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Diode Laser Hygrometer

The DLH has been successfully flown during many previous field campaigns on several aircraft, most recently ACTIVATE (Falcon); FIREX-AQ, ATom, KORUS-AQ, and SEAC4RS (DC-8); POSIDON (WB-57); CARAFE (Sherpa); CAMP2Ex and DISCOVER-AQ (P-3); and ATTREX (Global Hawk). This sensor measures water vapor (H2O(v)) via absorption by one of three strong, isolated spectral lines near 1.4 μm and is comprised of a compact laser transceiver and a sheet of high grade retroflecting road sign material to form the optical path. Optical sampling geometry is aircraft-dependent, as each DLH instrument is custom-built to conform to aircraft geometric constraints. Using differential absorption detection techniques, H2O(v) is sensed along the external path negating any potential wall or inlet effects inherent in extractive sampling techniques. A laser power normalization scheme enables the sensor to accurately measure water vapor even when flying through clouds. An algorithm calculates H2O(v) concentration based on the differential absorption signal magnitude, ambient pressure, and temperature, and spectroscopic parameters found in the literature and/or measured in the laboratory. Preliminary water vapor mixing ratio and derived relative humidities are provided in real-time to investigators.

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Charged-coupled device Actinic Flux Spectroradiometers

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.

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Chemical Ionization Mass Spectrometer

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.

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