NASA - National Aeronautics and Space Administration

The measurement of gas phase peroxide species, H2O2 and CH3OOH, contribute to our scientific understanding of the photochemistry of trace gases and particles prior to and after their transport and processing through deep convective clouds. The PCIMS instrument used to make these measurements in the DC3/SEAC4RS mission is new and this will be its first use in an airborne science campaign.

The PCIMS instrument is a slightly modified CIMS instrument manufactured by THS Instruments LLC. Mechanically it consists of a differentially pumped quadrupole mass spectrometer. The instrument operates in negative ion mode and currently I^- and O2^- reagent ions are used to measure hydrogen peroxide and methylhydroperoxide, respectively, by the formation of cluster ions at masses 80 and 161. The reagent ions are produced by flowing a N2/CH3I/O2 mixture past a ²¹⁰Po foil.

On the G-V, the PCIMS inlet system starts with a PFA Teflon lined heated G-V HIMIL inlet. From the HIMIL the inlet line is comprised of PFA Teflon and is also heated (Hot-Tube, Clayborn Lab). Analytical blanks are performed by diverting the ambient sample flow through a trap filled with Carulite 200 catalyst. Gas phase calibrations are performed through standard additions to ambient air. H2O2 is added from a urea hydrogen peroxide solid decomposition source or by the evaporation of a nano-fluidic flow of a dilute aqueous solution. CH3OOH is added by the evaporation of a nano-fluidic flow of a dilute aqueous solution. The ambient, calibration and reagent gases are vented overboard through the G-V common exhaust.

POPS measures CH2O, H2O2, and CH3OOH.

CH2O is measured by aqueous collection followed by enzyme fluorescence detection.

H2O2 and CH3OOH is measured by aqueous collection followed by HPLC separation and enzyme fluorescence detection.

The MkIV interferometer operates in solar absorption mode, meaning that direct sunlight is spectrally analyzed and the amount of various gases at different heights in the Earth's atmosphere is derived from the shapes and depths of their absorption lines. The optical design of the MkIV interferometer is based largely on that of the ATMOS instrument, which has flown four times on the Space Shuttle. The first three mirrors in the optical path comprise the suntracker. Two of these mirrors are servo-controlled in order to compensate for any angular motion of the observation platform. The subsequent wedged KBr plates, flats, and cube-corner retro-reflectors comprise a double-passed Michelson interferometer, whose function is to impart a wavelength-dependent modulation to the solar beam. This is achieved by sliding one of the retro-reflectors at a uniform velocity so that the recombining beams interfere with each other. A paraboloid then focusses the solar beam onto infrared detectors, which measure the interferometrically modulated solar signal. Finally, Fourier transformation of the recorded detector outputs yields the solar spectrum. An important advantage of the MkIV Interferometer is that by employing a dichroic to feed two detectors in parallel, a HgCdTe photoconductor for the low frequencies (650-1850 cm-1) and a InSb photodiode for the high frequencies (1850-5650 cm-1), the entire mid-infrared region can be observed simultaneously with good linearity and signal-to-noise ratio. In this region over 30 different gases have identifiable spectral signatures including H2O, O3, N2O, CO, CH4, NO, NO2, HNO3, HNO4, N2O5, H2O2, ClNO3, HOCl, HCl, HF, COF2, CF4, SF6, CF2ClCFCl2, CHF2Cl, CF2Cl2, CFCl3, CCl4, CH3Cl, C2H2, C2H6, OCS, HCN, N2, O2, CO2 and many isotopic variants. The last three named gases, having well known atmospheric abundances, are important in establishing the observation geometry of each spectrum, which otherwise can be a major source of uncertainty. Similarly, from analysis of T-sensitive CO2 lines, the temperature profile can be accurately determined. The simultaneity of the observations of all these gases greatly simplifies the interpretation of the results, which are used for testing computer models of atmospheric transport and chemistry, validation of satellite data, and trend determination.

Although the MkIV can measure gas column abundances at any time during the day, the highest sensitivity to atmospheric trace gases is obtained by observing sunrise or sunset from a balloon. The very long (~ 400 km) atmospheric paths traversed by incoming rays in this observation geometry also make this so-called solar occultation technique insensitive to local contamination.

The Charged-coupled device Actinic Flux Spectroradiometers (CAFS) instruments measure in situ down- and up-welling radiation and combine to provide 4 pi steradian actinic flux density spectra from 280 to 650 nm. The sampling resolution is ~0.8 nm with a full width at half maximum (FWHM) of 1.7 nm at 297 nm. From the measured flux, photolysis frequencies are calculated for ~40 important atmospheric trace gases including O3, NO2, HCHO, HONO and NO3 using a modified version of the NCAR Tropospheric Ultraviolet and Visible (TUV) radiative transfer model. The absolute spectral sensitivity of the instruments is determined in the laboratory with 1000 W NIST-traceable tungsten-halogen lamps with a wavelength dependent uncertainty of 3–5%. During deployments, spectral sensitivity is assessed with secondary calibration lamps while wavelength assignment is tracked with Hg line sources and comparisons to spectral features in the extraterrestrial flux. The optical collectors are characterized for angular and azimuthal response and the effective planar receptor distance. CAFS have an excellent legacy of performance on the NASA DC-8 and WB-57 platforms during atmospheric chemistry and satellite validation mission. These include AVE Houston 2004 and 2005, PAVE, CR-AVE, TC4, ARCTAS, DC3, SEAC4RS, KORUS-AQ, ATom and FIREX-AQ. For FIREX-AQ, upgraded electronics and cooling reduced noise and allowed for a decrease to 1 Hz acquisition.

The single mass analyzer CIMS (S-CIMS) was developed for use on NASA’s ER-2 aircraft. Its first measurements were made in 2000 (SOLVE, see photo). Subsequently, it has flown on the NASA DC-8 aircraft for INTEX-NA, DICE, TC4, ARCTAS, ATom, KORUS, FIREX, as well as on the NCAR C-130 during MILAGRO/INTEX-B. HNO3 is measured by selective ion chemical ionization via the fluoride transfer reaction: CF3O^- + HNO3 → HF • NO3^- + CF2O In addition to its fast reaction rate with HNO3, CF3O^- can be used to measure additional acids and nitrates as well as SO2 [Amelynck et al., 2000; Crounse et al., 2006; Huey et al., 1996]. We have further identified CF3O^- chemistry as useful for the measurement of less acidic species via clustering reactions [Crounse et al., 2006; Paulot et al., 2009a; Paulot et al., 2009b; St. Clair et al., 2010]: CF3O^- + HX → CF3O^- • HX where, e.g., HX = HCN, H2O2, CH3OOH, CH3C(O)OOH (PAA) The mass analyzer of the S-CIMS instrument was first upgraded from a quadrupole to a unit-mass resolution time-of-flight (ToF) analyzer. In 2023, the mass filter was again upgraded to an 1m flight path (~5000 deltaM/M).  The ToF admits the sample ion beam to the ion extractor, where a pulse of high voltage orthogonally deflects and accelerates the ions into the reflectron, which in turn redirects the ions toward the multichannel plate detector. Ions in the ToF follow a V-shaped from the extractor to detector, separating by mass as the smaller ions are accelerated to greater velocities by the high voltage pulse. The detector collects the ions as a function of time following each extractor pulse. The rapid-scan collection of the ToF guarantees a high temporal resolution (1 Hz or faster) and simultaneous data products from the S-CIMS instrument for all mass channels [Drewnick et al., 2005]. We have flown a tandem CIMS (TCIMS) instrument in addition to the SCIMS since INTEX-B (2006). The T-CIMS provides parent-daughter mass analysis, enabling measurement of compounds precluded from quantification by the S-CIMS due to mass interferences (e.g. MHP) or the presence of isobaric compounds (e.g. isoprene oxidation products) [Paulot et al., 2009b; St. Clair et al., 2010]. Calibrations of both CIMS instruments are performed in flight using isotopically-labeled reagents evolved from a gas cylinders or from a thermally-stabilized permeation tube oven [Washenfelder et al., 2003]. By using an isotopically labeled standard, the product ion signals are distinct from the natural analyte and calibration can be performed at any time without adversely affecting the ambient measurement.

The Airborne Scanning Microwave Limb Sounder (A-SMLS) makes wide-swath vertical profile observations of the composition
of the upper troposphere and lower stratosphere (the atmospheric region from ~10–20km altitude). A-SMLS measurements are
well suited to studies of convective outflow, long-range pollution transport, and exchange of air between the
troposphere and stratosphere. These atmospheric processes have strong impacts on climate and air quality but are
currently incompletely understood. Improved understanding of these issues is one of the main goals of NASA’s atmospheric
composition Earth science focus area. A-SMLS airborne observations reflect the priority spaceborne “Ozone and Trace Gas”
observables identified in the recent Decadal Survey.

A-SMLS was initially developed and flown on the WB-57 under the NASA Instrument Incubator Program (IIP), following
which, it was adapted to the ER-2 platform. Subsequent work, funded under an additional IIP, has upgraded the receivers
to ones that require cooling to only 70K rather than the previously needed 4K, and to use newer technology digital
spectrometers. Test flights for A-SMLS in this new configuration are planned, but further work, proposed here, is needed
to make the instrument fully “campaign ready”.

A-SMLS observes a ~300km-wide swath ~300km ahead of the aircraft in a 2D raster scan (azimuth and elevation), with
~10x10km horizontal sampling (across and along-track). As typically configured, A-SMLS measures water vapor, ozone, and
carbon monoxide. Retuning of the instrument (including in flight) can provide measurements of other species (including
N2O, HCN, CH3CN, H2CO, and others).

The instrument would be a particularly valuable addition to multi-aircraft campaigns. The broad swath A-SMLS
observations from the ER-2 could be used in near-real-time to help guide lower altitude aircraft carrying in situ
sensors to regions of interest.

As part of NASA's Airborne Instrument Technology Transition (AITT) program, the instrument is currently being updated to
help cement its suitability for campaign-mode operations, specifically, this involves:

- Addition of a liquid cooling loop to transfer waste heat from the existing ~70K cryocooler to the outer skin of the
ER-2 wing pod.

- Development of an “intelligent scan” system that accounts for aircraft orientation etc. when performing the 2D
raster limb scan on the atmosphere.

- Completion of a thorough ground-based instrument calibration.

- Development of an on-board radiance compression scheme that will enable key data to be transferred to the ground for
use in real-time flight planning as described above.

- Updates to the analysis algorithms software used for Aura MLS, enabling their application to A-SMLS observations.