Biogenic Emissions and Air Quality Impacts | Dr. Eva Pfannerstill

Ecosystem-scale quantification of emissions of stressed vs. less-stressed forests

Using Zeppelin-based airborne flux observations, we will map and quantify BVOC emissions from forests. These data will then be compared with emission models and inventories to test their ability to represent real-world stress-BVOC emissions.

Quantification and chemical characterization of

1. Tree emissions under combined stressors. In the real world, trees experience several stressors at the same time - we will do the same in the plant chamber PLUS.
2. Atmospheric oxidation processes towards particles from stressed emissions in the oxidation chamber SAPHIR. Chemical ionization mass spectrometry with NH₄⁺ and H₃O⁺ ionization enables the detection of a wide range of volatilities.

Combining chamber and field work to study the impact of plant stress on atmospheric chemistry

Biogenic VOCs are rapidly oxidized in the atmosphere. Their oxidation products can condensate to form secondary organic aerosol (SOA), which impacts light scattering, cloud formation and human health. In the presence of NO_x, these processes also lead to ozone formation.

In this project, we will apply field and chamber experiments to study both the primary emissions from healthy and stressed trees/forests, and the oxidation products in the gas and particle phases. Measurement techniques used will be, amongst others, PTR-ToF-MS, NH₄⁺-CIMS, and GC-MS.

PLUS (plant chamber only)

• Species of interest: English oak (quercus robur), European beech (fagus sylvatica)
• Combined stressors (herbivory, drought) – quantify emission rates with and without stress
• Quantify uptake rates of oxygenated VOCs
• Fingerprint mass spectra / tracers to be used in field observations to identify stress

PLUS + SAPHIR (plant chamber + oxidation chamber)

• Identify oxidation products of interest
• Derive SOA yields at high and low NO_x
• (Chemical) differences in SOA from stressed and unstressed emissions (cooperation with Goldstein Group, UC Berkeley)

Airborne eddy covariance provides measurements of emission and deposition at ecosystem scale. High time resolution (usually 10 Hz) observations of vertical wind speed and trace gas concentrations are necessary for airborne eddy covariance calculations. The flux, i.e. the emission or deposition per area and time, is calculated from the covariance of vertical wind speed and trace gas concentration. In airborne eddy covariance, the method of choice is wavelet transformation.

This project will for the first time use a Zeppelin NT airship for airborne flux measurements.

In contrast to concentration measurements, airborne eddy covariance has several advantages:

• Direct emission measurement
• No influence of meteorology
• Spatially resolved
• Enables source separation

Examples for volatile organic compound (VOC) fluxes at landscape scale are shown in the maps below (from Pfannerstill et al. 2023, ACP). In contrast to concentration measurements, the fluxes are localized to where the emission sources are (e.g. the forest for isoprene or the highway and cities for aromatics).

Footprint models allow us to estimate the spatial origin of the measured emissions. These footprints can be matched with emission inventories to validate how well they represent the observed emissions (Pfannerstill et al., ES&T 2023). Matching with landcover information also helps to find out about the sources of the emissions, and multilinear regression allows to quantify the emissions of each source type (Pfannerstill et al, ACP 2023).

The planned Zeppelin payload will enable us to measure fluxes of volatile organic compounds and greenhouse gases, and to investigate particle composition. To understand the completeness of our gas phase observations, we will also observe the total OH reactivity (loss rate of the hydroxyl radical). Cameras will be used to identify plants and their stress state, as well as the surface temperature.

Selected Publications:

Eva Y. Pfannerstill et al.: Temperature-dependent emissions dominate aerosol and ozone formation in Los Angeles. Science 384,1324-1329 (2024). DOI: 10.1126/science.adg8204

Coggon, M. M., Stockwell, C. E., Claflin, M. S., Pfannerstill, E. Y., Xu, L., Gilman, J. B., Marcantonio, J., Cao, C., Bates, K., Gkatzelis, G. I., Lamplugh, A., Katz, E. F., Arata, C., Apel, E. C., Hornbrook, R. S., Piel, F., Majluf, F., Blake, D. R., Wisthaler, A., Canagaratna, M., Lerner, B. M., Goldstein, A. H., Mak, J. E., and Warneke, C.: Identifying and correcting interferences to PTR-ToF-MS measurements of isoprene and other urban volatile organic compounds, Atmos. Meas. Tech., 17, 801–825 (2024). DOI: 10.5194/amt-17-801-2024

Zhu, Q., Schwantes, R. H., Coggon, M., Harkins, C., Schnell, J., He, J., Pye, H. O. T., Li, M., Baker, B., Moon, Z., Ahmadov, R., Pfannerstill, E. Y., Place, B., Wooldridge, P., Schulze, B. C., Arata, C., Bucholtz, A., Seinfeld, J. H., Warneke, C., Stockwell, C. E., Xu, L., Zuraski, K., Robinson, M. A., Neuman, J. A., Veres, P. R., Peischl, J., Brown, S. S., Goldstein, A. H., Cohen, R. C., and McDonald, B. C.: A better representation of volatile organic compound chemistry in WRF-Chem and its impact on ozone over Los Angeles, Atmos. Chem. Phys., 24, 5265–5286 (2024). DOI: 10.5194/acp-24-5265-2024

Benjamin C. Schulze, Ryan X. Ward, Eva Y. Pfannerstill, Qindan Zhu, Caleb Arata, Bryan Place, Clara Nussbaumer, Paul Wooldridge, Roy Woods, Anthony Bucholtz, Ronald C. Cohen, Allen H. Goldstein, Paul O. Wennberg, and John H. Seinfeld: Methane Emissions from Dairy Operations in California’s San Joaquin Valley Evaluated Using Airborne Flux Measurements, Environ. Sci. Technol., 57, 48, 19519–19531 (2023). DOI: 10.1021/acs.est.3c03940

Nussbaumer, C. M., Place, B. K., Zhu, Q., Pfannerstill, E. Y., Wooldridge, P., Schulze, B. C., Arata, C., Ward, R., Bucholtz, A., Seinfeld, J. H., Goldstein, A. H., and Cohen, R. C.: Measurement report: Airborne measurements of NO_x fluxes over Los Angeles during the RECAP-CA 2021 campaign, Atmos. Chem. Phys., 23, 13015–13028 (2023). DOI: 10.5194/acp-23-13015-2023

Pfannerstill, E. Y., Arata, C., Zhu, Q., Schulze, B. C., Woods, R., Seinfeld, J. H., Bucholtz, A., Cohen, R. C., and Goldstein, A. H.: Volatile organic compound fluxes in the agricultural San Joaquin Valley – spatial distribution, source attribution, and inventory comparison, Atmos. Chem. Phys., 23, 12753–12780 (2023). DOI: 10.5194/acp-23-12753-2023

Eva Y. Pfannerstill, Caleb Arata, Qindan Zhu, Benjamin C. Schulze, Roy Woods, Colin Harkins, Rebecca H. Schwantes, Brian C. McDonald, John H. Seinfeld, Anthony Bucholtz, Ronald C. Cohen, and Allen H. Goldstein: Comparison between Spatially Resolved Airborne Flux Measurements and Emission Inventories of Volatile Organic Compounds in Los Angeles, Environ. Sci. Technol., 57, 41, 15533–15545 (2023). DOI: 10.1021/acs.est.3c03162

Akima Ringsdorf, Achim Edtbauer, Jordi Vila-Guerau de Arellano et al.: Inferring the diurnal variability of OH radical concentrations over the Amazon from BVOC measurements, 13 June 2022, PREPRINT (Version 1) available at Research Square. DOI: 10.21203/rs.3.rs-1686416/v1

Zhu, Q., Place, B., Pfannerstill, E. Y., Tong, S., Zhang, H., Wang, J., Nussbaumer, C. M., Wooldridge, P., Schulze, B. C., Arata, C., Bucholtz, A., Seinfeld, J. H., Goldstein, A. H., and Cohen, R. C.: Direct observations of NOx emissions over the San Joaquin Valley using airborne flux measurements during RECAP-CA 2021 field campaign, Atmos. Chem. Phys., 23, 9669–9683 (2023). DOI: 10.5194/acp-23-9669-2023

Pugliese, G., Ingrisch, J., Meredith, L.K. et al.: Effects of drought and recovery on soil volatile organic compound fluxes in an experimental rainforest. Nat Commun 14, 5064 (2023). DOI: 10.1038/s41467-023-40661-8

Honeker, L.K., Pugliese, G., Ingrisch, J. et al.: Drought re-routes soil microbial carbon metabolism towards emission of volatile metabolites in an artificial tropical rainforest. Nat Microbiol 8, 1480–1494 (2023). DOI: 10.1038/s41564-023-01432-9

Carter, T. S., Heald, C. L., Kroll, J. H., Apel, E. C., Blake, D., Coggon, M., Edtbauer, A., Gkatzelis, G., Hornbrook, R. S., Peischl, J., Pfannerstill, E. Y., Piel, F., Reijrink, N. G., Ringsdorf, A., Warneke, C., Williams, J., Wisthaler, A., and Xu, L.: An improved representation of fire non-methane organic gases (NMOGs) in models: emissions to reactivity, Atmos. Chem. Phys., 22, 12093–12111 (2022). DOI: 10.5194/acp-22-12093-2022

Edtbauer, A., Pfannerstill, E.Y., Pires Florentino, A.P. et al. Cryptogamic organisms are a substantial source and sink for volatile organic compounds in the Amazon region.: Commun Earth Environ 2, 258 (2021). DOI: 10.1038/s43247-021-00328-y

Christiane Werner et al.: Ecosystem fluxes during drought and recovery in an experimental forest. Science 374, 1514-1518 (2021). DOI: 10.1126/science.abj6789

Dienhart, D., Crowley, J. N., Bourtsoukidis, E., Edtbauer, A., Eger, P. G., Ernle, L., Harder, H., Hottmann, B., Martinez, M., Parchatka, U., Paris, J.-D., Pfannerstill, E. Y., Rohloff, R., Schuladen, J., Stönner, C., Tadic, I., Tauer, S., Wang, N., Williams, J., Lelieveld, J., and Fischer, H.: Measurement report: Observation-based formaldehyde production rates and their relation to OH reactivity around the Arabian Peninsula, Atmos. Chem. Phys., 21, 17373–17388 (2021). DOI: 10.5194/acp-21-17373-2021

Friedrich, N., Eger, P., Shenolikar, J., Sobanski, N., Schuladen, J., Dienhart, D., Hottmann, B., Tadic, I., Fischer, H., Martinez, M., Rohloff, R., Tauer, S., Harder, H., Pfannerstill, E. Y., Wang, N., Williams, J., Brooks, J., Drewnick, F., Su, H., Li, G., Cheng, Y., Lelieveld, J., and Crowley, J. N.: Reactive nitrogen around the Arabian Peninsula and in the Mediterranean Sea during the 2017 AQABA ship campaign, Atmos. Chem. Phys., 21, 7473–7498 (2021). DOI: 10.5194/acp-21-7473-2021

Pfannerstill, E. Y., Reijrink, N. G., Edtbauer, A., Ringsdorf, A., Zannoni, N., Araújo, A., Ditas, F., Holanda, B. A., Sá, M. O., Tsokankunku, A., Walter, D., Wolff, S., Lavrič, J. V., Pöhlker, C., Sörgel, M., and Williams, J.: Total OH reactivity over the Amazon rainforest: variability with temperature, wind, rain, altitude, time of day, season, and an overall budget closure, Atmos. Chem. Phys., 21, 6231–6256 (2021). DOI: 10.5194/acp-21-6231-2021

Edtbauer, A., Stönner, C., Pfannerstill, E. Y., Berasategui, M., Walter, D., Crowley, J. N., Lelieveld, J., and Williams, J.: A new marine biogenic emission: methane sulfonamide (MSAM), dimethyl sulfide (DMS), and dimethyl sulfone (DMSO2) measured in air over the Arabian Sea, Atmos. Chem. Phys., 20, 6081–6094 (2020). DOI: 10.5194/acp-20-6081-2020

Bourtsoukidis, E., Pozzer, A., Sattler, T. et al.: The Red Sea Deep Water is a potent source of atmospheric ethane and propane. Nat Commun 11, 447 (2020). DOI: 10.1038/s41467-020-14375-0

Pfannerstill, E. Y., Wang, N., Edtbauer, A., Bourtsoukidis, E., Crowley, J. N., Dienhart, D., Eger, P. G., Ernle, L., Fischer, H., Hottmann, B., Paris, J.-D., Stönner, C., Tadic, I., Walter, D., Lelieveld, J., and Williams, J.: Shipborne measurements of total OH reactivity around the Arabian Peninsula and its role in ozone chemistry, Atmos. Chem. Phys., 19, 11501–11523 (2019). DOI: 10.5194/acp-19-11501-2019

Pfannerstill E Y, Nölscher AC, Yáñez-Serrano AM, Bourtsoukidis E, Keßel S, Janssen RHH, Tsokankunku A, Wolff S, Sörgel M, Sá MO, Araújo A, Walter D, Lavrič J, Dias-Júnior CQ, Kesselmeier J and Williams J: Total OH Reactivity Changes Over the Amazon Rainforest During an El Niño Event, Front. For. Glob. Change 1:12 (2018). DOI: 10.3389/ffgc.2018.00012

Weiss, G. M., Pfannerstill, E. Y., Schouten, S., Sinninghe Damsté, J. S., and van der Meer, M. T. J.: Effects of alkalinity and salinity at low and high light intensity on hydrogen isotope fractionation of long-chain alkenones produced by Emiliania huxleyi, Biogeosciences, 14, 5693–5704 (2017). DPO: 10.5194/bg-14-5693-2017

Fuchs, H., Novelli, A., Rolletter, M., Hofzumahaus, A., Pfannerstill, E. Y., Kessel, S., Edtbauer, A., Williams, J., Michoud, V., Dusanter, S., Locoge, N., Zannoni, N., Gros, V., Truong, F., Sarda-Esteve, R., Cryer, D. R., Brumby, C. A., Whalley, L. K., Stone, D., Seakins, P. W., Heard, D. E., Schoemaecker, C., Blocquet, M., Coudert, S., Batut, S., Fittschen, C., Thames, A. B., Brune, W. H., Ernest, C., Harder, H., Muller, J. B. A., Elste, T., Kubistin, D., Andres, S., Bohn, B., Hohaus, T., Holland, F., Li, X., Rohrer, F., Kiendler-Scharr, A., Tillmann, R., Wegener, R., Yu, Z., Zou, Q., and Wahner, A.: Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR, Atmos. Meas. Tech., 10, 4023–4053 (2017). DOI: 10.5194/amt-10-4023-2017

Arnaud P. Praplan, Eva Y. Pfannerstill, Jonathan Williams, Heidi Hellén: OH reactivity of the urban air in Helsinki, Finland, during winter, Atmospheric Environment, Volume 169, 150-161 (2017). DOI: 10.1016/j.atmosenv.2017.09.013

Recent Publications of the Institute