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Proton-Transfer-Reaction Mass Spectrometer

PTR-MS is a state-of-the-art chemical ionization mass spectrometry technique that allows for fast (seconds) and highly sensitive (detection limits in the tens of pptv range) of volatile organic compounds (VOCs). A detailed description of the measurement principle and the instrument can be found at: http://en.wikipedia.org/wiki/Proton-transfer-reaction_mass_spectrometry

The technique was developed in the mid-1990s at the University of Innsbruck in Austria and has since then become a routine and integral part of most tropospheric chemistry field campaigns including INDOEX 1999, SOS 1999, TEXAQS 2000, AOE 2001, BEWA 2002, ECHO 2003, ARCTAS-2008, DISCOVER-AQ 2011 – just to name a few of the campaigns in which the University of Innsbruck measurement team has been involved. An interactive presentation of the airborne PTR-MS instrument can be found at: http://discover-aq.larc.nasa.gov/instruments.php (click on interactive viewer and on PTR-MS)

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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.

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Differential Absorption Lidar

The NASA Langley Airborne Differential Absorption Lidar (DIAL) system uses four lasers to make DIAL O3 profile measurements in the ultraviolet (UV) simultaneously with aerosol profile measurements in the visible and IR. Recent changes incorporate an additional laser and modifications to the receiver system that will provide aerosol backscatter, extinction, and depolarization profile measurements at three wavelengths (UV, visible, and NIR). For SEAC4RS, the DIAL instrument will include for the first time aerosol and cloud measurements implementing the High Spectral Resolution Lidar (HSRL) technique [Hair, 2008]. The modifications include integrating an additional 3-wavelength (355 nm, 532 nm, 1064 nm) narrowband laser and the receiver to make the following measurements; depolarization at all three wavelengths, aerosol/cloud backscatter and extinction at 532 nm via the HSRL technique, and aerosol/cloud backscatter at the 355 and 1064 nm via the standard backscatter lidar technique. Integration of the aerosol extinction profile at 532nm above and below the aircraft also provides aerosol optical depth (AOD) along the aircraft flight track.

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HOx Chemical Ionization Mass Spectrometer

An inlet collects ambient air from the free air stream and adds reagents, including O2 or N2 dilutents, and NO and SO2 reagent gases. This method, called "oxygen dilution modulation" leads to nearly 100% measurement of HO2 and RO2 in the O2 dilution/low reagent concentration mode, whereas RO2 is measured with less than 10% efficiency in the N2 dilution/higher reagent concentration mode. This is because the chemistry converts peroxy radicals to H2SO4 efficiently in the O2 mode, but RO2 radicals are converted to RONO in the N2 mode. The H2SO4 thus produced is ionized by reaction with NO3- ions. The reagent and product ions are detected by mass spectrometry using quadrupole mass filtering and counting by a channel electron multiplier operating in the negative ion mode.

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Difference Frequency Generation Absorption Spectrometer

The DFGAS instrument utilizes a room temperature infrared (IR) laser source based upon non-linear difference frequency generation (DFG) in the measurement of CH2O.

Mid-IR laser light is generated in the DFG system by mixing the output of two near-IR room temperature laser sources (one at 1562-nm and the other at 1083-nm) in a periodically poled lithium niobate (PPLN) non-linear wavelength conversion crystal. The mid-IR difference frequency at 2831.6 cm-1 (3.53-μm) is generated at the PPLN output and directed through a multipass astigmatic Herriott cell (100-m pathlength using ~ 4-liter sampling volume) and ultimately onto IR detectors employing a number of optical elements. A portion of the IR beam is split off by a special beam splitter (BS) before the multipass cell and focused onto an Amplitude Modulation Detector (AMD) to capture and remove optical noise from various components in the difference frequency generation process. A third detection channel from light emanating out the back of the beam splitter is directed through a low pressure CH2O reference cell and onto a reference detector (RD) for locking the center of the wavelength scan to the absorption line center. The mid-IR DFG output is simultaneously scanned and modulated over the CH2O absorption feature, and the second harmonic signals at twice the modulation frequency from the 3 detectors are processed using a computer lock-in amplifier [Weibring et al. [2006].

Ambient air is continuously drawn through a heated rear-facing inlet at flow rates around 9 standard liters per minute (slm), through a pressure controller, and through the multipass Herriott cell maintained at a constant pressure around 50-Torr. Ambient measurements are acquired in 1-second increments for time periods as long as 60 to 120-seconds (to be determined during the campaign), and this will be followed by 15-seconds of background zero air acquisition, using an onboard CH2O scrubbing unit. The zero air is added back to the inlet a few centimeters from the tip at flow rates ~ 2 to 3 slm higher than the cell flow. This frequent zeroing procedure very effectively captures and removes optical noise as well as residual outgassing from inlet line and cell contaminants. Retrieved CH2O mixing ratios are determined for each 1-second ambient spectrum by fitting to a reference spectrum, obtained by introducing high concentration calibration standards (~ 3 to 7-ppbv) from an onboard permeation calibration system into the inlet approximately every hour. The calibration outputs for the two permeation tubes employed are determined before and after the field campaign using multiple means, including direct absorption employing the Beer-Lambert Law relationship. The 1-second ambient CH2O results can be further averaged into longer time intervals for improved precision. However, in all cases the 1-second results are retained. This flexibility allows one to further study pollution plumes with high temporal resolution, and at the same time study more temporally constant background CH2O levels in the upper troposphere using longer integration times.

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Alan Fried (Co-I)

Atmospheric Vertical Observations of CO2 in the Earth's Troposphere

The NASA Langley CO2 sampling system (AVOCET) has an extensive measurement heritage in tropospheric field campaigns, delivering high reliability over 3400 flight hours (452 science flights) and is recognized within the CO2 community as a benchmark for evaluating newly evolving remote CO2. This instrument was adapted by the investigators for airborne sampling and has been successfully deployed aboard NASA research aircraft beginning with the PEM-West A mission in 1992, and more recently during the 2016 KORUS-AQ, 2017 ACSENDS/ABoVE, and 2019 FIREX-AQ missions. The newest iteration of the technique as of 2017 has at its core a modified LI-COR model 7000 non-dispersive infrared spectrometer (NDIR). The basic instrument is small (13 x 25 x 37 cm) and composed of dual 11.9 cm^3 sample/reference cells, a feedback stabilized infrared source, 500 Hz chopper, thermoelectrically-cooled solid state PbSe detector, and a narrow band (150 nm) interference filter centered on the 4.26 μm CO2 absorption band. Using synchronous signal detection techniques, it operates by sensing the difference in light absorption between the continuously flowing sample and reference gases occupying each side of the dual absorption cell. Thus, by selecting a reference gas of approximately the same concentration as background air (~405 ppm), minute fluctuations in atmospheric concentration can be quantified with high precision. Calbrations are peformed frequently during flight using WMO-traceable standards from NOAA ESRL. Precisions of ≤ 0.1 ppm (±1σ) for 1 Hz sampling rates are typical for our present airborne CO2 system when operated at 600 torr sample pressure.

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CU Aircraft High-Resolution Time-of-Flight Aerosol Mass Spectrometer

Principle: The CU aircraft version of the Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) detects non-refractory submicron aerosol composition by impaction on a vaporizer at 600°C, followed by electron ionization and time-of-flight mass spectral analysis. Size-resolved composition can be quantified by measuring the arrival times of the aerosol at the vaporizer.

Aircraft Operation: (1 min cycles, can be adjusted to meet mission goals):
46 s total concentration measurements (1 s resolution, can be increased to up to 10 Hz upon request)
5 s speciated size distribution measurements (with improved S/N detection due to ePToF acquisition)
9 s Background + Overhead
Higher accuracy due to flight day calibrations using built-in system
Custom pressure controlled inlet with confirmed performance up to 41 kft

Real Time Data Products: 
PM1 Aerosol Mass Concentrations:
Organic aerosol (OA) , SO4, NO3, NH4, Chloride 
OA Chemical Markers: f44 (Secondary OA), f57 (hydrocarbon-like OA), f60 (biomass burning OA), f82 (isoprene epoxide-SOA), other fx upon request

More Advanced Products:
- PM1 Seasalt, ClO4, total I, total Br, MSA concentrations
- O/C, H/C, OA/OC, OSc
- Particle organic nitrates (pRONO2)
- Ammonium Balance, estimated pH
- OA components by positive matrix factorization (PMF)
- Particle eddy covariance fluxes of all species
- Speciated Aerosol size distributions

Detection Limits (1s, ng sm-3), (1 min, ng sm-3) from start of the flight (due to custom cyropump):
Sulfate: 40, 15
Nitrate: 15, 6
Ammonium: 3, 1
Chloride: 30, 12
OA: 200, 80
For detailed OA analysis, longer averaging (3-30 s, depending on OA concentration) is needed. A 1 min product is hence provided as well.


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DC-8 - AFRC, C-130 - NSF
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High Spectral Resolution Lidar

The NASA Langley airborne High Spectral Resolution Lidar (HSRL) is used to characterize clouds and small particles in the atmosphere, called aerosols. From an airborne platform, the HSRL scientist team studies aerosol size, composition, distribution and movement.

The HSRL instrument is an innovative technology that is similar to radar; however, with lidar, radio waves are replaced with laser light. Lidar allows researchers to see the vertical dimension of the atmosphere, and the advanced HSRL makes measurements that can even distinguish among different aerosol types and their sources. The HSRL technique takes advantage of the spectral distribution of the lidar return signal to discriminate aerosol and molecular signals and thereby measure aerosol extinction and backscatter independently.

The HSRL provides measurements of aerosol extinction at 532 nm and aerosol backscatter and depolarization at 532 and 1064 nm. The HSRL measurements of aerosol extinction, backscattering, and depolarization profiles are being used to:

1) characterize the spatial and vertical distributions of aerosols
2) quantify aerosol extinction and optical thickness contributed by various aerosol types
3) investigate aerosol variability near clouds
4) evaluate model simulations of aerosol transport
5) assess aerosol optical properties derived from a combination of surface, airborne, and satellite measurements.

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B-200 - LARC, DC-8 - AFRC, NASA P-3 Orion - WFF
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