Iron Mineral Catalyzed C-H Activation As a Potential Pathway for Halogenation Processes

Thursday, 18 December 2014
Heinz Friedrich Schoeler, Christoph Tubbesing, Kathrin Benzing, Torsten Krause, Sabine Lippe and Maik Rudloff, University of Heidelberg, Heidelberg, Germany
Due to increasing drinking water demand of mankind and an expected climate change the impact of salt lakes and salt deserts will increase within the next decades. Furthermore, a rising sea level influences coastal areas like salt marshes and abets processes which will lead to elevated organohalogen formation. An additional increase of the global warming potential, of particle formation and stratospheric ozone depletion is expected. Understanding these multifaceted processes is essential for mankind to be prepared for these alterations of the atmosphere.

For example, Keppler et al. (2000) described the production of volatile halogenated organic compounds via oxidation of organic matter driven by ferric iron. However, the formation of long-chained alkyl halides in salt lakes is yet undisclosed. Despite the relative “inertness” of alkanes a direct halogenation of these compounds might be envisaged.

In 2005 Vaillancourt et al. discovered a nonheme iron enzyme which is able to halogenate organic compounds via generating the high valent ferryl cation as reaction center. Based on various publications about C-H activation (Bergman, 2007) we postulate a halogenation process in which an iron containing minerals catalyse the C-H bond cleavage of organic compounds in soils. The generated organic radicals are highly reactive towards halides connected to the iron complex.

We suggest that next to diagenetically altered iron containing enzymes, minerals such as oxides, hydroxides and sulfides are involved in abiotic halogenation processes.

We applied the amino acid methionine as organic model compound and soluble iron species as reactants. All samples were incubated in aqueous phases containing various NaCl concentrations. As a result various halogenated ethanes and ethenes were identified as reaction products.


Bergman, R. G. (2007) Nature, 446(7134) 391-393

Keppler, F., et al. (2000) Nature, 403(6767) 298-301

Vaillancourt, F. H., et al. (2005) Nature, 436(7054) 1191-1194