluorescence emission spectrum. These measurements allow for the determination of the most appropriate bandpass filters to optimize the fluorescence signal, while reducing the instrumental background. Because many aromatic species fluoresce in the same spectral region as SO2, fluorescence spectra were also measured for naphthalene and anisole to determine if ambient SO2 measurements could be biased in the presence of such species. Improvement in the laser system resulted in better tunability, and a significant reduction in the 216.9&thinsp;nm laser linewidth. This increases the online/offline signal ratio which, in turn, improves the precision and specificity of the measurement. The effects of these improvements on the instrumental sensitivity were determined by analyzing the signal and background of the instrument, using varying optical bandpass filter ranges and cell pressures and calculating the resulting limit of detection. As a result, we report an improvement to the instrumental sensitivity by as much as 50&thinsp;%. &nbsp;</p

A42F-03: Small-Scale Variability in Tropical Tropopause Layer Humidity

Recent advances in statistical parameterizations of cirrus cloud processes for use in global models are highlighting the need for information about small-scale fluctuations in upper tropospheric humidity and the physical processes that control the humidity variability. To address these issues, we have analyzed high-resolution airborne water vapor measurements obtained in the Airborne Tropical TRopopause EXperiment (ATTREX) over the tropical Pacific between 14 and 20 km. Using accurate and precise 1-Hz water vapor measurements along approximately-level aircraft flight legs, we calculate structure functions spanning horizontal scales ranging from about 0.2 to 50 km, and we compare the water vapor variability in the lower (about 14 km) and upper (16-19 km) Tropical Tropopause Layer (TTL). We also compare the magnitudes and scales of variability inside TTL cirrus versus in clear-sky regions. The measurements show that in the upper TTL, water vapor concentration variance is stronger inside cirrus than in clear-sky regions. Using simulations of TTL cirrus formation, we show that small variability in clear-sky humidity is amplified by the strong sensitivity of ice nucleation rate to supersaturation, which results in highly-structured clouds that subsequently drive variability in the water vapor field. In the lower TTL, humidity variability is correlated with recent detrainment from deep convection. The structure functions indicate approximately power-law scaling with spectral slopes ranging from about minus 5 divided by 3, to minus 2

A Review of Structural and Biomechanical Changes in the Cornea in Aging, Disease, and Photochemical Crosslinking

The study of corneal biomechanics is motivated by the tight relationship between biomechanical properties and visual function within the ocular system. For instance, variation in collagen fibril alignment and non-enzymatic crosslinks rank high among structural factors which give rise to the cornea's particular shape and ability to properly focus light. Gradation in these and other factors engender biomechanical changes which can be quantified by a wide variety of techniques. This review summarizes what is known about both the changes in corneal structure and associated changes in corneal biomechanical properties in aging, keratoconic, and photochemically crosslinked corneas. In addition, methods for measuring corneal biomechanics are discussed and the topics are related to both clinical studies and biomechanical modeling simulations

UAS Chromatograph for Atmospheric Trace Species (UCATS) – a versatile instrument for trace gas measurements on airborne platforms

UCATS (the UAS Chromatograph for Atmospheric Trace Species) was designed and built for observations of important atmospheric trace gases from unmanned aircraft systems (UAS) in the upper troposphere and lower stratosphere (UTLS). Initially it measured major chlorofluorocarbons (CFCs) and the stratospheric transport tracers nitrous oxide (N2O) and sulfur hexafluoride (SF6), using gas chromatography with electron capture detection. Compact commercial absorption spectrometers for ozone (O3) and water vapor (H2O) were added to enhance its capabilities on platforms with relatively small payloads. UCATS has since been reconfigured to measure methane (CH4), carbon monoxide (CO), and molecular hydrogen (H2) instead of CFCs and has undergone numerous upgrades to its subsystems. It has served as part of large payloads on stratospheric UAS missions to probe the tropical tropopause region and transport of air into the stratosphere; in piloted aircraft studies of greenhouse gases, transport, and chemistry in the troposphere; and in 2021 is scheduled to return to the study of stratospheric ozone and halogen compounds, one of its original goals. Each deployment brought different challenges, which were largely met or resolved. The design, capabilities, modifications, and some results from UCATS are shown and described here, including changes for future missions.Support was provided for HIPPO by NSF award no. AGS-0628452, for ATTREX by NASA Earth Venture program award no. NNA11AA55I, and for ATom by NASA award no. NNH17AE26I; additional support was provided by NASA Upper Atmosphere Research Program award no. NNH13AV69I. This work was also supported in part by the NOAA Cooperative Agreement with CIRES, NA17OAR4320101

Fermi Large Area Telescope Constraints on the Gamma-ray Opacity of the Universe

The Extragalactic Background Light (EBL) includes photons with wavelengths from ultraviolet to infrared, which are effective at attenuating gamma rays with energy above ~10 GeV during propagation from sources at cosmological distances. This results in a redshift- and energy-dependent attenuation of the gamma-ray flux of extragalactic sources such as blazars and Gamma-Ray Bursts (GRBs). The Large Area Telescope onboard Fermi detects a sample of gamma-ray blazars with redshift up to z~3, and GRBs with redshift up to z~4.3. Using photons above 10 GeV collected by Fermi over more than one year of observations for these sources, we investigate the effect of gamma-ray flux attenuation by the EBL. We place upper limits on the gamma-ray opacity of the Universe at various energies and redshifts, and compare this with predictions from well-known EBL models. We find that an EBL intensity in the optical-ultraviolet wavelengths as great as predicted by the "baseline" model of Stecker et al. (2006) can be ruled out with high confidence.Comment: 42 pages, 12 figures, accepted version (24 Aug.2010) for publication in ApJ; Contact authors: A. Bouvier, A. Chen, S. Raino, S. Razzaque, A. Reimer, L.C. Reye

The NASA Airborne Tropical TRopopause EXperiment (ATTREX): High-Altitude Aircraft Measurements in the Tropical Western Pacific

The February through March 2014 deployment of the NASA Airborne Tropical TRopopause EXperiment (ATTREX) provided unique in situ measurements in the western Pacific Tropical Tropopause Layer (TTL). Six flights were conducted from Guam with the long-range, high-altitude, unmanned Global Hawk aircraft. The ATTREX Global Hawk payload provided measurements of water vapor, meteorological conditions, cloud properties, tracer and chemical radical concentrations, and radiative fluxes. The campaign was partially coincident with the CONTRAST and CAST airborne campaigns based in Guam using lower-altitude aircraft (see companion articles in this issue). The ATTREX dataset is being used for investigations of TTL cloud, transport, dynamical, and chemical processes as well as for evaluation and improvement of global-model representations of TTL processes. The ATTREX data is openly available at https:espoarchive.nasa.gov

Physical Processes Controlling the Spatial Distributions of Relative Humidity in the Tropical Tropopause Layer over the Pacific

The spatial distribution of relative humidity with respect to ice (RHI) in the boreal wintertime tropical tropopause layer (TTL, is asymptotically Equal to 14-18 km) over the Pacific is examined with the measurements provided by the NASA Airborne Tropical TRopopause EXperiment. We also compare the measured RHI distributions with results from a transport and microphysical model driven by meteorological analysis fields. Notable features in the distribution of RHI versus temperature and longitude include (1) the common occurrence of RHI values near ice saturation over the western Pacific in the lower to middle TTL; (2) low RHI values in the lower TTL over the central and eastern Pacific; (3) common occurrence of RHI values following a constant mixing ratio in the middle to upper TTL (temperatures between 190 and 200 K); (4) RHI values typically near ice saturation in the coldest airmasses sampled; and (5) RHI values typically near 100% across the TTL temperature range in air parcels with ozone mixing ratios less than 50 ppbv. We suggest that the typically saturated air in the lower TTL over the western Pacific is likely driven by a combination of the frequent occurrence of deep convection and the predominance of rising motion in this region. The nearly constant water vapor mixing ratios in the middle to upper TTL likely result from the combination of slow ascent (resulting in long residence times) and wave-driven temperature variability. The numerical simulations generally reproduce the observed RHI distribution features, and sensitivity tests further emphasize the strong influence of convective input and vertical motions on TTL relative humidity

Physical Processes Controlling the Distribution of Relative Humidity in the Tropical Tropopause Layer over the Pacific

The distribution of relative humidity with respect to ice (RHI) in the Boreal wintertime Tropical Tropopause Layer (TTL - about 14-19 km) over the Pacific is examined with the extensive dataset of measurements from the NASA Airborne Tropical TRopopause EXperiment (ATTREX). Multiple deployments of the Global Hawk during ATTREX provided hundreds of vertical profiles spanning the Pacific with accurate measurements of temperature, pressure, water vapor concentration, ozone concentration, and cloud properties. We also compare the measured RHI distributions with results from a transport and microphysical model driven by meteorological analysis fields. Notable features in the distribution of RHI versus temperature and longitude include (1) the common occurrence of RHI values near ice saturation over the western Pacific in the lower TTL (temperatures greater than 200 K) and in airmasses with low ozone concentrations indicating recent detrainment from deep convection; (2) low RHI values in the lower TTL over the eastern Pacific where deep convection is infrequent; (3) RHI values following a constant H2O mixing ratio in the upper TTL (temperatures below about 195 degrees Kelvin), particularly for samples with ozone mixing ratios greater than about 50-100 parts-per-billion-volume indicating mixtures of tropospheric and stratospheric air, and (4) RHI values typically near ice saturation in the coldest airmasses sampled (temperatures less than about 190 degrees Kelvin). We find that the typically saturated air in the lower TTL over the western Pacific is largely driven by the frequent occurrence of deep convection in this region. The nearly-constant water vapor mixing ratios in the upper TTL result from the combination of slow ascent (resulting in long residence times) and wave-driven temperature variability on a range of time scales (resulting in most air parcels having experienced low temperature and dehydration)