Massive volcanic SO2 oxidation and sulphate aerosol deposition in Cenozoic North America

Abstract

Volcanic eruptions release a large amount of sulphur dioxide (SO2) into the atmosphere1,2. SO2 is oxidized to sulphate and can subsequently form sulphate aerosol3, which can affect the Earth's radiation balance, biologic productivity and high-altitude ozone concentrations, as is evident from recent volcanic eruptions4. SO2 oxidation can occur via several different pathways that depend on its flux and the atmospheric conditions3. An investigation into how SO2 is oxidized to sulphate—the oxidation product preserved in the rock record—can therefore shed light on past volcanic eruptions and atmospheric conditions. Here we use sulphur and triple oxygen isotope measurements of atmospheric sulphate extracted from tuffaceous deposits to investigate the specific oxidation pathways from which the sulphate was formed. We find that seven eruption-related sulphate aerosol deposition events have occurred during the mid-Cenozoic era (34 to 7 million years ago) in the northern High Plains, North America. Two extensively sampled ash beds display a similar sulphate mixing pattern that has two distinct atmospheric secondary sulphates. A three-dimensional atmospheric sulphur chemistry and transport model study reveals that the observed, isotopically discrete sulphates in sediments can be produced only in initially alkaline cloudwater that favours an ozone-dominated SO2 oxidation pathway in the troposphere. Our finding suggests that, in contrast to the weakly acidic conditions today5, cloudwater in the northern High Plains may frequently have been alkaline during the mid-Cenozoic era. We propose that atmospheric secondary sulphate preserved in continental deposits represents an unexploited geological archive for atmospheric SO2 oxidation chemistry linked to volcanism and atmospheric conditions in the past.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Figure 1: Geological context of the samples.
Figure 2: Three sulphate endmember mixings.
Figure 3: Modelling results on sulphate fluxes and Δ 17 O values.

References

  1. 1

    Wallace, P. J. Volcanic SO2 emissions and the abundance and distribution of exsolved gas in magma bodies. J. Volcanol. Geotherm. Res. 108, 85–106 (2001)

    ADS  CAS  Article  Google Scholar 

  2. 2

    Self, S., Widdowson, M., Thordarson, T. & Jay, A. E. Volatile fluxes during flood basalt eruptions and potential effects on the global environment: a Deccan perspective. Earth Planet. Sci. Lett. 248, 518–532 (2006)

    ADS  CAS  Article  Google Scholar 

  3. 3

    Seinfeld, J. H. & Pandis, S. N. Atmospheric Chemistry and Physics: From Air Pollution to Climate Change Ch. 6 (Wiley, 1998)

    Google Scholar 

  4. 4

    Robock, A. Pinatubo eruption: the climatic aftermath. Science 295, 1242–1244 (2002)

    CAS  Article  Google Scholar 

  5. 5

    National Atmospheric Deposition Program. 2008 Annual Summary. 15 〈http://nadp.sws.uiuc.edu/lib/data/2008as.pdf〉 (NADP Program Office, Illinois State Water Survey, 2009)

  6. 6

    Wignall, P. The link between large igneous province eruptions and mass extinctions. Elements 1, 293–297 (2005)

    Article  Google Scholar 

  7. 7

    Ward, P. L. Sulfur dioxide initiates global climate change in four ways. Thin Solid Films 517, 3188–3203 (2009)

    ADS  CAS  Article  Google Scholar 

  8. 8

    Thordarson, T. & Self, S. Atmospheric and environmental effects of the 1783–1784 Laki eruption: a review and reassessment. J. Geophys. Res. Atmos. 108 10.1029/2001JD002042 (2003)

  9. 9

    Mather, T. A. et al. Oxygen and sulfur isotopic composition of volcanic sulfate aerosol at the point of emission. J. Geophys. Res. Atmos. 111 D18205 10.1029/2005jd006584 (2006)

    ADS  Article  Google Scholar 

  10. 10

    Rose, W. I. et al. Atmospheric chemistry of a 33–34 hour old volcanic cloud from Hekla volcano (Iceland): insights from direct sampling and the application of chemical box modeling. J. Geophys. Res. Atmos. 111 10.1029/2005JD006872 (2006)

  11. 11

    Morin, S. et al. Tracing the origin and fate of NOx in the Arctic atmosphere using stable isotopes in nitrate. Science 322, 730–732 (2008)

    ADS  CAS  Article  Google Scholar 

  12. 12

    Bao, H. M. et al. Anomalous 17O compositions in massive sulphate deposits on the Earth. Nature 406, 176–178 (2000)

    ADS  CAS  Article  Google Scholar 

  13. 13

    Bao, H. M., Thiemens, M. H., Loope, D. B. & Yuan, X. L. Sulfate oxygen-17 anomaly in an Oligocene ash bed in mid-North America: was it the dry fogs? Geophys. Res. Lett. 30 10.1029/2003GL016869 (2003)

  14. 14

    Loope, D. B., Mason, J. A., Bao, H. M., Kettler, R. M. & Zanner, C. W. Deformation structures and an alteration zone linked to deposition of volcanogenic sulphate in an ancient playa (Oligocene of Nebraska, USA). Sedimentology 52, 123–139 (2005)

    ADS  CAS  Article  Google Scholar 

  15. 15

    Bindeman, I. N., Eiler, J. M., Wing, B. A. & Farquhar, J. Rare sulfur and triple oxygen isotope geochemistry of volcanogenic sulfate aerosols. Geochim. Cosmochim. Acta 71, 2326–2343 (2007)

    ADS  CAS  Article  Google Scholar 

  16. 16

    Lyons, J. R. Transfer of mass-independent fractionation in ozone to other oxygen-containing radicals in the atmosphere. Geophys. Res. Lett. 28, 3231–3234 (2001)

    ADS  CAS  Article  Google Scholar 

  17. 17

    Savarino, J., Bekki, S., Cole-Dai, J. & Thiemens, M. H. Evidence from sulfate mass independent oxygen isotopic compositions of dramatic changes in atmospheric oxidation following massive volcanic eruptions. J. Geophys. Res. Atmos. 108 10.1029/2003jd003737 (2003)

  18. 18

    Noda, T. & Shimada, K. Water mixing model calculation for evaluation of deep geothermal water. Geothermics 22, 165–180 (1993)

    CAS  Article  Google Scholar 

  19. 19

    Savarino, J., Lee, C. C. W. & Thiemens, M. H. Laboratory oxygen isotopic study of sulfur (IV) oxidation: origin of the mass-independent oxygen isotopic anomaly in atmospheric sulfates and sulfate mineral deposits on Earth. J. Geophys. Res. Atmos. 105, 29079–29088 (2000)

    ADS  CAS  Article  Google Scholar 

  20. 20

    Savarino, J. & Thiemens, M. H. Analytical procedure to determine both δ18O and δ17O of H2O2 in natural water and first measurements. Atmos. Environ. 33, 3683–3690 (1999)

    ADS  CAS  Article  Google Scholar 

  21. 21

    Johnston, J. C. & Thiemens, M. H. The isotopic composition of tropospheric ozone in three environments. J. Geophys. Res. Atmos. 102, 25395–25404 (1997)

    ADS  CAS  Article  Google Scholar 

  22. 22

    Jenkins, K. A. & Bao, H. M. Multiple oxygen and sulfur isotope compositions of atmospheric sulfate in Baton Rouge, LA, USA. Atmos. Environ. 40, 4528–4537 (2006)

    ADS  CAS  Article  Google Scholar 

  23. 23

    Bao, H. M. Sulfate in modern playa settings and in ash beds in hyperarid deserts: implication on the origin of 17O-anomalous sulfate in an Oligocene ash bed. Chem. Geol. 214, 127–134 (2005)

    ADS  CAS  Article  Google Scholar 

  24. 24

    Howell, K. J. & Bao, H. M. Caliche as a geological repository for atmospheric sulfate. Geophys. Res. Lett. 33 10.1029/2006GL026518 (2006)

  25. 25

    Alexander, B., Savarino, J., Barkov, N. I., Delmas, R. J. & Thiemens, M. H. Climate driven changes in the oxidation pathways of atmospheric sulfur. Geophys. Res. Lett. 29 1685 10.1029/2002GL014879 (2002)

    ADS  Article  Google Scholar 

  26. 26

    Bao, H. M. & Marchant, D. R. Quantifying sulfate components and their variations in soils of the McMurdo Dry Valleys, Antarctica. J. Geophys. Res. Atmos. 111 10.1029/2005JD006669 (2006)

  27. 27

    Armstrong, R. L. & Ward, P. L. Evolving geographic patterns of Cenozoic magmatism in the North American Cordillera; the temporal and spatial association of magmatism and metamorphic core complexes Mid-Tertiary Cordilleran magmatism; plate convergence versus intraplate processes. J. Geophys. Res. B 96, 13201–13224 (1991)

    ADS  Article  Google Scholar 

  28. 28

    Bao, H., Thiemens, M. H. & Heine, K. Oxygen-17 excesses of the Central Namib gypcretes: spatial distribution. Earth Planet. Sci. Lett. 192, 125–135 (2001)

    ADS  CAS  Article  Google Scholar 

  29. 29

    Eder, B. & Yu, S. C. A performance evaluation of the 2004 release of Models-3 CMAQ. Atmos. Environ. 40 4811–4824 10.1016/j.atmosenv.2005.08.045 (2006)

    ADS  CAS  Article  Google Scholar 

  30. 30

    Zhang, D. D. et al. Precipitation chemistry of Lhasa and other remote towns, Tibet. Atmos. Environ. 37, 231–240 (2003)

    ADS  CAS  Article  Google Scholar 

Download references

Acknowledgements

H.B. thanks D. Loope, H. LaGarry and J. Swinehart for guidance in the field, M. Khachaturyan, K. Jenkins, K. Howell, I. Kohl and A. J. Kaufman for technical assistance, B. Li for statistical treatment, and the National Park Service for sampling permission at Scotts Bluff National Monument (permit numbers SCBL-2000-SCI-000, BADL-2004-SCI-0012 and SCBL-2004-SCI-0005). Financial support was provided by the NSF (EAR-0408986 to H.B.). S.Y. thanks S. T. Rao, D. Mobley, K. Schere, R. Mathur, J. Pleim, J. Godowitch and S. Roselle for comments. The United States Environmental Protection Agency through its Office of Research and Development funded and managed the part of the research that is related to sulphur chemistry modelling. It has been subjected to the Agency’s administrative review and approved for publication. D.Q.T. is grateful to S. Fine, D. Byun and R. Artz for discussion and acknowledges constructive internal Air Resources Laboratory comments.

Author information

Affiliations

Authors

Contributions

H.B. designed the research, and did field and laboratory studies. S.Y. and D.Q.T. did the three-dimensional sulphur oxidation and transport modelling study. H.B. wrote the manuscript. All authors contributed to manuscript revisions.

Corresponding authors

Correspondence to Huiming Bao or Shaocai Yu.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Tables S1-S5, Supplementary Methods, Supplementary Figures S1-S8 with legends and References. (PDF 593 kb)

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Bao, H., Yu, S. & Tong, D. Massive volcanic SO2 oxidation and sulphate aerosol deposition in Cenozoic North America. Nature 465, 909–912 (2010). https://doi.org/10.1038/nature09100

Download citation

Further reading

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.