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Creators/Authors contains: "Agnese, Michael"

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  1. Abstract. A closed-path quantum-cascade tunable infrared laserdirect absorption spectrometer (QC-TILDAS) was outfitted with an inertialinlet for filter-less separation of particles and several custom-designedcomponents including an aircraft inlet, a vibration isolation mountingplate, and a system for optionally adding active continuous passivation forgas-phase measurements of ammonia (NH3) from a research aircraft. Theinstrument was then deployed on the NSF/NCAR C-130 aircraft during researchflights and test flights associated with the Western wildfire Experiment forCloud chemistry, Aerosol absorption and Nitrogen (WE-CAN) field campaign.The instrument was configured to measure large, rapid gradients in gas-phaseNH3, over a range of altitudes, in smoke (e.g., ash and particles), inthe boundary layer (e.g., during turbulence and turns), in clouds, and in ahot aircraft cabin (e.g., average aircraft cabin temperatures expected toexceed 30 ∘C during summer deployments). Important designgoals were to minimize motion sensitivity, maintain a reasonable detectionlimit, and minimize NH3 “stickiness” on sampling surfaces to maintainfast time response in flight. The observations indicate that adding ahigh-frequency vibration to the laser objective in the QC-TILDAS andmounting the QC-TILDAS on a custom-designed vibration isolation plate weresuccessful in minimizing motion sensitivity of the instrument during flight.Allan variance analyses indicate that the in-flight precision of theinstrument is 60 ppt at 1 Hz corresponding to a 3σ detection limitof 180 ppt. Zero signals span ±200, or 400 pptv total, withcabin pressure and temperature and altitude in flight. The option for activecontinuous passivation of the sample flow path with1H,1H-perfluorooctylamine, a strong perfluorinated base, preventedadsorption of both water and basic species to instrument sampling surfaces.Characterization of the time response in flight and on the ground showedthat adding passivant to a “clean” instrument system had little impact onthe time response. In contrast, passivant addition greatly improved the timeresponse when sampling surfaces became contaminated prior to a test flight.The observations further show that passivant addition can be used tomaintain a rapid response for in situ NH3 measurements over the duration of anairborne field campaign (e.g., ∼2 months) since passivantaddition also helps to prevent future buildup of water and basic species oninstrument sampling surfaces. Therefore, we recommend the use of activecontinuous passivation with closed-path NH3 instruments when rapid(>1 Hz) collection of NH3 is important for the scientificobjective of a field campaign (e.g., sampling from aircraft or anothermobile research platform). Passivant addition can be useful for maintainingoptimum operation and data collection in NH3-rich and humid environments orwhen contamination of sampling surfaces is likely, yet frequent cleaning isnot possible. Passivant addition may not be necessary for fast operation,even in polluted environments, if sampling surfaces can be cleaned when thetime response has degraded. 
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