Small carbon chains in circumstellar envelopes

Observations were made for a number of carbon-rich circumstellar envelopes using the Phoenix spectrograph on the Gemini South telescope to determine the abundance of small carbon chain molecules. Vibration-rotation lines of the $\nu_{3}$ antisymmetric stretch of C$_{3}$ near 2040 cm$^{-1}$ (4.902 $\mu$m) have been used to determine the column density for four carbon-rich circumstellar envelopes: CRL 865, CRL 1922, CRL 2023 and IRC +10216. We additionally calculate the column density of C$_{5}$ for IRC +10216, and provide an upper limit for 5 more objects. An upper limit estimate for the C$_{7}$ column density is also provided for IRC+10216. A comparison of these column densities suggest a revision to current circumstellar chemical models may be needed

Emission spectrum of hot HDO below 4000 cm-1

Fourier transform emission spectra were recorded using a mixture of H2O and D2O at a temperature of 1500 °C. The spectra were recorded in three overlapping sections and cover the wavenumber range 1800–3932 cm−1. This spectrum is analyzed together with a previously reported one spanning the 380–2190 cm−1 range [Parekunnel et al., J. Mol. Spectrosc. 2001 (28) 101]. This analysis leads to 4409 newly assigned HDO emission lines. This work particularly extends data on the (200) and (120) states of HDO for which newly determined energy levels are presented

Balloon-borne radiometer measurement of Northern Hemisphere mid-latitude stratospheric HNO3 profiles spanning 12 years

Low-resolution atmospheric thermal emission spectra collected by balloon-borne radiometers over the time span of 1990–2002 are used to retrieve vertical profiles of HNO3, CFC-11 and CFC-12 volume mixing ratios between approximately 10 and 35 km altitude. All of the data analyzed have been collected from launches from a Northern Hemisphere mid-latitude site, during late summer, when stratospheric dynamic variability is at a minimum. The retrieval technique incorporates detailed forward modeling of the instrument and the radiative properties of the atmosphere, and obtains a best fit between modeled and measured spectra through a combination of onion-peeling and global optimization steps. The retrieved HNO3 profiles are consistent over the 12-year period, and are consistent with recent measurements by the Atmospheric Chemistry Experiment-Fourier transform spectrometer satellite instrument. This suggests that, to within the errors of the 1990 measurements, there has been no significant change in the HNO3 summer mid-latitude profile

Molecular astronomy of cool stars and sub-stellar objects

The optical and infrared spectra of a wide variety of `cool' astronomical objects including the Sun, sunspots, K-, M- and S-type stars, carbon stars, brown dwarfs and extrasolar planets are reviewed. The review provides the necessary astronomical background for chemical physicists to understand and appreciate the unique molecular environments found in astronomy. The calculation of molecular opacities needed to simulate the observed spectral energy distributions is discussed

The High Arctic in Extreme Winters: Vortex, Temperature, and MLS and ACE-FTS Trace Gas Evolution

The first three Canadian Arctic Atmospheric Chemistry Experiment (ACE) Validation Campaigns at Eureka (80° N, 86° W) were during two extremes of Arctic winter variability: Stratospheric sudden warmings (SSWs) in 2004 and 2006 were among the strongest, most prolonged on record; 2005 was a record cold winter. New satellite measurements from ACE-Fourier Transform Spectrometer (ACE-FTS), Sounding of the Atmosphere using Broadband Emission Radiometry, and Aura Microwave Limb Sounder (MLS), with meteorological analyses and Eureka lidar and radiosonde temperatures, are used to detail the meteorology in these winters, to demonstrate its influence on transport and chemistry, and to provide a context for interpretation of campaign observations. During the 2004 and 2006 SSWs, the vortex broke down throughout the stratosphere, reformed quickly in the upper stratosphere, and remained weak in the middle and lower stratosphere. The stratopause reformed at very high altitude, above where it could be accurately represented in the meteorological analyses. The 2004 and 2006 Eureka campaigns were during the recovery from the SSWs, with the redeveloping vortex over Eureka. 2005 was the coldest winter on record in the lower stratosphere, but with an early final warming in mid-March. The vortex was over Eureka at the start of the 2005 campaign, but moved away as it broke up. Disparate temperature profile structure and vortex evolution resulted in much lower (higher) temperatures in the upper (lower) stratosphere in 2004 and 2006 than in 2005. Satellite temperatures agree well with Eureka radiosondes, and with lidar data up to 50–60 km. Consistent with a strong, cold upper stratospheric vortex and enhanced radiative cooling after the SSWs, MLS and ACE-FTS trace gas measurements show strongly enhanced descent in the upper stratospheric vortex during the 2004 and 2006 Eureka campaigns compared to that in 2005

Pulmonary artery banding: long-term telemetric adjustment

Objective: Adjustment of pulmonary blood flow is difficult in pulmonary artery banding for complex congenital heart defects. A new wireless, battery free, telemetrically controlled, implantable device (FloWatch®, EndoArt, S.A., Lausanne, Switzerland) allowing for progressive occlusion/reopening of the device through a remote control at the wanted percentage of occlusion (adjustable pulmonary artery banding) underwent experimental evaluation. Methods: Eleven mini-pigs underwent FloWatch® implantation around the main pulmonary artery through left thoracotomy. The first group (n=4), mean age 18.2±0.1 weeks, mean body weight 12.0±0.1 kg, underwent FloWatch® implantation as device tolerance test. The second group (n=7), mean age 8.6±3.4 weeks, mean body weight 5.1±1.5 kg, underwent functional evaluation: at implantation, 1, 3, 5, 8 and 10 weeks after implantation, the device was progressively occluded and reopened, with Doppler evaluation of the developed pressure gradient. Results: The four mini-pigs of first group were sacrificed at mean age of 42.3±0.1 weeks, mean body weight 25.1±3.2 kg (mean interval of 24 weeks after implantation); the device was still functioning and histology revealed almost normal morphology of the pulmonary artery. In all seven mini-pigs of second group the possibility of narrowing/releasing the pulmonary artery was confirmed at implantation and during follow-up: at last control their mean age was 20.5±2.8 weeks and the body weight 12.7±3.7 kg. Conclusions: Complete adjustment of pulmonary blood flow is now possible with an implantable device allowing for pulmonary artery banding with early and late telemetric flow contro

Laboratory spectroscopy of hot water near 2-microns and sunspot spectroscopy in the H-band region

The infrared spectrum of sunspots is analyzed in the H-band region (55406997 cm-1) with the aid of a new, hot (T = 1800 K) laboratory emission spectrum of water covering 48787552 cm-1. There are 682 lines in the sunspot spectrum and 5589 lines in the laboratory spectrum assigned quantum numbers corresponding to transitions due to H216O using a combination of previously known experimental energy levels for water and variational line lists. A further 201 unassigned lines common to both spectra can also be associated with water

Intercomparison of ground-based ozone and NO2 measurements during the MANTRA 2004 campaign

The MANTRA (Middle Atmosphere Nitrogen TRend Assessment) 2004 campaign took place in Vanscoy, Saskatchewan, Canada (52° N, 107° W) from 3 August to 15 September, 2004. In support of the main balloon launch, a suite of five zenith-sky and direct-Sun-viewing UV-visible ground-based spectrometers was deployed, primarily measuring ozone and NO2 total columns. Three Fourier transform spectrometers (FTSs) that were part of the balloon payload also performed ground-based measurements of several species, including ozone. Ground-based measurements of ozone and NO2 differential slant column densities from the zenith-viewing UV-visible instruments are presented herein. They are found to partially agree within NDACC (Network for the Detection of Atmospheric Composition Change) standards for instruments certified for process studies and satellite validation. Vertical column densities of ozone from the zenith-sky UV-visible instruments, the FTSs, a Brewer spectrophotometer, and ozonesondes are compared, and found to agree within the combined error estimates of the instruments (15%). NO2 vertical column densities from two of the UV-visible instruments are compared, and are also found to agree within combined error (15%)

Derivation of tropospheric methane from TCCON CH₄ and HF total column observations

The Total Carbon Column Observing Network (TCCON) is a global ground-based network of Fourier transform spectrometers that produce precise measurements of column-averaged dry-air mole fractions of atmospheric methane (CH₄). Temporal variability in the total column of CH₄ due to stratospheric dynamics obscures fluctuations and trends driven by tropospheric transport and local surface fluxes that are critical for understanding CH₄ sources and sinks. We reduce the contribution of stratospheric variability from the total column average by subtracting an estimate of the stratospheric CH₄ derived from simultaneous measurements of hydrogen fluoride (HF). HF provides a proxy for stratospheric CH₄ because it is strongly correlated to CH₄ in the stratosphere, has an accurately known tropospheric abundance (of zero), and is measured at most TCCON stations. The stratospheric partial column of CH₄ is calculated as a function of the zonal and annual trends in the relationship between CH₄ and HF in the stratosphere, which we determine from ACE-FTS satellite data. We also explicitly take into account the CH₄ column averaging kernel to estimate the contribution of stratospheric CH₄ to the total column. The resulting tropospheric CH₄ columns are consistent with in situ aircraft measurements and augment existing observations in the troposphere

Retrieval of Carbon Dioxide Vertical Profiles From Solar Occultation Observations and Associated Error Budgets for ACE-FTS and CASS-FTS

An algorithm is developed to retrieve the vertical profile of carbon dioxide in the 5 to 25 km altitude range using mid-infrared solar occultation spectra from the main instrument of the ACE (Atmospheric Chemistry Experiment) mission, namely the Fourier transform spectrometer (FTS). The main challenge is to find an atmospheric phenomenon which can be used for accurate tangent height determination in the lower atmosphere, where the tangent heights (THs) calculated from geometric and timing information are not of sufficient accuracy. Error budgets for the retrieval of CO2 from ACE-FTS and the FTS on a potential follow-on mission named CASS (Chemical and Aerosol Sounding Satellite) are calculated and contrasted. Retrieved THs have typical biases of 60m relative to those retrieved using the ACE version 3. x software after revisiting the temperature dependence of the N2 CIA (collision-induced absorption) laboratory measurements and accounting for sulfate aerosol extinction. After correcting for the known residual high bias of ACE version 3. x THs expected from CO2 spectroscopic/isotopic inconsistencies, the remaining bias for tangent heights determined with the N2 CIA is -20 m. CO2 in the 5-13 km range in the 2009-2011 time frame is validated against aircraft measurements from CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container), CONTRAIL (Comprehensive Observation Network for Trace gases by Airline), and HIPPO HIAPER Pole-to-Pole Observations), yielding typical biases of -1.7 ppm in the 5-13 km range. The standard error of these biases in this vertical range is 0.4 ppm. The multiyear ACE-FTS data set is valuable in determining the seasonal variation of the latitudinal gradient which arises from the strong seasonal cycle in the Northern Hemisphere troposphere. The annual growth of CO2 in this time frame is determined to be 2.6±0.4 ppm year-1, in agreement with the currently accepted global growth rate based on ground-based measurements