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Soluble Acidic Gases and Aerosols

As part of the measurement team on the NASA DC-8 we operate two related installations: a mist chamber/ion chromatograph (MC/IC) sampling/analysis system providing near real time results for selected species, and a bulk aerosol system that collects particulates onto filters for subsequent analysis. We use ion chromatography on aqueous extracts of the bulk aerosol samples collected on Teflon filters to quantify soluble ions (Cl-, Br-, NO3-, SO42-, C2O42-, Na+, NH4+, K+, Ca+, and Mg+). Filters are exposed on all level flight legs. Below 3 km exposure times are 5 minutes or less, increasing at higher altitudes to a maximum sample time of 15 minutes. Aerosols participate in heterogeneous chemistry, impact radiative transfer, and can be detected from space. Our measurements help to validate and extend retrievals of aerosol distributions and properties by MODIS, MISR and CALIPSO. In addition, several of the particle-associated ions are tracers of sources of gas and aerosol pollutants (e.g., SO42- from industrial emissions of SO2, enhancements of C2O42-, K+, and NH4+ indicate encounters with biomass burning plumes, Na+, and Cl- are tracers of seasalt, Mg2+ and Ca2+ are tracers of dust). Our system has two inlets, allowing collection of paired samples simultaneously.

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Chemical Ionization Mass Spectrometer

The CIMS instrument consists of a low pressure ion molecule reactor (IMR) coupled to a quadrupole mass filter by an actively pumped collisional dissociation chamber (CDC) and an octopole ion guide. The vacuum system is a 100 mm outer diameter stainless steel chamber evacuated with two small turbo pumps (70 l s-1). The mass filter is a set of 9.5 mm diameter quadrupole rods housed in the main vacuum chamber. The CDC is a short 80 mm diameter chamber that houses an octopole ion guide and is evacuated with a hybrid molecular drag pump. The IMR is evacuated with a scroll pump (300 l min-1) that also serves as the backing pump for the mass spectrometer.

Click here for the Collaborative Ground and Airborne Observations description page.

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DC-8 - AFRC, Gulfstream V - NSF
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Whole Air Sampler

The UC-Irvine research group collected whole air samples aboard the NASA DC-8 aircraft during the summer 2019 NASA Fire Influence on Regional to Global Environments Experiment - Air Quality (FIREX-AQ) field mission. More than 70 trace gases were identified and quantified at our Irvine laboratory, including C2-C10 NMHCs, C1-C2 halocarbons, C1-C5 alkyl nitrates, and selected sulfur compounds using our established technique of airborne whole air sampling followed by laboratory analysis using gas chromatography (GC) with flame ionization detection (FID), electron capture detection (ECD), and mass spectrometric detection (MSD). Our experimental procedures build on those that have been successfully employed for numerous prior NASA field missions, for example PEM Tropics A and B, TRACE-P, INTEX-A and B, ARCTAS, DC-3, SEAC4RS, ATom, KORUS-AQ, and SARP.

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Single Particle Soot Photometer (NOAA)

The SP2 is a laser-induced incandescence instrument primarily used for measuring the refractory BC  (rBC) mass content of individual accumulation-mode aerosol particles. It is able to provide this data product independently of the total particle morphology and mixing state, and thus delivers detailed information not only about BC loadings, but also size distributions, even in exceptionally clean air. The instrument can also provide the optical size of individual particles containing rBC, and identify the presence of materials associated with the BC fraction (i.e. identify the rBC’s mixing state). Since its introduction in 2003, the SP2 has been substantially improved, and now can be considered a highly competent instrument for assessing BC loadings and mixing state in situ.  NOAA deploys multiple SP2s with different designs: the first was built for the WB-57F research aircraft. Two others are rack-mounted units customized at NOAA; one of the rack mounted units can be humidified, and has been deployed with a paired dry rack-mounted SP2 as the "Humidified-Dual SP2" (HD-SP2). The rack mounted units are suitable for in-cabin operations.

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PAN and Trace Hydrohalocarbon ExpeRiment

PANTHER uses Electron Capture Detection and Gas Chromatography (ECD-GC) and Mass Selective Detection and Gas Chromatography (MSD-GC) to measure numerous trace gases, including Methyl halides, HCFCs, PAN, N20, SF6, CFC-12, CFC-11, Halon-1211, methyl chloroform, carbon tetrachloride.

3 ECD (electron capture detectors), packed columns (OV-101, Porpak-Q, molecular sieve).

1 ECD with a TE (thermal electric) cooled RTX-200 capillary column.

2-channel MSD (mass selective detector). The MSD analyses two independent samples concentrated onto TE cooled Haysep traps, then passed through two temperature programmed RTX-624 capillary columns.

With the exception of PAN, all channels of chromatography are normalized to a stable in-flight calibration gas references to NOAA scales. The PAN data is normalized to an in-flight PAN source of ≈ 100 ppt with ±5 % reproducibility. This source is generated by efficient photolytic conversion of NO in the presence of acetone. Detector non-linearity is taken out by lab calibrations for all molecules.

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Particle Analysis By Laser Mass Spectrometry

The NOAA PALMS instrument measures single-particle aerosol composition using UV laser ablation to generate ions that are analyzed with a time-of-flight mass spectrometer.  The PALMS size range is approximately 150 to >3000 nm and encompasses most of the accumulation and coarse mode aerosol volume. Individual aerosol particles are classified into compositional classes.  The size-dependent composition data is combined with aerosol counting instruments from Aerosol Microphysical Properties (AMP), the Langley Aerosol Research Group Experiment (LARGE), and other groups to generate quantitative, composition-resolved aerosol concentrations.  Background tropospheric concentrations of climate-relevant aerosol including mineral dust, sea salt, and biomass burning particles are the primary foci for the ATom campaigns.  PALMS also provides a variety of compositional tracers to identify aerosol sources, probe mixing state, track particle aging, and investigate convective transport and cloud processing.

*_Standard data products_**: *

Particle type number fractions: sulfate/organic/nitrate mixtures, biomass burning, EC, sea salt, mineral dust, meteoric, alkali salts, heavy fuel combustion, and other. Sampling times range from 1-5 mins.

*_Advanced data products_**:*

Number, surface area, volume, and mass concentrations of the above particle types. Total sulfate and organic mass concentrations. Relative and absolute abundance of various chemical markers and aerosol sub-components: methanesulfonic acid, sulfate acidity, organic oxidation level, iodine, bromine, organosulfates, pyridine, and other species.

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Meteorological Measurement System

The Meteorological Measurement System (MMS) is a state-of-the-art instrument for measuring accurate, high resolution in situ airborne state parameters (pressure, temperature, turbulence index, and the 3-dimensional wind vector). These key measurements enable our understanding of atmospheric dynamics, chemistry and microphysical processes. The MMS is used to investigate atmospheric mesoscale (gravity and mountain lee waves) and microscale (turbulence) phenomena. An accurate characterization of the turbulence phenomenon is important for the understanding of dynamic processes in the atmosphere, such as the behavior of buoyant plumes within cirrus clouds, diffusions of chemical species within wake vortices generated by jet aircraft, and microphysical processes in breaking gravity waves. Accurate temperature and pressure data are needed to evaluate chemical reaction rates as well as to determine accurate mixing ratios. Accurate wind field data establish a detailed relationship with the various constituents and the measured wind also verifies numerical models used to evaluate air mass origin. Since the MMS provides quality information on atmospheric state variables, MMS data have been extensively used by many investigators to process and interpret the in situ experiments aboard the same aircraft.

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Diode Laser Hygrometer

The DLH has been successfully flown during many previous field campaigns on several aircraft, most recently ATom, KORUS-AQ, and SEAC4RS (DC-8), POSIDON (WB-57), CARAFE (Sherpa), DISCOVER-AQ (P-3), and ATTREX (Global Hawk). This sensor measures water vapor (H2O(v)) via absorption by one of three strong, isolated lines in the (101) combination band near 1.4 μm and is comprised of a compact laser transceiver mounted to a DC-­8 window plate and a sheet of high grade retroflecting road sign material applied to an outboard DC‐8 engine housing to complete the optical path. Using differential absorption detection techniques, H2O(v) is sensed along the 28.5m 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 that are measured in the laboratory. Preliminary water vapor mixing ratio and derived relative humidities are provided in real-time to investigators aboard the DC-8.

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CCD Actinic Flux Spectroradiometers

The CCD Actinic Flux Spectroradiometers (CAFS) developed in the ARIM laboratory will be deployed on the NASA DC-8 for SEAC4RS and DC3 field campaigns. The instruments measure spectrally resolved down- and up-welling in situ ultraviolet and visible actinic flux from approximately 280-650 nm. Photolysis frequencies for photodissociation reactions for species including O3, NO2, CH2O, HONO, HNO3, N2O5, HO2NO2, PAN, H2O2, CH3OOH, CH3ONO2, CH3CH2ONO2, CH3COCH3, CH3CHO, CH3CH2CHO, CHOCHO, CH3COCHO, CH3CH2CH2CHO, CH3COCH2CH3, Br2, BrO, Br2O, BrNO3, BrCl, HOBr, BrONO2, Cl2, ClO, and ClONO2 are calculated from the radiative measurements. Careful calibration techniques and comparison to the NCAR/TUV radiative transfer model improves the accuracy and precision of the measurements. CAFS instruments have a successful heritage of radiation measurements during atmospheric chemistry and satellite validation missions including NASA AVE, PAVE, CR-AVE, TC-4 and ARCTAS campaigns on the WB-57 and DC-8 platforms and during the NSF OASIS ground campaign in Barrow, AK. Similar instruments will be deployed on the NCAR G-V platform as part of the HIAPER Airborne Radiation Package (HARP) as a part of DC3 and SEAC4RS. In situ solar radiation measurements are critical to NASA atmospheric composition research. Actinic flux radiation drives the chemistry of the atmosphere, including the evolution of ozone, greenhouse gases, biomass burning, and other anthropogenic and natural trace constituents. The evolution of boundary layer and tropospheric constituents convected to the upper troposphere and lower stratosphere requires knowledge of the complex radiative fields expected during the campaigns. The gases, in turn, control the chemical evolution of aerosols.

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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). Subsequently, it has flown on the NASA DC-8 aircraft for INTEX-NA, DICE, TC4, and ARCTAS, 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 has recently been upgraded from a quadrupole to a time-of-flight (ToF) analyzer. 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, 43 cm path from 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 for HNO3 and organic acids are performed in flight using isotopically-labeled reagents evolved 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. We also fly calibration standards for H2O2 (evolved from urea-hydrogen peroxide) and MHP (from a diffusion vial).

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