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Open ocean and coastal new particle formation from sulfuric acid and amines around the Antarctic Peninsula

Nature Geoscience volume 14, pages 383–388 (2021)Cite this article

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Abstract

New particle formation is globally one of the major sources of aerosol particles and cloud condensation nuclei. As primary emissions are a minor contributor to particle concentrations, secondary new particle formation processes are probably key in determining Antarctic aerosol number concentrations. However, our knowledge of new particle formation and its mechanisms in Antarctica is very limited. Here we study summertime open ocean and coastal new particle formation in the Antarctic Peninsula region based on both ship and station measurements. The rates of particle formation relative to sulfuric acid concentrations, as well as the sulfuric acid dimer-to-monomer ratios, were similar to those seen for sulfuric acid–dimethylamine–water nucleation. Numerous sulfuric acid–amine peaks were identified during new particle formation events, providing evidence that alkylamines were the bases that facilitated sulfuric acid nucleation. Most new particle formation events occurred in air masses arriving from the ice-covered Weddell Sea and its marginal ice zone, which are an important source of volatile sulfur and alkylamines. This nucleation mechanism is more efficient than the ion-induced sulfuric acid–ammonia pathway previously observed in Antarctica, and one that can occur rapidly under neutral conditions. This hitherto overlooked pathway to biologically driven aerosol formation should be considered for estimating aerosol and cloud condensation nuclei numbers in ocean–sea ice–aerosols–climate feedback models.

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Fig. 1: Mean diurnal cycles on NPF event and non-NPF event days.
Fig. 2: Evidence for H2SO4–amine nucleation.
Fig. 3: Association between sea-ice extent and NPF.

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Data availability

Data supporting this publication are openly available from the UBIRA eData repository at https://doi.org/10.25500/edata.bham.00000400. Daily sea-ice concentrations49 are available from the NSIDC at https://doi.org/10.7265/N5K072F8.

Code availability

Code required to produce the figures is available from J.B. (J.brean@bham.ac.uk) upon reasonable request.

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Acknowledgements

We thank the Spanish Armada, and particularly the captains and crew of the BIO A-33 Hesperides, for their invaluable collaboration. We are also indebted to the UTM, and especially M. Ojeda, for logistic and technical support on the Antarctic Spanish BAE JC1. We also thank A. Sotomayor for help with mapping. This study was funded by the Spanish Ministry of Economy (grant number PI‐ICE‐CTM 2017–89117‐R and RYC-2012-11922, both awarded to M.D.’O.). This work was also supported by the National Centre for Atmospheric Science funded by the UK Natural Environment Research Council (grant number R8/H12/83/011 to R.M.H. and D.C.S.B., which also supported a studentship (ncasstu009) for J.B.).

Author information

Authors and Affiliations

  1. Division of Environmental Health and Risk Management, School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham, UK

    James Brean, Zongbo Shi, David C. S. Beddows & Roy M. Harrison

  2. Institute of Marine Science, Consejo Superior de Investigaciones Científicas (CSIC), Barcelona, Spain

    Manuel Dall’Osto & Rafel Simó

  3. Department of Environmental Sciences/Center of Excellence in Environmental Studies, King Abdulaziz University, Jeddah, Saudi Arabia

    Roy M. Harrison

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Contributions

M.D.’O., J.B. and D.C.S.B. made the field measurements. M.D.’O. organized the campaign and the cruise. J.B. processed the data and led the data interpretation and produced the first draft of the paper. R.M.H., Z.S. and R.S. supported the data interpretation and manuscript drafting.

Corresponding authors

Correspondence to Manuel Dall’Osto or Roy M. Harrison.

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Peer review information Nature Geoscience thanks the anonymous reviewers for their contribution to the peer review of this work. Primary Handling Editors: Clare Davis; Xujia Jiang.

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Extended data

Extended Data Fig. 1 Characteristics of amine signals.

(a–d) correlations of each ammonia/amine measurement as the form (Am)(HNO3)NO3- and (Am)(HNO3)2NO3-, where Am is NH3, methylamine, C2 or C4 amine, coloured by date for (a) C2 amines, (b) C4 amines, (c) methylamine and (d) ammonia, and (e-f) mass spectral peak fits for C2 amine clustered with the nitrate dimer and trimer.

Extended Data Fig. 2 GR4.5-10 by different methods.

Bars corresponding to ‘Calc H2SO4 + MSA + HIO3’ and ‘Calc H2SO4’ represent the theoretical growth rate as calculated by ref. 46 due to several vapours, and H2SO4 respectively, the rightmost bars show growth rates calculated by the lognormal fitting method applied to NanoSMPS data. Errors on growth rates fitted to SMPS data are ±50%, errors on calculated growth rates are +100%/-50%.

Extended Data Fig. 3 Diurnal cycles of ions for station measurements.

Separated by NPF and non-NPF days, for (a) oxygenated organics, containing C5 and C6 oxygenated organics, (b) dicarboxylic acids, (c) iodic acid, (d) methanesulphonic acid, and (e) SO3- and SO5- ions. Shaded regions show 95% confidence regions on the mean.

Extended Data Fig. 4 NO3- CI-APi-ToF PMF results for 8 factors.

showing (a) diurnals, where shaded region shows 1 standard deviation on the mean, (b) time series, and (c) mass spectra per factor. Data included 300 peaks between 150 – 400 m/Q for 1 week of CI-APi-ToF data. Q/Qexp for this solution = 1.004.

Extended Data Fig. 5 Measurement locations.

showing the measurement site (a) within Antarctica, and (b) within the Antarctic peninsula. BAE JC1 is the location for station measurements, and the coloured line shows the ship track, where red signifies that an NPF event was occurring.

Extended Data Fig. 6 Potential new particle sources during cruise measurements.

Signals of gas phase H2SO4, MSA, HIO3, oxygenated organic molecules, C2 amines, and C4 amines. ‘NPF’ refers to periods where NPF was actively occurring (presuming a 0.5 nm h-1 growth rate below 4.5 nm), ‘Non NPF’ refers to the rest of the measurement period. Error bars represent 1 standard error on measured values.

Extended Data Fig. 7 Features of sulphuric acid clusters.

Showing (a) time series, (b) diurnal cycles and (c) relative signals of a series of sulphuric acid clusters. Signals for the time series and diurnals have been normalised to a maximum of 1. Purple line shows the sulphuric acid dimer for comparison, and the black line shows the average of all these dimer peaks. Nucleation events occurred on 28/02 and 05/03.

Extended Data Fig. 8 HR fits for each cluster.

Titles show the assigned cluster formula assigned to the red line. The purple and orange dashed line show unassigned peaks. The sum of these cluster and unknown peak fits is shown with the blue line, and the raw mass spectral data with the green points. Clusters seen with multiple nitrogen atoms are presumed to contain multiple bases.

Extended Data Table 1 Nucleation statistics per event
Full size table
Extended Data Table 2 Sulphuric acid clusters identified during NPF events
Full size table

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Brean, J., Dall’Osto, M., Simó, R. et al. Open ocean and coastal new particle formation from sulfuric acid and amines around the Antarctic Peninsula. Nat. Geosci. 14, 383–388 (2021). https://doi.org/10.1038/s41561-021-00751-y

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