Simultaneous Transmission/Absorption Photometry of Particle-Laden Filters from Wildland Fires during the Biomass Burning Observation Project (BBOP) Field Campaign.

Transmissivity and absorptivity measurements were carried out simultaneously in the visible (wavelength of 532 nm) at laboratory conditions using particle-laden filters obtained from a three-wavelength particle/soot absorption photometer (PSAP). The particles were collected on filters from wildland fires over the Pacific Northwest during the Department of Energy Biomass Burning Observation Project (BBOP) field campaign in 2013. The objective of this investigation was to apply this measurement approach, referred to as simultaneous transmission/absorption photometry (STAP), to estimate the aerosol extinction coefficient from actual field-campaign filter aerosol, and compare results with the PSAP. The STAP approach offers several advantages over the PSAP, including estimation of the extinction coefficient from temperature measurements (avoiding the complexities associated with filter reflectivity/scattering measurements), as well as determination of the filter optical properties and filter effects on particle absorption (resulting in particle absorption enhancement). The experimental arrangement included a laser probe beam impinging normal to the particle-coated surface of a vertically mounted filter, and a thermocouple placed flush in the middle of (and in thermal contact with) the filter uncoated back surface. With this simple arrangement, the transmissivity and absorptivity were determined simultaneously at a given laser beam wavelength. The measurement repeatability was better than 0.3 K (95 % confidence level) for temperature and 0.4 mW for laser power. The limit of detection for the extinction coefficient was estimated to be (8 to 12) Mm-1 (95 % confidence level) at about 1.9 mW laser power. The extinction coefficient was determined through measurement of both PSAP blank and exposed filters. Filters were obtained from nine different aircraft flights conducted during the BBOP campaign, representing different flight patterns, days, stages of burning, landscapes, and wildland fires. The STAP extinction coefficient matched the darkness of the filter coating, however the PSAP-filter results did not follow the same order. Although there were differences in transmissivity between the two techniques, the estimated values for absorption coefficient were in good agreement.

Spherical tarball particles form through rapid chemical and physical changes of organic matter in biomass-burning smoke.

Biomass burning (BB) emits enormous amounts of aerosol particles and gases into the atmosphere and thereby significantly influences regional air quality and global climate. A dominant particle type from BB is spherical organic aerosol particles commonly referred to as tarballs. Currently, tarballs can only be identified, using microscopy, from their uniquely spherical shapes following impaction onto a grid. Despite their abundance and potential significance for climate, many unanswered questions related to their formation, emission inventory, removal processes, and optical properties still remain. Here, we report analysis that supports tarball formation in which primary organic particles undergo chemical and physical processing within ∼3 h of emission. Transmission electron microscopy analysis reveals that the number fractions of tarballs and the ratios of N and O relative to K, the latter a conserved tracer, increase with particle age and that the more-spherical particles on the substrates had higher ratios of N and O relative to K. Scanning transmission X-ray spectrometry and electron energy loss spectrometry analyses show that these chemical changes are accompanied by the formation of organic compounds that contain nitrogen and carboxylic acid. The results imply that the chemical changes increase the particle sphericity on the substrates, which correlates with particle surface tension and viscosity, and contribute to tarball formation during aging in BB smoke. These findings will enable models to better partition tarball contributions to BB radiative forcing and, in so doing, better help constrain radiative forcing models of BB events.

Absorption/Transmission Measurements of PSAP Particle-Laden Filters from the Biomass Burning Observation Project (BBOP) Field Campaign.

Absorptivity measurements with a laser-heating approach, referred to as the laser-driven thermal reactor (LDTR), were carried out in the infrared and applied at ambient (laboratory) non-reacting conditions to particle-laden filters from a three-wavelength (visible) particle/soot absorption photometer (PSAP). The particles were obtained during the Biomass Burning Observation Project (BBOP) field campaign. The focus of this study was to determine the particle absorption coefficient from field-campaign filter samples using the LDTR approach, and compare results with other commercially available instrumentation (in this case with the PSAP, which has been compared with numerous other optical techniques). Advantages of the LDTR approach include 1) direct estimation of material absorption from temperature measurements (as opposed to resolving the difference between the measured reflection/scattering and transmission), 2) information on the filter optical properties, and 3) identification of the filter material effects on particle absorption (e.g., leading to particle absorption enhancement or shadowing). For measurements carried out under ambient conditions, the particle absorptivity is obtained with a thermocouple placed flush with the filter back surface and the laser probe beam impinging normal to the filter particle-laden surface. Thus, in principle one can employ a simple experimental arrangement to measure simultaneously both the transmissivity and absorptivity (at different discrete wavelengths) and ascertain the particle absorption coefficient. For this investigation, LDTR measurements were carried out with PSAP filters (pairs with both blank and exposed filters) from eight different days during the campaign, having relatively light but different particle loadings. The observed particles coating the filters were found to be carbonaceous (having broadband absorption characteristics). The LDTR absorption coefficient compared well with results from the PSAP. The analysis was also expanded to account for the filter fiber scattering on particle absorption in assessing particle absorption enhancement and shadowing effects. The results indicated that absorption enhancement effects were significant, and diminished with increased filter particle loading.

Fast in situ airborne measurement of ammonia using a mid-infrared off-axis ICOS spectrometer.

A new ammonia (NH3) analyzer was developed based on off-axis integrated cavity output spectroscopy. Its feasibility was demonstrated by making tropospheric measurements in flights aboard the Department of Energy Gulfstream-1 aircraft. The ammonia analyzer consists of an optical cell, quantum-cascade laser, gas sampling system, control and data acquisition electronics, and analysis software. The NH3 mixing ratio is determined from high-resolution absorption spectra obtained by tuning the laser wavelength over the NH3 fundamental vibration band near 9.67 µm. Excellent linearity is obtained over a wide dynamic range (0-101 ppbv) with a response rate (1/e) of 2 Hz and a precision of ±90 pptv (1σ in 1 s). Two research flights were conducted over the Yakima Valley in Washington State. In the first flight, the ammonia analyzer was used to identify signatures of livestock from local dairy farms with high vertical and spatial resolution under low wind and calm atmospheric conditions. In the second flight, the analyzer captured livestock emission signals under windy conditions. Our results demonstrate that this new ammonia spectrometer is capable of providing fast, precise, and accurate in situ observations of ammonia aboard airborne platforms to advance our understanding of atmospheric compositions and aerosol formation.