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Halocarbons produced by natural oxidation processes during degradation of organic matter

A Correction to this article was published on 18 January 2001


Volatile halogenated organic compounds (VHOC) play an important role in atmospheric chemical processes—contributing, for example, to stratospheric ozone depletion1,2,3,4. For anthropogenic VHOC whose sources are well known5, the global atmospheric input can be estimated from industrial production data. Halogenated compounds of natural origin can also contribute significantly to the levels of VHOC in the atmosphere6. The oceans have been implicated as one of the main natural sources7,8,9,10, where organisms such as macroalgae and microalgae can release large quantities of VHOC to the atmosphere11,12. Some terrestrial sources have also been identified, such as wood-rotting fungi13, biomass burning14 and volcanic emissions15. Here we report the identification of a different terrestrial source of naturally occurring VHOC. We find that, in soils and sediments, halide ions can be alkylated during the oxidation of organic matter by an electron acceptor such as Fe( III): sunlight or microbial mediation are not required for these reactions. When the available halide ion is chloride, the reaction products are CH3Cl, C2H5Cl, C3H7Cl and C4H9Cl. (The corresponding alkyl bromides or alkyl iodides are produced when bromide or iodide are present.) Such abiotic processes could make a significant contribution to the budget of the important atmospheric compounds CH3Cl, CH3Br and CH3I.

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Figure 1
Figure 2: Abiotic reduction of Fe(III) in soils and the production of alkyl iodides in the presence of iodide.
Figure 3: Influence of Fe(III) and halide ions on the formation of alkyl halides.
Figure 4: Data supporting the abiotic production of methyl halides by the interaction of guaiacol with ferrihydrite and halide.


  1. Crutzen, P. J. & Arnold, F. Nitric acid clouds formation in the cold Antarctic stratosphere: a major cause for the springtime ‘ozone hole’. Nature 324, 651– 655 (1986).

    Article  ADS  CAS  Google Scholar 

  2. Solomon, S. Progress towards a quantitative understanding of Antarctic ozone depletion. Nature 347, 347–354 (1990).

    Article  ADS  CAS  Google Scholar 

  3. Anderson, J. G., Toohey, D. W. & Brune, W. H. Free radicals within the Antarctic vortex: The role of CFCs in the Antarctic ozone loss. Science 251, 39–46 (1991).

    Article  ADS  CAS  PubMed  Google Scholar 

  4. Wever, R. Ozone destruction by algae in the Arctic atmosphere. Science 355, 501 (1988).

    Google Scholar 

  5. Butler, J. H. et al. A record of atmospheric halocarbons during the twentieth century from polar firn air. Nature 399, 749– 755 (1999).

    Article  ADS  CAS  Google Scholar 

  6. Gribble, G. W. Naturally occurring organohalogen compounds—a survey. J. Natural Prod. 55, 1353–1395 (1992).

    Article  CAS  Google Scholar 

  7. Lovelock, J. E. Natural halocarbons in the air and in the sea. Nature 256, 193–194 (1975).

    Article  ADS  CAS  PubMed  Google Scholar 

  8. Singh, H. B., Salas, L. J. & Stiles, R. E. Methylhalides in and over the Eastern Pacific (40° N-32° S). J. Geophys. Res. 88, 3684– 3690 (1983).

    Article  ADS  CAS  Google Scholar 

  9. Class, T. & Ballschmiter, K. Sources and distribution of bromo- and bromochloromethanes in marine air and surface water of the Atlantic Ocean. J. Atmos. Chem. 6, 35– 46 (1988).

    Article  CAS  Google Scholar 

  10. Moore, R. M., Groszko, W. & Niven, S. J. Ocean-atmosphere exchange of methyl chloride: Results from NW Atlantic and Pacific Ocean studies. J. Geophys. Res. 101, 28529–28538 (1988).

    Article  ADS  Google Scholar 

  11. Sturges, W. T., Sullivan, C. W., Schnell, R. C., Heidt, L. E. & Pollack, W. H. Bromoalkane production by Antarctic ice algae. Tellus B 45, 120– 126 (1993).

    Article  ADS  Google Scholar 

  12. Laturnus, F. & Adams, F. C. Methylhalides from Antarctic macroalgae. Geophys. Res. Lett. 25, 773– 776 (1998).

    Article  ADS  CAS  Google Scholar 

  13. Harper, D. B. Halomethane from halide ion—a highly efficient fungal conversion of environmental significance. Nature 315, 55–57 (1985).

    Article  ADS  CAS  Google Scholar 

  14. Andreae, M. O. et al. Methylhalide emissions from savanna fires in southern Africa. J. Geophys. Res. 101, 23603– 23613 (1996).

    Article  ADS  CAS  Google Scholar 

  15. Rasmussen, R. A., Rasmussen, L. E., Khalil, M. A. K. & Dalluge, R. W. Concentration of methyl chloride in the atmosphere. J. Geophys. Res. 85, 7350–7356 ( 1980).

    Article  ADS  CAS  Google Scholar 

  16. Hoekstra, E. J., Lassen, P., van Leeuwen, J. G. E., De Leer, E. W. B. & Carlsen, L. in Naturally Produced Organohalogens (eds Grimvall, A. & De Leer, E. W. B.) 149– 158 (Kluwer Academic, Dordrecht, 1995).

    Book  Google Scholar 

  17. Desjardins, S., Landry, J. A. & Farant, J. P. Effects of water and pH on the oxidative oligomerization of chloro and methoxyphenol by a montmorillonite clay. J. Soil Contamin. 8, 175–195 ( 1999).

    Article  CAS  Google Scholar 

  18. Lovley, D. R. Dissimilatory Fe(III) and Mn(IV) reduction. Microbiol. Rev. 55, 259–287 (1991).

    CAS  PubMed  PubMed Central  Google Scholar 

  19. Post, W. M., Emanuel, W. R., Zinke, P. J. & Stangenberger, A. L. Soil carbon pools and world life zones. Nature 298, 156–159 (1982).

    Article  ADS  CAS  Google Scholar 

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We thank D. Schlösser and K. Kratz for the instrumental neutron activation analysis (INAA) measurements and I. Fahimi and L. Warr for reviewing the manuscript.

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Correspondence to F. Keppler.

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Keppler, F., Eiden, R., Niedan, V. et al. Halocarbons produced by natural oxidation processes during degradation of organic matter. Nature 403, 298–301 (2000).

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