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Comprehensive characterization of atmospheric organic carbon at a forested site

Abstract

Atmospheric organic compounds are central to key chemical processes that influence air quality, ecological health, and climate. However, longstanding difficulties in predicting important quantities such as organic aerosol formation and oxidant lifetimes indicate that our understanding of atmospheric organic chemistry is fundamentally incomplete, probably due in part to the presence of organic species that are unmeasured using standard analytical techniques. Here we present measurements of a wide range of atmospheric organic compounds—including previously unmeasured species—taken concurrently at a single site (a ponderosa pine forest during summertime) by five state-of-the-art mass spectrometric instruments. The combined data set provides a comprehensive characterization of atmospheric organic carbon, covering a wide range in chemical properties (volatility, oxidation state, and molecular size), and exhibiting no obvious measurement gaps. This enables the first construction of a measurement-based local organic budget, highlighting the high emission, deposition, and oxidation fluxes in this environment. Moreover, previously unmeasured species, including semivolatile and intermediate-volatility organic species (S/IVOCs), account for one-third of the total organic carbon, and (within error) provide closure on both OH reactivity and potential secondary organic aerosol formation.

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Figure 1: Campaign-average measurements of non-methane organic carbon loadings and properties during BEACHON-RoMBAS, coloured by analytical technique used (see legend).
Figure 2: Total observed organic carbon concentrations, calculated OH reactivity (OHR), and SOA formation, coloured by instrument and organized into major classes of organic species.
Figure 3: Observationally constrained budget of atmospheric reactive carbon in the study region, based on campaign-averaged loading measurements and estimated rates of emission, deposition, and oxidation.

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Acknowledgements

Compilation of the multi-instrument data was supported by NOAA grant NA10OAR4310106. Contributions from individual researchers were supported by NOAA NA10OAR4310106 (J.F.H., E.S.C., A.J.C. and J.H.K.); NSF ATM-0919189, NSF AGS-1243354, and DOE DE-SC0011105 (D.A.D., R.L.N.Y., P.L.H., B.B.P., P.C.-J., H.S. and J.L.J.); US EPA STAR Graduate Fellowship FP-91761701-0 (B.B.P.); NSF RAPID 1135745 (A.W.H.C., Y.Z. and A.H.G.); the Drefyus Foundation (E.S.C.); Austrian Science Fund (FWF) project number L518-N20 (A.H. and L.K.) DOC-FORTE-fellowship of the Austrian Academy of Science (L.K.) and NSF AGS-1238109 (C.L.H.). The SV-TAG, CIMS, and TD-EIMS were developed with support from the DOE SBIR program, grants DE-FG02-08ER85160, DE-FG02-08ER85160, DE-SC0004577, and DE-SC0001666. The authors are grateful to A. Turnipseed and the management of the Manitou Experimental Forest Observatory for field support, to N. Grossberg and B. Lefer for their measurements of boundary layer heights, to N. Kreisberg and S. Hering for their development and support of the SV-TAG, and to A. Steiner for helpful discussions regarding vertical mixing.

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Contributions

Instrument deployment, operation, and data analysis were carried out by: J.F.H., E.S.C., A.J.C. and J.H.K. (TD-EIMS); R.L.N.Y., D.A.D., H.S., J.A.T. and J.L.J. (CIMS); P.L.H., B.B.P., D.A.D., P.C.-J. and J.L.J. (TD-AMS); L.K., L.C., A.H. and T.K. (PTR-MS); A.W.H.C., Y.Z. and A.H.G. (SV-TAG). D.A.D. organized the BEACHON-RoMBAS field campaign along with J.N.S., A.G. and J.L.J. J.F.H. and D.A.D. compiled the multi-instrument data; J.F.H., D.A.D., D.R.W., C.L.H., J.L.J. and J.H.K., interpreted the compiled data set. J.F.H. and J.H.K. wrote the paper. All authors commented on the manuscript.

Corresponding author

Correspondence to Jesse H. Kroll.

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Competing interests

E.S.C., H.S., and D.R.W. are employees of Aerodyne Research, Inc. (ARI), which developed and commercialized several of the advanced mass spectrometric instruments utilized in this study.

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Hunter, J., Day, D., Palm, B. et al. Comprehensive characterization of atmospheric organic carbon at a forested site. Nature Geosci 10, 748–753 (2017). https://doi.org/10.1038/ngeo3018

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