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Pollution drives multidecadal decline in subarctic methanesulfonic acid

Nature Geoscience (2024)Cite this article

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Abstract

An industrial-era decline in Greenland ice-core methanesulfonic acid is thought to herald a collapse in North Atlantic marine phytoplankton stocks related to a weakening of the Atlantic meridional overturning circulation. By contrast, stable levels of total marine biogenic sulfur contradict this interpretation and point to changes in atmospheric oxidation as a potential cause of the methanesulfonic acid decline. However, the impact of oxidation on methanesulfonic acid production has not been quantified, nor has this hypothesis been rigorously tested. Here we present a multi-century methanesulfonic acid record from the Denali, Alaska, ice core, which shows a methanesulfonic acid decline similar in magnitude but delayed by 93 years relative to the Greenland record. Box-model results using updated dimethyl sulfide oxidation pathways indicate that oxidation by pollution-driven nitrate radicals has suppressed atmospheric methanesulfonic acid production, explaining most, if not all, of Denali’s and Greenland’s methanesulfonic acid declines without requiring a change in phytoplankton production. The delayed timing of the North Pacific methanesulfonic acid decline, relative to the North Atlantic, reflects the distinct history of industrialization in upwind regions and is consistent with the Denali and Greenland ice-core nitrate records. These results demonstrate that multidecadal trends in industrial-era Arctic ice-core methanesulfonic acid reflect rising anthropogenic pollution rather than declining marine primary production.

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Fig. 1: Our motivating hypothesis and broad conclusions.
Fig. 2: Ice-core MSA records alongside F0AM box-model results examining PI–IE DMS oxidation changes.
Fig. 3: Ice-core MSA records alongside oxidant precursor emissions.

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Data availability

Denali ice-core (DEN13A and DEN13B) MSA data are available from the Arctic Data Center (https://doi.org/10.18739/A2Q814T9K). The Greenland MSA composite record is available from ref. 10, and Summit07 MSA data are available from ref. 22. Denali NO3– is available at the National Oceanic and Atmospheric Administration (NOAA) palaeoclimatology database (https://doi.org/10.25921/6cpm-kr44), and Summit07 NO3– is available from ref. 49. GEOS-Chem output is from ref. 54. CEDS emissions data used in this study are from ref. 30. All data shown in the Main and Extended Data Figures are available at the preceding references or can be recreated following the Code Availability Statement.

Code availability

The F0AM source code can be downloaded from https://github.com/AirChem/F0AM. Gas-phase MSA mechanisms were implemented following reactions listed in Supplementary Tables 1–4. GEOS-Chem source code can be downloaded from https://github.com/geoschem/geos-chem/tree/13.2.1. Code for Bayesian changepoint analysis was modified from the BEAST package (MATLAB version), which can be downloaded from https://github.com/zhaokg/Rbeast.

References

  1. Andreae, M. O. Ocean–atmosphere interactions in the global biogeochemical sulfur cycle. Mar. Chem. 30, 1–29 (1990).

    Article  CAS  Google Scholar 

  2. Fung, K. M. et al. Exploring dimethyl sulfide (DMS) oxidation and implications for global aerosol radiative forcing. Atmos. Chem. Phys. 22, 1549–1573 (2022).

    Article  CAS  Google Scholar 

  3. Cala, B. A. et al. Development, intercomparison, and evaluation of an improved mechanism for the oxidation of dimethyl sulfide in the UKCA model. Atmos. Chem. Phys. 23, 14735–14760 (2023).

    Article  CAS  Google Scholar 

  4. Novak, G. A. et al. Rapid cloud removal of dimethyl sulfide oxidation products limits SO2 and cloud condensation nuclei production in the marine atmosphere. Proc. Natl Acad. Sci. USA 118, e2110472118 (2021).

    Article  CAS  Google Scholar 

  5. Chen, Q., Sherwen, T., Evans, M. & Alexander, B. DMS oxidation and sulfur aerosol formation in the marine troposphere: a focus on reactive halogen and multiphase chemistry. Atmos. Chem. Phys. 18, 13617–13637 (2018).

    Article  CAS  Google Scholar 

  6. Weller, R. et al. Postdepositional losses of methane sulfonate, nitrate, and chloride at the European Project for Ice Coring in Antarctica deep-drilling site in Dronning Maud Land, Antarctica. J. Geophys. Res. Atmos. 109, D07301 (2004).

    Article  Google Scholar 

  7. Maselli, O. J. et al. Sea ice and pollution-modulated changes in Greenland ice core methanesulfonate and bromine. Clim. Past 13, 39–59 (2017).

    Article  Google Scholar 

  8. Legrand, M. et al. Sulfur-containing species (methanesulfonate and SO4) over the last climatic cycle in the Greenland Ice Core Project (central Greenland) ice core. J. Geophys. Res. Oceans 102, 26663–26679 (1997).

    Article  CAS  Google Scholar 

  9. Isaksson, E., Kekonen, T., Moore, J. & Mulvaney, R. The methanesulfonic acid (MSA) record in a Svalbard ice core. Ann. Glaciol. 42, 345–351 (2005).

    Article  CAS  Google Scholar 

  10. Osman, M. B. et al. Industrial-era decline in subarctic Atlantic productivity. Nature 569, 551–555 (2019).

    Article  CAS  Google Scholar 

  11. Kurosaki, Y., Matoba, S., Iizuka, Y., Fujita, K. & Shimada, R. Increased oceanic dimethyl sulfide emissions in areas of sea ice retreat inferred from a Greenland ice core. Commun. Earth Environ. 3, 327 (2022).

    Article  Google Scholar 

  12. Curran, M. A. J., van Ommen, T. D., Morgan, V. I., Phillips, K. L. & Palmer, A. S. Ice core evidence for Antarctic sea ice decline since the 1950s. Science 302, 1203–1206 (2003).

    Article  CAS  Google Scholar 

  13. Welch, K. A., Mayewski, P. A. & Whitlow, S. I. Methanesulfonic acid in coastal Antarctic snow related to sea-ice extent. Geophys. Res. Lett. 20, 443–446 (1993).

    Article  Google Scholar 

  14. Criscitiello, A. S. et al. Marine aerosol records of Arctic sea-ice and polynya variability from New Ellesmere and Devon Island firn cores, Nunavut, Canada. J. Geophys. Res. Oceans 126, e2021JC017205 (2021).

    Article  CAS  Google Scholar 

  15. Polashenski, D. J. et al. Denali ice core methanesulfonic acid records North Pacific marine primary production. J. Geophys. Res. Atmos. 123, 4642–4653 (2018).

    Article  CAS  Google Scholar 

  16. Lotze, H. K. et al. Global ensemble projections reveal trophic amplification of ocean biomass declines with climate change. Proc. Natl Acad. Sci. USA 116, 12907–12912 (2019).

    Article  CAS  Google Scholar 

  17. Falkowski, P. G., Barber, R. T. & Smetacek, V. Biogeochemical controls and feedbacks on ocean primary production. Science 281, 200–206 (1998).

    Article  CAS  Google Scholar 

  18. Wilson, J. D. et al. The biological carbon pump in CMIP6 models: 21st century trends and uncertainties. Proc. Natl Acad. Sci. USA 119, e2204369119 (2022).

    Article  CAS  Google Scholar 

  19. Carslaw, K. S. et al. Large contribution of natural aerosols to uncertainty in indirect forcing. Nature 503, 67–71 (2013).

    Article  CAS  Google Scholar 

  20. O’Dowd, C. D. & de Leeuw, G. Marine aerosol production: a review of the current knowledge. Phil. Trans. R. Soc. A 365, 1753–1774 (2007).

    Article  Google Scholar 

  21. Park, K.-T. et al. Dimethyl sulfide-induced increase in cloud condensation nuclei in the Arctic atmosphere. Glob. Biogeochem. Cycles 35, e2021GB006969 (2021).

    Article  CAS  Google Scholar 

  22. Jongebloed, U. A. et al. Industrial-era decline in Arctic methanesulfonic acid is offset by increased biogenic sulfate aerosol. Proc. Natl Acad. Sci. USA 120, e2307587120 (2023).

    Article  CAS  Google Scholar 

  23. Veres, P. R. et al. Global airborne sampling reveals a previously unobserved dimethyl sulfide oxidation mechanism in the marine atmosphere. Proc. Natl Acad. Sci. USA 117, 4505–4510 (2020).

    Article  CAS  Google Scholar 

  24. Zhao, K. et al. Detecting change-point, trend, and seasonality in satellite time series data to track abrupt changes and nonlinear dynamics: a Bayesian ensemble algorithm. Remote Sens. Environ. 232, 111181 (2019).

    Article  Google Scholar 

  25. Bey, I. et al. Global modeling of tropospheric chemistry with assimilated meteorology: model description and evaluation. J. Geophys. Res. Atmos. 106, 23073–23095 (2001).

    Article  CAS  Google Scholar 

  26. Wang, X. et al. Global tropospheric halogen (Cl, Br, I) chemistry and its impact on oxidants. Atmos. Chem. Phys. 21, 13973–13996 (2021).

    Article  CAS  Google Scholar 

  27. Khan, M. A. H. et al. Global modeling of the nitrate radical (NO3) for present and pre-industrial scenarios. Atmos. Res. 164–165, 347–357 (2015).

    Article  Google Scholar 

  28. Karset, I. H. H. et al. Strong impacts on aerosol indirect effects from historical oxidant changes. Atmos. Chem. Phys. 18, 7669–7690 (2018).

    Article  CAS  Google Scholar 

  29. Archer-Nicholls, S., Allen, R., Abraham, N. L., Griffiths, P. T. & Archibald, A. T. Large simulated future changes in the nitrate radical under the CMIP6 SSP scenarios: implications for oxidation chemistry. Atmos. Chem. Phys. 23, 5801–5813 (2023).

    Article  CAS  Google Scholar 

  30. Hoesly, R. M. et al. Historical (1750–2014) anthropogenic emissions of reactive gases and aerosols from the Community Emissions Data System (CEDS). Geosci. Model Dev. 11, 369–408 (2018).

    Article  CAS  Google Scholar 

  31. Frey, M. M., Savarino, J., Morin, S., Erbland, J. & Martins, J. M. F. Photolysis imprint in the nitrate stable isotope signal in snow and atmosphere of East Antarctica and implications for reactive nitrogen cycling. Atmos. Chem. Phys. 9, 8681–8696 (2009).

    Article  CAS  Google Scholar 

  32. Shi, G. et al. Investigation of post-depositional processing of nitrate in East Antarctic snow: isotopic constraints on photolytic loss, re-oxidation, and source inputs. Atmos. Chem. Phys. 15, 9435–9453 (2015).

    Article  CAS  Google Scholar 

  33. Fibiger, D. L., Hastings, M. G., Dibb, J. E. & Huey, L. G. The preservation of atmospheric nitrate in snow at Summit, Greenland. Geophys. Res. Lett. 40, 3484–3489 (2013).

    Article  CAS  Google Scholar 

  34. Fibiger, D. L. et al. Analysis of nitrate in the snow and atmosphere at Summit, Greenland: chemistry and transport. J. Geophys. Res. Atmos. 121, 5010–5030 (2016).

    Article  CAS  Google Scholar 

  35. Berndt, T., Hoffmann, E. H., Tilgner, A., Stratmann, F. & Herrmann, H. Direct sulfuric acid formation from the gas-phase oxidation of reduced-sulfur compounds. Nat. Commun. 14, 4849 (2023).

    Article  CAS  Google Scholar 

  36. Zhai, S. et al. Anthropogenic influence on tropospheric reactive bromine since the pre-industrial: implications for Arctic ice-core bromine trends. Geophys. Res. Lett. 51, e2023GL107733 (2024).

    Article  CAS  Google Scholar 

  37. Mungall, E. L., Wong, J. P. S. & Abbatt, J. P. D. Heterogeneous oxidation of particulate methanesulfonic acid by the hydroxyl radical: kinetics and atmospheric implications. ACS Earth Space Chem. 2, 48–55 (2018).

    Article  CAS  Google Scholar 

  38. Kwong, K. C. et al. Chemical transformation of methanesulfonic acid and sodium methanesulfonate through heterogeneous OH oxidation. ACS Earth Space Chem. 2, 895–903 (2018).

    Article  CAS  Google Scholar 

  39. Pye, H. O. T. et al. The acidity of atmospheric particles and clouds. Atmos. Chem. Phys. 20, 4809–4888 (2020).

    Article  CAS  Google Scholar 

  40. Sharma, S. et al. Influence of transport and ocean ice extent on biogenic aerosol sulfur in the Arctic atmosphere. J. Geophys. Res. Atmos. 117, D12209 (2012).

    Article  Google Scholar 

  41. Abram, N. J., Wolff, E. W. & Curran, M. A. J. A review of sea ice proxy information from polar ice cores. Quat. Sci. Rev. 79, 168–183 (2013).

    Article  Google Scholar 

  42. Gregg, W. W. & Conkright, M. E. Decadal changes in global ocean chlorophyll. Geophys. Res. Lett. 29, 1730 (2002).

    Article  Google Scholar 

  43. Polovina, J. J., Howell, E. A. & Abecassis, M. Ocean’s least productive waters are expanding. Geophys. Res. Lett. 35, L03618 (2008).

    Article  Google Scholar 

  44. Oziel, L., Massicotte, P., Babin, M. & Devred, E. Decadal changes in Arctic Ocean chlorophyll a: bridging ocean color observations from the 1980s to present time. Remote Sens. Environ. 275, 113020 (2022).

    Article  Google Scholar 

  45. Boyce, D. G., Lewis, M. R. & Worm, B. Global phytoplankton decline over the past century. Nature 466, 591–596 (2010).

    Article  CAS  Google Scholar 

  46. Wernand, M. R., van der Woerd, H. J. & Gieskes, W. W. C. Trends in ocean colour and chlorophyll concentration from 1889 to 2000, worldwide. PLoS ONE 8, e63766 (2013).

    Article  CAS  Google Scholar 

  47. Caesar, L., McCarthy, G. D., Thornalley, D. J. R., Cahill, N. & Rahmstorf, S. Current Atlantic meridional overturning circulation weakest in last millennium. Nat. Geosci. 14, 118–120 (2021).

    Article  CAS  Google Scholar 

  48. Spooner, P. T. et al. Exceptional 20th century ocean circulation in the northeast Atlantic. Geophys. Res. Lett. 47, e2020GL087577 (2020).

    Article  Google Scholar 

  49. Geng, L. et al. Nitrogen isotopes in ice core nitrate linked to anthropogenic atmospheric acidity change. Proc. Natl Acad. Sci. USA 111, 5808–5812 (2014).

    Article  CAS  Google Scholar 

  50. Osterberg, E. C., Handley, M. J., Sneed, S. B., Mayewski, P. A. & Kreutz, K. J. Continuous ice core melter system with discrete sampling for major ion, trace element, and stable isotope analyses. Environ. Sci. Technol. 40, 3355–3361 (2006).

    Article  CAS  Google Scholar 

  51. Osterberg, E. C. et al. The 1200 year composite ice core record of Aleutian Low intensification. Geophys. Res. Lett. 44, 7447–7454 (2017).

    Article  Google Scholar 

  52. Winski, D. et al. Industrial-age doubling of snow accumulation in the Alaska Range linked to tropical ocean warming. Sci. Rep. 7, 17869 (2017).

    Article  Google Scholar 

  53. Wolfe, G. M., Marvin, M. R., Roberts, S. J., Travis, K. R. & Liao, J. The Framework for 0-D Atmospheric Modeling (F0AM) v3.1. Geosci. Model Dev. 9, 3309–3319 (2016).

    Article  Google Scholar 

  54. Jongebloed, U. A. et al. Underestimated passive volcanic sulfur degassing implies overestimated anthropogenic aerosol forcing. Geophys. Res. Lett. 50, e2022GL102061 (2023).

    Article  CAS  Google Scholar 

  55. Ghahreman, R. et al. Dimethyl sulfide and its role in aerosol formation and growth in the Arctic summer—a modelling study. Atmos. Chem. Phys. 19, 14455–14476 (2019).

    Article  Google Scholar 

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Acknowledgements

Retrieval and analysis of the Denali ice core is supported by the National Science Foundation (NSF) Paleo Perspectives on Climate Change Program (P2C2), grants AGS-1204035 (E.C.O.), AGS-1203838 (K.J.K.) and AGS-1203863 (C.P.W.). Denali National Park and Preserve, Polar Field Services and Talkeetna Air Taxi provided aircraft support and field logistical assistance. We thank M. Waszkiewicz, S. Campbell, B. Markle, E. Burakowski, D. Silverstone and T. Godaire for field assistance, and over 25 students for their assistance sampling and analysing the Denali ice cores in the Dartmouth Ice, Climate, and Environment Laboratory. The Denali ice cores were processed at the NSF Ice Core Facility in Denver, Colorado. J.I.C. acknowledges travel support from the Dartmouth Dickey Center. NSF grants PLR-1904128 (B.A.), PLR-2230350 (B.A.) and AGS-2202287 (B.A.) supported analysis of the Summit07 ice core.

Author information

Authors and Affiliations

  1. Department of Earth Sciences, Dartmouth College, Hanover, NH, USA

    Jacob I. Chalif, Erich C. Osterberg & David G. Ferris

  2. Department of Atmospheric and Climate Science, University of Washington, Seattle, WA, USA

    Ursula A. Jongebloed & Becky Alexander

  3. Department of Geology, Colby College, Waterville, ME, USA

    Bess G. Koffman

  4. Climate Change Institute and School of Earth and Climate Sciences, University of Maine, Orono, ME, USA

    Dominic A. Winski & Karl J. Kreutz

  5. Department of Geosciences, University of Alaska, Fairbanks, AK, USA

    David J. Polashenski

  6. Bigelow Laboratory for Ocean Sciences, East Boothbay, ME, USA

    Karen Stamieszkin

  7. Center for North Atlantic Studies, University of New England, Portland, ME, USA

    Cameron P. Wake

  8. Department of Chemistry and Biochemistry, South Dakota State University, Brookings, SD, USA

    Jihong Cole-Dai

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  1. Jacob I. Chalif
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Contributions

J.I.C. and U.A.J. conceived of and carried out this study. E.C.O., B.G.K. and B.A. provided critical guidance and input throughout. E.C.O., K.J.K. and C.P.W. wrote the initial proposal to drill and chemically analyse the Denali ice core. D.G.F. melted the core and, with D.A.W. and E.C.O., developed the timescale. J.C.-D. obtained funding to drill and measure major ions, including MSA and NO3–, in the Summit07 ice core. K.S. and B.G.K. developed a set of initial hypotheses for MSA decline, and K.S. and D.J.P. investigated linkages between Denali MSA and North Pacific production. J.I.C. wrote the paper with input from E.C.O., B.G.K. and U.A.J. All authors discussed the results and reviewed the manuscript.

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Correspondence to Jacob I. Chalif.

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Nature Geoscience thanks Alex Archibald, M. Anwar Khan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Xujia Jiang, in collaboration with the Nature Geoscience team.

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Extended data

Extended Data Fig. 1 Ice core MSA records with changepoint probability.

(a) Denali MSA changepoint probability, based on an irregular Bayesian changepoint analysis (see Methods). The likeliest changepoint year (1962) indicated by a vertical dark orange dashed line. (b) Denali MSA. (c) The Greenland composite MSA records, with the record’s 50th percentile (dark blue) and 95% confidence interval (light blue) given10. (d) Greenland MSA changepoint probability, with the three likeliest changepoint years (1854, 1869, and 1953) indicated by vertical dark blue dashed lines.

Extended Data Fig. 2 F0AM box model results, including Ross Sea, Antarctica.

(a) The PI–IE percent change in MSA under several F0AM model runs, using atmospheric oxidant concentrations from the Denali source region (orange), the Greenland source region (blue), and the Ross Sea, Antarctica (green). The shapes represent the different DMS oxidation mechanisms we used. The APC (leftmost) column shows the change in MSA when all oxidants and temperature (that is, ‘parameters’) change from the PI to the IE. The columns to the right show the change when one parameter is held constant from the PI to the IE and the rest are allowed to change (CNSTp). (b) The MSA-impact score, which is the fraction change between CNSTp and APC. The magnitude of the MSA-impact score represents the oxidative effect of the increase of each parameter from the PI to the IE. Note that the impacts of O3 and OH in the Ross Sea is unusually high because the Ross Sea APC is close to 0. (c) An alternative calculation of MSA impact (MSA-delta), calculated by the difference between CNSTp and APC, which corrects the unusually high Ross Sea MSA-impact score in (b).

Extended Data Fig. 3 Denali MSA from cores 1 and 2.

The MSA record from Denali core 2 (orange; this study) and core 1 (red). Core 1 was only analyzed to 1866 and its raw record contains anomalous dips to near 0, leading to an overall lower annual average than core 2. Despite the data issues, core 1 contains a mean decline in MSA of 1.79 ppb from 1962–2011 compared with 1866–1961. Core 2, likewise, contains a mean drop of 1.77 ppb over the same period.

Extended Data Fig. 4 F0AM model parameter sensitivity testing of the Denali source region.

These are model runs in which all parameters (that is, oxidant concentrations and temperature) change from PI to IE, using the Fung mechanism. The red markers indicate the mean modeled changes for the Denali source region. Each panel shows the sensitivity of the model to different selections of the labeled parameter. See Methods for details.

Extended Data Fig. 5 F0AM model parameter sensitivity testing of the Greenland source region.

As with Extended Data Fig. 4, but with the Greenland MSA source region.

Extended Data Table 1 F0AM box model parameters
Full size table

Supplementary information

Supplementary Information

Supplementary Figs. 1–4, Tables 1–5, discussion and references.

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Chalif, J.I., Jongebloed, U.A., Osterberg, E.C. et al. Pollution drives multidecadal decline in subarctic methanesulfonic acid. Nat. Geosci. (2024). https://doi.org/10.1038/s41561-024-01543-w

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