NASA - National Aeronautics and Space Administration

The NASA GSFC Compact Airborne NO2 Experiment (CANOE) instrument measures nitrogen dioxide (NO2) on both pressurized and unpressurized (high-altitude) aircraft. Using non-resonant laser induced fluorescence (LIF), CANOE possesses the high sensitivity, fast time response, and dynamic range needed to observe NO2 throughout the troposphere and lower stratosphere.

Instrument: Reactive Nitrogen

Principal Investigator: David W. Fahey

Organization:
NOAA Aeronomy Laboratory
325 Broadway,R/E/AL6
Boulder, CO 80303

Principle of Operation:
The instrument is designed to measure nitric oxide (NO) and the sum of reactive nitrogen oxides (NOy). Species included in NOy are NO, NO2, HNO3, N2O5 and ClONO2. NO is measured by detecting light from the chemiluminescent reaction between reagent ozone and NO in the ambient sample. NOy is reduced to NO by catalytic reduction on a gold surface with carbon monoxide (CO) acting as a reducing agent. The catalyst is located outside the aircraft fuselage in order to avoid inlet line losses. Two reaction vessels are incorporated in the instrument to allow for simultaneous measurement of NO and NOy. Ca1ibration with NO or NO2 is made by standard addition several times during a flight. The baseline of each measurement is determined in part by the addition of synthetic air that contains no reactive nitrogen. The difference between the sample flow velocity in the inlet opening and the aircraft velocity cause aerosol particles in the atmosphere to be oversampled. For sizes below 5 micrometers in diameter, this feature assists in the identification of aerosol particles that contain NOy.

Accuracy: < 20% plus precision
Detection limit: < 0.1 ppbv NOy, ~0.02 ppbv NO
Response time: 1 sec
Location on the ER2: Lower Q-bay rack

Reference: D.W. Fahey et al., In situ aerosol measurements of total reactive nitrogen, total water, and aerosol in a polar stratospheric cloud in the Antarctic, J. Geophys. Res. 94 11-99-11315, 1959.

4STAR (Spectrometers for Sky-Scanning Sun-Tracking Atmospheric Research; Dunagan et al., 2013) is an airborne sun-sky spectrophotometer measuring direct solar beam transmittance (i.e., 4STAR determines direct solar beam transmission by detecting direct solar irradiance) and narrow field-of-view sky radiance to retrieve and remotely sense column-integrated and, in some cases, vertically resolved information on aerosols, clouds, and trace gases. The 4STAR team is a world leader in airborne sun-sky photometry, building on 4STAR’s predecessor instrument, AATS-14 (the NASA Ames Airborne Tracking Sun photometers; Matsumoto et al., 1987; Russell et al. 1999, and cited in more than 100 publication) and greatly expanding aerosol observations from the ground-based AERONET network of sun-sky photometers (Holben et al., 1998) and the Pandora network of ground-based direct-sun and sky spectrometer (e.g, Herman et al., 2009).

4STAR is used to quantify the attenuated solar light (from 350 to 1650 nm) and retrieve properties of various atmospheric constituents: spectral Aerosol Optical Depth (AOD) from ultraviolet to the shortwave infrared (e.g., LeBlanc et al., 2020, Shinozuka et al., 2013); aerosol intensive properties - Single Scattering Albedo (SSA; e.g., Pistone et al., 2019), asymmetry parameter, scattering phase function, absorption angstrom exponent, size distribution, and index of refraction; various column trace gas components (NO₂, Ozone, Water Vapor; e.g., Segal-Rosenheimer et al., 2014, with potential for SO₂ and CH₂O); and cloud optical depth, effective radius and thermodynamic phase (e.g., LeBlanc et al., 2015).

Some examples of the science questions that 4STAR have pursued in the past and will continue to address:

• What is the Direct Aerosol Radiative Effect on climate and its uncertainty? (1)
• How much light is absorbed by aerosol emitted through biomass burning? (1)
• How does heating of the atmosphere by absorbing aerosol impact large scale climate and weather patterns? (1)
• How does aerosol spatial consistency of extensive and intensive properties compare? (2)
• How does the presence of aerosol impact Earth’s radiative transfer, with co-located high concentration of trace gas? (3, 5)
• What is the impact of air quality from long-range transport of both aerosol particulates and column NO2 and Ozone, and their evolution? (3, 6)
• What are the governing properties and spatial patterns of local and transported aerosol? (1)
• How are cloud properties impacted near the sea-ice edge? (4)
• In heterogeneous environments where clouds and aerosols are present, how much solar radiation is impacted by 3D radiative transfer? And how does that impact the aerosol properties? (5)

(1) ORACLES: Zuidema et al., doi:10.1175/BAMS-D-15-00082.1., 2016; LeBlanc et al., doi:10.5194/acp-20-1565-2020, 2020; Pistone et al., https://doi.org/10.5194/acp-2019-142, 2019;Cochrane et al., https://doi.org/10.5194/amt-12-6505-2019, 2019; Shinozuka et al., https://doi.org/10.5194/acp-20-11275-2020, 2020; Shinozuka et al., https://doi.org/10.5194/acp-20-11491-2020, 2020
(2) KORUS-AQ:  LeBlanc et al., doi:https://doi.org/10.5194/acp-22-11275-2022, 2022

(3) KORUS-AQ: Herman et al., doi:10.5194/amt-11-4583-2018, 2018
(4) ARISE: Smith et al., https://doi.org/10.1175/BAMS-D-14-00277.1, 2017; Segal-Rosenheimer et al., doi:10.1029/2018JD028349, 2018
(5) SEAC4RS: Song et al., doi: 10.5194/acp-16-13791-2016, 2016; Toon et al., https://doi.org/10.1002/2015JD024297, 2016
(6) TCAP: Shinozuka et al., doi:10.1002/2013JD020596, 2013; Segal-Rosenheimer et al., doi:10.1002/2013JD020884, 2014

The NOAA NOyO₃ 4-channel chemiluminescence (CL) instrument will provide in-situ measurements of nitric oxide (NO), nitrogen dioxide (NO₂), total reactive nitrogen oxides (NO_y), and ozone (O₃) on the NASA DC-8 during the FIREX-AQ project. Different versions of this instrument have flown on the NASA DC-8 and NOAA WP-3D research aircraft on field projects since 1995. It provides fast-response, specific, high precision, and calibrated measurements of nitrogen oxides and ozone at a spatial resolution of better than 100m at typical DC-8 research flight speeds. Detection is based on the gas-phase CL reaction of NO with O₃ at low pressure, resulting in photoemission from electronically excited NO₂. Photons are detected and quantified using pulse counting techniques, providing ~5 to 10 part-per-trillion by volume (pptv) precision at 1 Hz data rates. One detector of the integrated 4-channel instrument is used to measure ambient NO directly, a second detector is equipped with a UV-LED converter to photodissociate ambient NO₂ to NO, and a third detector is equipped with a heated gold catalyst to reduce ambient NOy species to NO. Reagent ozone is added to these sample streams to drive the CL reactions with NO. Ambient O₃ is detected in the fourth channel by adding reagent NO.

This is a 2-channel instrument based on the chemiluminescence detection of NO via reaction with O3 to form excited NO2, which is detected via photon counting. One sample channel is used to measure nitric oxide, NO, and the second measures nitrogen dioxide, NO2, by flowing ambient air through a glass cell illuminated by light-emitting diodes at 395 nm, for the conversion of NO2 to NO via photolysis. The instrument is similar to instruments previously built at NCAR [Ridley and Grahek, 1990; Ridley et al., 2004]. In the UTLS region, NOx (= NO + NO2) is mostly in the form of NO and is formed in situ by lightning, is emitted by aircraft, and may be transported to the UTLS from the boundary layer by convection.

The UC Berkeley thermal-dissociation laser-induced fluorescence (TD- LIF) instrument detects NO2 directly and detects total peroxynitrates (ΣPNs ≡ PAN + PPN +N2O5 + HNO4. . .), total alkyl- and other thermally stable organic nitrates (ΣANs), and HNO3 following thermal dissociation of these NOy species to NO2. The sensitivity for NO2 at 1 Hz is 30 pptv (S/N=2) with a slope uncertainty of 5%. The uncertainties for the dissociated species are 10% for ΣPNs and 15% for ΣANs and HNO3.

The NCAR NOxyO3 instrument is a 4-channel chemiluminescence instrument for the measurement of NO, NO2, NOy, and O3. NOx (NO and NO2) is critical to fast chemical processes controlling radical chemistry and O3 production. Total reactive nitrogen (NOy = NO + NO2 + HNO3 + PANs + other organic nitrates + HO2NO2 + HONO + NO3 + 2*N2O5 + particulate NO3- + …) is a useful tracer for characterizing air masses since it has a tendency to be conserved during airmass aging, as NOx is oxidized to other NOy species.

NOx (NO and NO2), NOy (total reactive nitrogen), and O3 are measured using the NCAR 4-channel chemiluminescence instrument, previously flown on the NASA WB-57F and the NCAR C130. NO is measured via addition of reagent O3 to the sample flow to generate the chemiluminescent reaction producing excited NO2, which is detected by photon counting with a dry-ice cooled photomultiplier tube. NO2 is measured as NO following photolytic conversion of NO2, with a time response of about 3 sec due to the residence time in the photolysis cell. NO is measured with an identical time response due to use of a matching volume. NOy is measured via Au-catalyzed conversion of reactive nitrogen species to NO, in the presence of CO, with a time response of slightly better than 1 sec. O3 is measured using the same chemiluminescent reaction but with the addition of reagent NO to the sample flow. Time response for the ozone measurement is slightly better than 1 s.

The Particle Into Liquid Sampler (PILS) was developed for rapid automated on-line and continuous measurement of ambient aerosol bulk composition. The general approach is based on earlier devices in which ambient particles are mixed with saturated water vapor to produce droplets easily collected by inertial techniques. The resulting liquid stream is analyzed with an ion chromatograph to quantitatively measure the bulk aerosol ionic components. In this instrument, a modified version of a particle size magnifier is employed to activate and grow particles comprising the fine aerosol mass. A single jet inertial impactor is used to collect the droplets onto a vertical glass plate that is continually washed with a constant water diluent flow of nominally 0.10 ml min-1. The flow is divided and then analyzed by a dual channel ion chromatograph. In its current form, 4.3 min integrated samples were measured every 7 min. The instrument provides bulk composition measurements with a detection limit of approximately 0.1 µg m-3 for chloride, nitrate, sulfate, sodium, ammonium, calcium, and potassium.

The NOy instrument has three independent chemiluminescence detectors for simultaneous measurements of NOy, NO2, and NO. Each detector utilizes the reaction between NO in the sample with reagent O3. The NO/O3 reaction produces excited state NO2 which emits light of near 1µ m wavelength. Emitted photons are detected with a cooled photomultiplier tube.

Because NOy species other than NO do not respond in the chemiluminescence detector, NOy component species are reduced to NO by catalytic reduction on a gold surface with carbon monoxide (CO) acting as a reducing agent. Conversion efficiencies are > 90% at surface temperatures of 300°C. An NO signal representing NOy is then detected by chemiluminescence in the detector module. The catalyst is located outside the aircraft fuselage in order to avoid inlet line losses. NO2 is photolytically converted to NO in a glass cell in the presence of intense UV light between 300 and 400 nm. The conversion fraction is > 50% for a residence time of 1 s. The chemiluminescence detector detects NO as well as the additional NO from NO2. The third channel measures NO directly by passing the ambient sample through the detector module.

The response of each detector is checked several times in flight by standard addition of NO or NO2 calibration gas. The baseline of each measurement is determined in part by the addition of synthetic air that contains no reactive nitrogen. A continuous flow of water vapor is added directly to the sample flow in order to reduce the background signal in the detectors.

The sampling inlet for NOy is located outside the fuselage of the aircraft in a separate football-shaped housing. The shape of the housing allows for the inertial separation of large aerosols (> 5 µm diameter) from the NOy inlet at the downstream end of the housing.