Skip to main content
SpringerLink
Log in

Speciation analysis of iodine and bromine at picogram-per-gram levels in polar ice

  • Original Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Iodine and bromine species participate in key atmospheric reactions including the formation of cloud condensation nuclei and ozone depletion. We present a novel method coupling a high-performance liquid chromatography with ion chromatography and inductively coupled plasma mass spectrometry, which allows the determination of iodine (I) and bromine (Br) species (IO −3 , I−, Br−, BrO −3 ) at the picogram-per-gram levels presents in Antarctic ice. Chromatographic separation was achieved using an IONPAC® AS16 Analytical Column with NaOH as eluent. Detection limits for I and Br species were 5 to 9 pg g−1 with an uncertainty of less than 2.5% for all considered species. Inorganic iodine and bromine species have been determined in Antarctic ice core samples, with concentrations close to the detection limits for iodine species, and approximately 150 pg g−1 for Br−. Although iodate (IO −3 ) is the most abundant iodine species in the atmosphere, only the much rarer iodide (I−) species was present in Antarctic Holocene ice. Bromine was found to be present in Antarctic ice as Br−.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. Charlson RJ, Schwartz SE, Hales JM, Cess RD, Coakley JA, Hansen JE, Hofmann DJ (1992) Climate forcing by anthropogenic aerosols. Science 255(5043):423–430

    Article  CAS  Google Scholar 

  2. Pechtl S, Lovejoy ER, Burkholder JB, von Glasow R (2006) Modeling the possible role of iodine oxides in atmospheric new particle formation. Atmos Chem Phys 6:505–523

    Article  CAS  Google Scholar 

  3. McFiggans G, Coe H, Burgess R, Allan J, Cubison M, Alfarra MR, Saunders R, Saiz-Lopez A, Plane JMC, Wevill DJ, Carpenter LJ, Rickard AR, Monks PS (2004) Direct evidence for coastal iodine particles from Laminaria macroalgae—linkage to emissions of molecular iodine. Atmos Chem Phys 4:701–713

    Article  CAS  Google Scholar 

  4. Calvert JG, Lindberg SE (2004) Potential influence of iodine-containing compounds on the chemistry of the troposphere in the polar spring. I. Ozone depletion. Atmos Environ 38(30):5087–5104. doi:10.1016/j.atmosenv.2004.05.049

    Article  CAS  Google Scholar 

  5. Gilfedder BS, Petri M, Biester H (2007) Iodine and bromine speciation in snow and the effect of orographically induced precipitation. Atmos Chem Phys 7(10):2661–2669

    Article  CAS  Google Scholar 

  6. McFiggans G (2000) A model study of iodine chemistry in the marine boundary layer. J Geophys Res 105:14371–14386

    Article  CAS  Google Scholar 

  7. Hou X, Hansen V, Aldahan A, Possnert G, Lind O, Lujaniene G (2009) A review on speciation of iodine-129 in the environmental and biological samples. Anal Chim Acta 632(2):181–196

    Article  CAS  Google Scholar 

  8. Wong GTF (1991) The marine geochemistry of iodine. Rev Aquat Sci 4(1):45–73

    CAS  Google Scholar 

  9. Tian RC, Nicolas E (1995) Iodine speciation in the northwestern Mediterranean Sea, method and vertical profile. Mar Chem 48(2):151–156

    Article  CAS  Google Scholar 

  10. De Luca RA, Herms FW, Wagener K (1990) The cycling of iodine as iodate and iodide in a tropical estuarine system. Mar Chem 29:77–93

    Article  Google Scholar 

  11. Luther GW III, Campbell T (1991) Iodine speciation in the water column of the Black Sea. Deep Sea Res A Oceanogr Res Pap 38(Supplement 2):S875–S882, 0

    Article  Google Scholar 

  12. Vogt R, Sander R, Von Glasow R, Crutzen PJ (1999) Iodine chemistry and its role in halogen activation and ozone loss in the marine boundary layer: a model study. J Atmos Chem 32(3):375–395

    Article  CAS  Google Scholar 

  13. Saiz-Lopez A, Plane J (2004) Novel iodine chemistry in the marine boundary layer. Geophys Res Lett 31(4):L04112. doi:10.1029/2003GL019215

    Article  Google Scholar 

  14. Baker AR (2004) Inorganic iodine speciation in tropical Atlantic aerosol. Geophys Res Lett 31(23):L23S02. doi:10.1029/2004gl020144

    Article  Google Scholar 

  15. Sander R, Keene WC, Pszenny AAP, Arimoto R, Ayers GP, Baboukas E, Cainey JM, Crutzen PJ, Duce RA, Hoenninger G, Huebert BJ, Maenhaut W, Mihalopoulos N, Turekian VC, Van Dingenen R (2003) Inorganic bromine in the marine boundary layer: a critical review. Atmos Chem Phys 3(5):1301–1336. doi:10.5194/acp-3-1301-2003

    Article  CAS  Google Scholar 

  16. Greenwood NN, Earnshaw A (2005) Chemistry of the elements. Elsevier, Amsterdam, The Netherlands, 1342

    Google Scholar 

  17. Salawitch R (2006) Biogenic bromine. Nature 439(7074):275–277

    Article  CAS  Google Scholar 

  18. Simpson WR, Alvarez-Aviles L, Douglas TA, Sturm M, Domine F (2005) Halogens in the coastal snow pack near Barrow, Alaska: evidence for active bromine air-snow chemistry during springtime. Geophys Res Lett 32(4):L04811. doi:10.1029/2004gl021748

    Article  Google Scholar 

  19. Ayers GP, Gillett RW, Cainey JM, Dick AL (1999) Chloride and bromide loss from sea-salt particles in Southern Ocean Air. J Atmos Chem 33(3):299–319. doi:10.1023/a:1006120205159

    Article  CAS  Google Scholar 

  20. Baker J, Reeves C, Nightingale P, Penkett S, Gibb S, Hatton A (1999) Biological production of methyl bromide in the coastal waters of the North Sea and open ocean of the northeast Atlantic. Mar Chem 64(4):267–285

    Article  CAS  Google Scholar 

  21. Laturnus F, Adams FC, Wiencke C (1998) Methyl halides from Antarctic macroalgae. Geophys Res Lett 25(6):773–776. doi:10.1029/98gl00490

    Article  CAS  Google Scholar 

  22. Baker A, Tunnicliffe C, Jickells T (2001) Iodine speciation and deposition fluxes from the marine atmosphere. J Geophys Res 106(D22):28743

    Article  CAS  Google Scholar 

  23. Gilfedder BS, Lai SC, Petri M, Biester H, Hoffmann T (2008) Iodine speciation in rain, snow and aerosols. Atmos Chem Phys 8(20):6069–6084

    Article  CAS  Google Scholar 

  24. Simpson WR, von Glasow R, Riedel K, Anderson P, Ariya P, Bottenheim J, Burrows J, Carpenter LJ, Friess U, Goodsite ME, Heard D, Hutterli M, Jacobi HW, Kaleschke L, Neff B, Plane J, Platt U, Richter A, Roscoe H, Sander R, Shepson P, Sodeau J, Steffen A, Wagner T, Wolff E (2007) Halogens and their role in polar boundary-layer ozone depletion. Atmos Chem Phys 7(16):4375–4418

    Article  CAS  Google Scholar 

  25. Wolff E, Barbante C, Becagli S, Bigler M, Boutron C, Castellano E, De Angelis M, Federer U, Fischer H, Fundel F (2010) Changes in environment over the last 800,000 years from chemical analysis of the EPICA Dome C ice core. Quat Sci Rev 29(1–2):285–295

    Article  Google Scholar 

  26. Gilfedder BS, Petri M, Biester H (2006) Iodine speciation and redox cycling in limnic systems: case studies from Lake Constance and the Mummelsee. Geochim Cosmochim Acta 70(18):A202–A202. doi:10.1016/J.Gca.2006.06.408

    Article  Google Scholar 

  27. Liu W, Yang H, Li B, Xu S (2011) Determination of bromine and iodine speciation in drinking water using high performance liquid chromatography-inductively coupled plasma mass spectrometry. Geostand Geoanal Res 35(1):69–74

    Article  CAS  Google Scholar 

  28. Huang Z, Ito K, Timerbaev A, Hirokawa T (2004) Speciation studies by capillary electrophoresis—simultaneous determination of iodide and iodate in seawater. Anal Bioanal Chem 378(7):1836–1841. doi:10.1007/s00216-004-2506-4

    Article  CAS  Google Scholar 

  29. Lyon TDB, Robin PA, Watson WS, Littlejohn D (2005) Determination of elevated concentrations of bromine in serum by ICP-MS and ICP-OES. J Anal At Spectrom 20(8):757–759

    Article  CAS  Google Scholar 

  30. Spokes LJ, Liss PS (1996) Photochemically induced redox reactions in seawater. II. Nitrogen and iodine. Mar Chem 54:1–10

    Article  CAS  Google Scholar 

  31. Saltzman ES, Aydin M, Tatum C, Williams MB (2008) 2,000-year record of atmospheric methyl bromide from a South Pole ice core. J Geophys Res 113(D5):D05304. doi:10.1029/2007jd008919

    Article  Google Scholar 

  32. Saiz-Lopez A, Plane JMC, Baker AR, Carpenter LJ, von Glasow R, Gomez Martin JC, McFiggans G, Saunders RW (2011) Atmospheric chemistry of iodine. Chem Rev. doi:10.1021/cr200029u

  33. Slaets S, Laturnus F, Adams FC (1999) Microwave induced plasma atomic emission spectrometry: a suitable detection system for the determination of volatile halocarbons. Fresenius J Anal Chem 364(1):133–140. doi:10.1007/s002160051312

    Article  CAS  Google Scholar 

  34. Gabrielli P, Varga A, Barbante C, Boutron C, Cozzi G, Gaspari V, Planchon F, Cairns W, Hong S, Ferrari C, Capodaglio G (2004) Determination of Ir and Pt down to the sub-femtogram per gram level in polar ice by ICP-SFMS using preconcentration and a desolvation system. J Anal At Spectrom 19(7):831–837

    Article  CAS  Google Scholar 

  35. Frezzotti M, Bitelli G, de Michelis P, Deponti A, Forieri A, Gandolfi S, Maggi V, Mancini F, Remy F, Tabacco IE, Urbini S, Vittuari L, Zirizzottl A (2004) Geophysical survey at Talos Dome, East Antarctica: the search for a new deep-drilling site. Ann Glaciol 39(1):423–432. doi:10.3189/172756404781814591

    Article  Google Scholar 

  36. Buiron D, Chappellaz J, Stenni B, Frezzotti M, Baumgartner M, Capron E, Landais A, Lemieux-Dudon B, Masson-Delmotte V, Montagnat M, Parrenin F, Schilt A (2010) TALDICE-1 age scale of the Talos Dome deep ice core, East Antarctica. Clim Past Discuss 6:1733–1776

    Article  Google Scholar 

  37. Stenni B, Buiron D, Frezzotti M, Albani S, Barbante C, Bard E, Barnola JM, Baroni M, Baumgartner M, Bonazza M, Capron E, Castellano E, Chappellaz J, Delmonte B, Falourd S, Genoni L, Iacumin P, Jouzel J, Kipfstuhl S, Landais A, Lemieux-Dudon B, Maggi V, Masson-Delmotte V, Mazzola C, Minster B, Montagnat M, Mulvaney R, Narcisi B, Oerter H, Parrenin F, Petit JR, Ritz C, Scarchilli C, Schilt A, Schupbach S, Schwander J, Selmo E, Severi M, Stocker TF, Udisti R (2011) Expression of the bipolar see-saw in Antarctic climate records during the last deglaciation. Nat Geosci 4(1):46–49. doi:10.1038/ngeo1026

    Article  CAS  Google Scholar 

  38. Kaufmann PR, Federer U, Hutterli MA, Bigler M, SchuÃàpbach S, Ruth U, Schmitt J, Stocker TF (2008) An improved continuous flow analysis system for high-resolution field measurements on ice cores. Environ Sci Technol 42(21):8044–8050. doi:10.1021/es8007722

    Article  CAS  Google Scholar 

  39. Ruth U, Barbante C, Bigler M, Delmonte B, Fischer H, Gabrielli P, Gaspari V, Kaufmann P, Lambert F, Maggi V (2008) Proxies and measurement techniques for mineral dust in Antarctic ice cores. Environ Sci Technol 42(15):5675–5681

    Article  CAS  Google Scholar 

  40. Vogt R (1999) Iodine compounds in the atmosphere. In: Fabian P, Singh ON (eds) Reactive halogen compounds in the atmosphere. Springer-Verlag, Berlin

    Google Scholar 

  41. Yang H, Liu W, Li B, Zhang H, Liu X, Chen D (2007) Speciation analysis for iodine in groundwater using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). Geostand Geoanal Res 31(4):345–351

    Article  CAS  Google Scholar 

  42. Enami S, Vecitis C, Cheng J, Hoffmann M, Colussi A (2007) Global inorganic source of atmospheric bromine. J Phys Chem A 111(36):8749–8752

    Article  CAS  Google Scholar 

  43. Chen H, Brandt R, Bandur R, Hoffmann T (2006) Characterization of iodine species in the marine aerosol: to understand their roles in particle formation processes. Front Chem China 1(2):119–129. doi:10.1007/s11458-006-0001-5

    Article  CAS  Google Scholar 

  44. Saiz-Lopez A, Saunders R, Joseph D, Ashworth S, Plane J (2004) Absolute absorption cross-section and photolysis rate of I-2. Atmos Chem Phys 4:1443–1450

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the University of Siena and IDPA-CNR. We are grateful to colleagues at the University of Venice for instrumental and technical assistance and in particular to Dr. Warren Cairns of the IDPA-CNR for the discussion on speciation. The Talos Dome Ice Core Project (TALDICE), a joint European program, is funded by contributions from Italy, France, Germany, Switzerland, and the UK. Logistical support was provided by PNRA. This is TALDICE publication no 17.

Author information

Authors and Affiliations

  1. Department of Earth Science, University of Siena, Via del Laterino 8, 53100, Siena, Italy

    Andrea Spolaor

  2. Institute for the Dynamics of Environmental Processes - CNR, University of Venice, Dorsoduro 2137, 30123, Venice, Italy

    Andrea Spolaor, Jacopo Gabrieli, Natalie Kehrwald, Clara Turetta, Giulio Cozzi & Carlo Barbante

  3. Centre for Ice and Climate, Niels Bohr Institute, Juliane Maries Vej 30, 2100, Copenhagen, Denmark

    Paul Vallelonga

  4. Department of Environmental Sciences, Informatics and Statistics, University Ca’ Foscari of Venice, Dorsoduro 2137, 30123, Venice, Italy

    Luisa Poto & Carlo Barbante

  5. School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK

    John M. C. Plane

  6. Laboratoire de Glaciologie et Géophysique de l’Environnement, UMR UJF/CNRS 5183, 54, rue Molière, Domaine Universitaire, B.P. 96, 38402, Saint Martin d’ Hères, France

    C. Boutron

  7. Accademia Nazionale dei Lincei, Centro B. Segre, via della Lungara 10, 00196, Rome, Italy

    Carlo Barbante

Authors
  1. Andrea Spolaor
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Paul Vallelonga
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jacopo Gabrieli
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Natalie Kehrwald
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Clara Turetta
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Giulio Cozzi
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Luisa Poto
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. John M. C. Plane
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. C. Boutron
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Carlo Barbante
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Carlo Barbante.

Additional information

Published in the special issue Analytical Science in Italy with guest editor Aldo Roda.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Spolaor, A., Vallelonga, P., Gabrieli, J. et al. Speciation analysis of iodine and bromine at picogram-per-gram levels in polar ice. Anal Bioanal Chem 405, 647–654 (2013). https://doi.org/10.1007/s00216-012-5806-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-012-5806-0

Keywords

Search

Navigation