Methods and Standards for Measurement of Atmospheric Aerosol Radiative Properties

Summary

Aerosols represent the second largest contributor to atmospheric heating after CO₂. Aerosol optical properties are poorly understood, resulting in the largest source of uncertainty in modelling atmospheric warming and hinder the extent to which models can interpret climate phenomena.  The quality of aerosol optical data is hindered by the lack of aerosolized materials with known properties (absorption and scattering), prohibiting instrument calibration and making quantitative aerosol measurements a challenge.

This project has three goals to address challenges associated with making quality aerosol optical measurements. First, is the development of techniques to enable mass traceable absorption and extinction measurements of an aerosol stream. Second, apply these techniques to atmospherically relevant aerosol systems. And lastly, to develop an aerosolizable material with known composition and morphology to enable reproducible and transferrable aerosol optical calibration.

Description

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We have recently developed a technique that can select an aerosol with known size and mass from a disperse aerosol distribution. The aerosol absorption and extinction (absorption + scattering) is measured in parallel and the particles are then counted. From these measurements we can measure aerosol optical properties as a function of particle density, independent of particle size and chemical composition. Using this technique for aerosols with known composition allows for quantitative optical measurements, and for the first time, truly quantitative comparisons of aerosol as a function of composition and size.  We have recently added the ability to make absorption measurements across the full visible solar spectrum and to generate aerosol spectra in a flowing stream. This gives us the capability to quantitatively calculate aerosol radiative forcings.

In the second area we have applied the techniques described above to atmospherically relevant materials. We have explored laboratory generated soot and brown carbon, both important contributors to atmospheric absorption. These experiments require manipulation of experimental parameters at the nanoscale, which in turn, allow us to influence chemical composition, morphology, and particle size. Through careful control of the aerosol stream the optical dependence of particle morphology can be determined for particles of the same mass, to allow for direct comparison of aerosol optical properties. In addition to chemical composition, we can study optical properties as a function of relative humidity, thereby better capturing the state of aerosol in the terrestrial environment where water plays an important role. 

To date no materials exist for aerosol optical calibration. This inhibits quantitative and comparative measurements to be made and represents a major challenge for technical advancement of the field. We have been addressing this need by researching and developing materials that are easy to prepare, have reproducible properties, and can be readily generated and used across a wide variety of experimental conditions. We have recently studied reduced graphene oxide, fullerene, graphene, and water soluble carbon black aerosol. Using the system described previously, we can tune aerosol morphology, size, and, in some systems, the chemical composition of the analyzed material.

Major Accomplishments

• We have recently published a study demonstrating the first quantitative absorption spectra as a function of aerosol mass. By measuring absorption across a side spectral region, the demonstrated technique allows comparison of data between laboratories. We demonstrated the technique on absorbing organic aerosol and flame generated soot.
• We have recently investigated the impact of relative humidity on aerosol absorption. Using an ultrafast, pulsed laser source allows for rapid heating of the aerosol interfacial region. The mechanism of aerosol heating differs from using a continuous laser source, allowing the impact of surface coatings on absorption to be investigated.
• Aerosol are often coated in the atmosphere, which can increase the amount of light that is absorbed. We have recently studied the impact of coatings on black carbon aerosol made coated aerosol by co-atomization of black carbon with absorbing and non-absorbing aerosol. The data show that coatings can increase the absorption of black carbon by as much as a factor of 3 across the visible portion of the spectrum.
• We have recently measured absorption spectra of smoldering smoke aerosol across the visible and near-infrared spectral regions for six different wood types. These data represent measurements aerosol with the smallest absorption cross sections reported to date, and will be useful in the parameterization of satellite retrievals used in climate change modelling.
• We currently have several ongoing investigations. We are investigating the absorption of carbon allotropes as a function of particle mass. In collaboration with Prof. M. Zachariah (University of Maryland, College Park), we are investigating the quantification of photoacoustic spectroscopy using well characterized metal nanoparticles. In collaboration with Prof. R. Dickerson (University of Maryland, College Park) we are using mobility and mass-selected aerosol to quantify filter-based aerosol measurements. In collaboration with Prof. M. Okumura (California Institute of Technology) we are investigating aerosol absorption from liquid and solid fueled light sources in the developing world.

associated pUBLICATIONS 

1. Yao, Q., Asa-Awuku, A., Zangmeister, C. D., and Radney, J. G., "Comparison of three essential sub-micrometer aerosol measurements: Mass, size and shape," Aerosol Science and Technology, 54, 1197-1209 (2020).
2. Zangmeister, C. D., Grimes, C. D., Dickerson, R. R., and Radney, J. G., "Characterization and demonstration of a black carbon aerosol mimic for instrument evaluation," Aerosol Science and Technology, 53, 1322-1333 (2019).
3. Atkinson, D. B., Pekour, M., Chand, D., Radney, J. G., Kolesar, K. R., Zhang, Q., Setyan, A., O'Neill, N. T., and Cappa, C. D., "Using spectral methods to obtain particle size information from optical data: applications to measurements from CARES 2010," Atmospheric Chemistry and Physics, 18, 5499-5514 (2018).
4. Radney, J. G. and Zangmeister, C. D., "Comparing aerosol refractive indices retrieved from full distribution and size- and mass-selected measurements," Journal of Quantitative Spectroscopy & Radiative Transfer, 220, 52-66 (2018).
5. Zangmeister, C. D., You, R., Lunny, E. M., Jacobson, A. E., Okumura, M., Zachariah, M. R., and Radney, J. G., "Measured in-situ mass absorption spectra for nine forms of highly-absorbing carbonaceous aerosol," Carbon, 136, 85-93 (2018).
6. Zangmeister, C. D., Radney, J. G., "Absorption Spectroscopy of Black and Brown Carbon Aerosol,". In: Multiphase Environmental Chemistry in the Atmosphere. ACS Publications, pp. 275-297 (2018).
7. Radney, J. G. and Zangmeister, C. D., "Light source effects on aerosol photoacoustic spectroscopy measurements," Journal of Quantitative Spectroscopy & Radiative Transfer, 187, 145-149 (2017).
8. Zangmeister, C., "Measured absorption spectra of aerosolized carbonaceous species and their influence on climate forcing," Abstracts of Papers of the American Chemical Society, 254, (2017).
9. Linteris, G. T., Babushok, V. I., Pagliaro, J. L., Burgess, D. R., Manion, J. A., Takahashi, F., Katta, V. R., and Baker, P. T., "Understanding overpressure in the FAA aerosol can test by C3H2F3Br (2-BTP)," Combustion and Flame, 167, 452-462 (2016).
10. Radney, J. G.; Zangmeister, C. D., Practical limitations of aerosol separation by a tandem differential mobility analyzer–aerosol particle mass analyzer. Aerosol Science & Technology. 2016, 50 (2), 160-172.
11. You, R.; Radney, J. G.; Zachariah, M. R.; Zangmeister, C. D., Measured Wavelength-Dependent Absorption Enhancement of Internally Mixed Black Carbon with Absorbing and Nonabsorbing Materials, Environmental Science & Technology. Environ. Sci. Technol., 50, 7982-7990 (2016).
12. Measurement of Gas and Aerosol Phase Absorption Spectra across the Visible and Near-IR Using Supercontinuum Photoacoustic Spectroscopy. Analytical Chemistry. 2015, 87, (14), 7356–7363.
13. Radney, J. G.; You, R.; Ma, X.; Conny, J. M.; Zachariah, M. R.; Hodges, J. T.; Zangmeister, C. D., Dependence of Soot Optical Properties on Particle Morphology: Measurements and Model Comparisons. Environmental Science & Technology. 2014, 48, (6), 3169 - 3176.
14. Zangmeister, C. D.; Radney, J. G.; Dockery, L. T.; Young, J. T.; Ma, X.; You, R.; Zachariah, M. R., Packing density of rigid aggregates is independent of scale. Proceedings of the National Academy of Sciences 2014, 111, (25), 9037–9041.
15. Kalafut-Pettibone, A. J. and McGivern, W. S., "Analytical Methodology for Determination of Organic Aerosol Functional Group Distributions," Analytical Chemistry, 85, 3553-3560 (2013).
16. Kalafut-Pettibone, A. J., Klems, J. P., and McGivern, W. S., "High Performance Liquid Chromatography Study of Complex Oxygenated Alkane Mixtures from Organic Aerosols," Nucleation and Atmospheric Aerosols, 1527, 449-452 (2013).
17. Kalafut-Pettibone, A. J., Klems, J. P., Burgess, D. R., and McGivern, W. S., "Alkylperoxy Radical Photochemistry in Organic Aerosol Formation Processes," Journal of Physical Chemistry A, 117, 14141-14150 (2013).
18. Radney, J. G.; Ma, X.; Gillis, K. A.; Zachariah, M. R.; Hodges, J. T.; Zangmeister, C. D., Direct measurements of mass-specific optical cross sections of single component aerosol mixtures. Analytical Chemistry. 2013, 85, (17), 8319-8325.
19. Zangmeister, C. and Ma, X. F., "Tunable laboratory generated aerosols linking experimental data to field measurements and theory," Abstracts of Papers of the American Chemical Society, 244, (2012).