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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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References

  1. Hallquist, M. et al. The formation, properties and impact of secondary organic aerosol: current and emerging issues. Atmos. Chem. Phys. 9, 5155–5236 (2009).

    Article  Google Scholar 

  2. Yang, Y. et al. Towards a quantitative understanding of total OH reactivity: a review. Atmos. Environ. 134, 147–161 (2016).

    Article  Google Scholar 

  3. Chung, M. Y., Maris, C., Krischke, U., Meller, R. & Paulson, S. E. An investigation of the relationship between total non-methane organic carbon and the sum of speciated hydrocarbons and carbonyls measured by standard GC/FID: measurements in the Los Angeles air basin. Atmos. Environ. 37, S159–S170 (2003).

    Article  Google Scholar 

  4. Goldstein, A. H. & Galbally, I. E. Known and unexplored organic constituents in the Earth’s atmosphere. Environ. Sci. Technol. 41, 1514–1521 (2007).

    Article  Google Scholar 

  5. Kroll, J. H. et al. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol. Nat. Chem. 3, 133–139 (2011).

    Article  Google Scholar 

  6. Donahue, N. M., Kroll, J. H., Pandis, S. N. & Robinson, A. L. A two-dimensional volatility basis set—Part 2: Diagnostics of organic-aerosol evolution. Atmos. Chem. Phys. 12, 615–634 (2012).

    Article  Google Scholar 

  7. Donahue, N. M., Robinson, A. L., Stanier, C. O. & Pandis, S. N. Coupled partitioning, dilution, and chemical aging of semivolatile organics. Environ. Sci. Technol. 40, 2635–2643 (2006).

    Article  Google Scholar 

  8. Ehn, M. et al. A large source of low-volatility secondary organic aerosol. Nature 506, 476–479 (2014).

    Article  Google Scholar 

  9. Heald, C. L. et al. Total observed organic carbon (TOOC) in the atmosphere: a synthesis of North American observations. Atmos. Chem. Phys. 8, 2007–2025 (2008).

    Article  Google Scholar 

  10. de Gouw, J. A. et al. Budget of organic carbon in a polluted atmosphere: results from the New England Air Quality Study in 2002. J. Geophys. Res. 110, D16305 (2005).

    Article  Google Scholar 

  11. Koss, A. R. et al. Photochemical aging of volatile organic compounds associated with oil and natural gas extraction in the Uintah Basin, UT, during a wintertime ozone formation event. Atmos. Chem. Phys. 15, 5727–5741 (2015).

    Article  Google Scholar 

  12. Ortega, J. et al. Overview of the Manitou Experimental Forest Observatory: site description and selected science results from 2008 to 2013. Atmos. Chem. Phys. 14, 6345–6367 (2014).

    Article  Google Scholar 

  13. DeCarlo, P. F. et al. Field-deployable, high-resolution, time-of-flight aerosol mass spectrometer. Anal. Chem. 78, 8281–8289 (2006).

    Article  Google Scholar 

  14. Huffman, J. A., Ziemann, P. J., Jayne, J. T., Worsnop, D. R. & Jimenez, J. L. Development and characterization of a fast-stepping/scanning thermodenuder for chemically-resolved aerosol volatility measurements. Aerosol Sci. Technol. 42, 395–407 (2008).

    Article  Google Scholar 

  15. Graus, M., Müller, M. & Hansel, A. High resolution PTR-TOF: quantification and formula confirmation of VOC in real time. J. Am. Soc. Mass Spectrom. 21, 1037–1044 (2010).

    Article  Google Scholar 

  16. Yatavelli, R. L. N. et al. A chemical ionization high-resolution time-of-flight mass spectrometer coupled to a Micro Orifice Volatilization Impactor (MOVI-HRToF-CIMS) for analysis of gas and particle-phase organic species. Aerosol Sci. Technol. 46, 1313–1327 (2012).

    Article  Google Scholar 

  17. Zhao, Y. et al. Development of an in situ thermal desorption gas chromatography instrument for quantifying atmospheric semi-volatile organic compounds. Aerosol Sci. Technol. 47, 258–266 (2013).

    Article  Google Scholar 

  18. Cross, E. S. et al. Online measurements of the emissions of intermediate-volatility and semi-volatile organic compounds from aircraft. Atmos. Chem. Phys. 13, 7845–7858 (2013).

    Article  Google Scholar 

  19. Canagaratna, M. R. et al. Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications. Atmos. Chem. Phys. 15, 253–272 (2015).

    Article  Google Scholar 

  20. Daumit, K. E., Kessler, S. H. & Kroll, J. H. Average chemical properties and potential formation pathways of highly oxidized organic aerosol. Faraday Discuss. 165, 181–202 (2013).

    Article  Google Scholar 

  21. Pankow, J. F. & Asher, W. E. SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds. Atmos. Chem. Phys. 8, 2773–2796 (2008).

    Article  Google Scholar 

  22. Nguyen, T. B. et al. Rapid deposition of oxidized biogenic compounds to a temperate forest. Proc. Natl Acad. Sci. USA 112, E392–E401 (2015).

    Article  Google Scholar 

  23. Park, J.-H. et al. Active atmosphere-ecosystem exchange of the vast majority of detected volatile organic compounds. Science 341, 643–647 (2013).

    Article  Google Scholar 

  24. Robinson, A. L. et al. Rethinking organic aerosols: semivolatile emissions and photochemical aging. Science 315, 1259–1262 (2007).

    Article  Google Scholar 

  25. Roberts, J. M., Bertman, S. B., Jobson, T., Niki, H. & Tanner, R. Measurement of total nonmethane organic carbon (Cy): development and application at Chebogue Point, Nova Scotia, during the 1993 North Atlantic Regional Experiment campaign. J. Geophys. Res. 103, 13581 (1998).

    Article  Google Scholar 

  26. Kim, S. et al. Evaluation of HOx sources and cycling using measurement-constrained model calculations in a 2-methyl-3-butene-2-ol (MBO) and monoterpene (MT) dominated ecosystem. Atmos. Chem. Phys. 13, 2031–2044 (2013).

    Article  Google Scholar 

  27. Nakashima, Y. et al. Total OH reactivity measurements in ambient air in a southern Rocky Mountain ponderosa pine forest during BEACHON-SRM08 summer campaign. Atmos. Environ. 85, 1–8 (2014).

    Article  Google Scholar 

  28. Palm, B. B. et al. In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor. Atmos. Chem. Phys. 16, 2943–2970 (2016).

    Article  Google Scholar 

  29. Kaser, L. et al. Undisturbed and disturbed above canopy ponderosa pine emissions: PTR-TOF-MS measurements and MEGAN 2.1 model results. Atmos. Chem. Phys. 13, 11935–11947 (2013).

    Article  Google Scholar 

  30. Hodzic, A. et al. Volatility dependence of Henry’s law constants of condensable organics: application to estimate depositional loss of secondary organic aerosols. Geophys. Res. Lett. 41, 4795–4804 (2014).

    Article  Google Scholar 

  31. Faulhaber, A. E. et al. Characterization of a thermodenuder-particle beam mass spectrometer system for the study of organic aerosol volatility and composition. Atmos. Meas. Tech. 2, 15–31 (2009).

    Article  Google Scholar 

  32. Bahreini, R. et al. Organic aerosol formation in urban and industrial plumes near Houston and Dallas, Texas. J. Geophys. Res. 114, D00F16 (2009).

    Article  Google Scholar 

  33. Stark, H. et al. Methods to extract molecular and bulk chemical information from series of complex mass spectra with limited mass resolution. Int. J. Mass Spectrom. 389, 26–38 (2015).

    Article  Google Scholar 

  34. Lopez-Hilfiker, F. D. et al. Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds. Atmos. Chem. Phys. 15, 7765–7776 (2015).

    Article  Google Scholar 

  35. Isaacman-VanWertz, G. et al. Ambient gas-particle partitioning of tracers for biogenic oxidation. Environ. Sci. Technol. 50, 9952–9962 (2016).

    Article  Google Scholar 

  36. Stark, H. et al. Impact of thermal decomposition on thermal desorption instruments: advantage of thermogram analysis for quantifying volatility distributions of organic species. Environ. Sci. Technol. 51, 8491–8500 (2017).

    Article  Google Scholar 

  37. Yatavelli, R. L. N. et al. Estimating the contribution of organic acids to northern hemispheric continental organic aerosol. Geophys. Res. Lett. 42, 6084–6090 (2015).

    Article  Google Scholar 

  38. Yatavelli, R. L. N. et al. Semicontinuous measurements of gas–particle partitioning of organic acids in a ponderosa pine forest using a MOVI-HRToF-CIMS. Atmos. Chem. Phys. 14, 1527–1546 (2014).

    Article  Google Scholar 

  39. Kaser, L. et al. Comparison of different real time VOC measurement techniques in a ponderosa pine forest. Atmos. Chem. Phys. 13, 2893–2906 (2013).

    Article  Google Scholar 

  40. Cappellin, L. et al. On quantitative determination of volatile organic compound concentrations using proton transfer reaction time-of-flight mass spectrometry. Environ. Sci. Technol. 46, 2283–2290 (2012).

    Article  Google Scholar 

  41. Chan, A. W. H. et al. Speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) in a pine forest during BEACHON-RoMBAS 2011. Atmos. Chem. Phys. 16, 1187–1205 (2016).

    Article  Google Scholar 

  42. Fry, J. L. et al. Observations of gas- and aerosol-phase organic nitrates at BEACHON-RoMBAS 2011. Atmos. Chem. Phys. 13, 8585–8605 (2013).

    Article  Google Scholar 

  43. US EPA Estimation Programs Interface SuiteTM for Microsoft® Windows 8 (2015).

  44. Donahue, N. M. et al. Why do organic aerosols exist? Understanding aerosol lifetimes using the two-dimensional volatility basis set. Environ. Chem. 10, 151–157 (2013).

    Article  Google Scholar 

  45. Donahue, N. M., Robinson, A. L. & Pandis, S. N. Atmospheric organic particulate matter: from smoke to secondary organic aerosol. Atmos. Environ. 43, 94–106 (2009).

    Article  Google Scholar 

  46. DiGangi, J. P. et al. First direct measurements of formaldehyde flux via eddy covariance: implications for missing in-canopy formaldehyde sources. Atmos. Chem. Phys. 11, 10565–10578 (2011).

    Article  Google Scholar 

  47. Zhang, L., Gong, S., Padro, J. & Barrie, L. A size-segregated particle dry deposition scheme for an atmospheric aerosol module. Atmos. Environ. 35, 549–560 (2001).

    Article  Google Scholar 

  48. Farmer, D. K. et al. Chemically resolved particle fluxes over tropical and temperate forests. Aerosol Sci. Technol. 47, 818–830 (2013).

    Article  Google Scholar 

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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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