Nanogoethite is the dominant reactive oxyhydroxide phase in lake and marine sediments

Iron oxides affect many elemental cycles in aquatic sediments via numerous redox reactions and their large sorption capacities for phosphate and trace elements. The reactive ferric oxides and oxyhydroxides are usually quantified by operationally defined selective chemical extractions that are not mineral specific. We have used cryogenic 57Fe Mossbauer spectroscopy to show that the reactive iron oxyhydroxide phase in a large variety of lacustrine and marine environments is nanophase goethite (α-FeOOH), rather than the assumed surface-complex–stabilized, two-line ferrihydrite and accompanying mixture of clay and oxyhydroxide Fe-bearing phases. This result implies that the kinetic and stability parameters of the type of nanogoethite that we observe to be present in sediments should be first determined and then used in models of early diagenesis. The identity and characteristics of the reactive phase will also set constraints on the mechanisms of its authigenesis.

[1]  P. Murphy,et al.  Chemistry of iron in soils. ferric hydrolysis products , 1975 .

[2]  D. Hammond,et al.  Early oxidation of organic matter in pelagic sediments of the eastern equatorial Atlantic: suboxic diagenesis , 1979 .

[3]  D. Rancourt Magnetism of Earth, Planetary, and Environmental Nanomaterials , 2001 .

[4]  C. Koch,et al.  Mössbauer spectroscopic studies on the iron forms of deep-sea sediments , 1997 .

[5]  Dianne K. Newman,et al.  A role for excreted quinones in extracellular electron transfer , 2000, Nature.

[6]  D. Lovley,et al.  Novel Mode of Microbial Energy Metabolism: Organic Carbon Oxidation Coupled to Dissimilatory Reduction of Iron or Manganese , 1988, Applied and environmental microbiology.

[7]  R. Berner,et al.  Phosphorus in sediments of the Amazon River and estuary: Implications for the global flux of phosphorus to the sea , 1994 .

[8]  Francisco P. Chavez,et al.  Continental-shelf sediment as a primary source of iron for coastal phytoplankton , 1999, Nature.

[9]  R. Morris,et al.  Mineralogy of a natural As-rich hydrous ferric oxide coprecipitate formed by mixing of hydrothermal fluid and seawater: Implications regarding surface complexation and color banding in ferrihydrite deposits , 2001 .

[10]  R. Berner Phosphate removal from sea water by adsorption on volcanogenic ferric oxides , 1973 .

[11]  U. Schwertmann,et al.  The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses , 2003 .

[12]  T. Beveridge,et al.  Bacterial Recognition of Mineral Surfaces: Nanoscale Interactions Between Shewanella and α-FeOOH , 2001, Science.

[13]  K. Telmer,et al.  GSC-MITE PHASE I: Lake sediment studies in the vicinity of the Horne smelter in Rouyn-Noranda, Quebec , 2001 .

[14]  D. Canfield,et al.  Sources of iron for pyrite formation in marine sediments , 1998 .

[15]  U. Schwertmann,et al.  Iron Oxides , 2003, SSSA Book Series.

[16]  C. Slomp,et al.  Enhanced regeneration of phosphorus during formation of the most recent eastern Mediterranean sapropel (S1) , 2002 .

[17]  U. Schwertmann,et al.  Aluminium Influence on Iron Oxides: XVIII. The Effect of Al Substitution and Crystal Size on Magnetic Hyperfine Fields of Natural Goethites , 1996, Clay Minerals.

[18]  C. Slomp,et al.  Authigenic P formation and reactive P burial in sediments of the Nazaré canyon on the Iberian margin (NE Atlantic) , 2002 .

[19]  U. Schwertmann,et al.  From Fe(III) Ions to Ferrihydrite and then to Hematite. , 1999, Journal of colloid and interface science.

[20]  Derek R. Lovley,et al.  Geobacter metallireducens accesses insoluble Fe(iii) oxide by chemotaxis , 2002, Nature.

[21]  F. Morel,et al.  Surface Complexation Modeling: Hydrous Ferric Oxide , 1990 .

[22]  B. Thamdrup Bacterial Manganese and Iron Reduction in Aquatic Sediments , 2000 .

[23]  J. Banfield,et al.  Aggregation-based crystal growth and microstructure development in natural iron oxyhydroxide biomineralization products. , 2000, Science.

[24]  W. Schneider Iron Hydrolysis and the Biochemistry of Iron. The Interplay of Hydroxide and Biogenic Ligands , 1988 .

[25]  P. Weidler,et al.  Controls on Fe reduction and mineral formation by a subsurface bacterium , 2003 .

[26]  Rob Fitzpatrick,et al.  Iron minerals in surface environments. , 1992 .

[27]  J. E. Dutrizac,et al.  Interplay of surface conditions, particle size, stoichiometry, cell parameters, and magnetism in synthetic hematite-like materials , 1998 .

[28]  E. Murad,et al.  Iron Oxides and Oxyhydroxides , 1989 .

[29]  D. Rancourt,et al.  Extended Voigt-based analytic lineshape method for determining N-dimensional correlated hyperfine parameter distributions in Mössbauer spectroscopy , 1997 .

[30]  C. Domingo,et al.  Kinetics of oxidative precipitation of iron oxide particles , 1993 .

[31]  John M. Zachara,et al.  Microbial Reduction of Crystalline Iron(III) Oxides: Influence of Oxide Surface Area and Potential for Cell Growth , 1996 .

[32]  A. Tessier,et al.  Interactions between arsenic and iron oxyhydroxides in lacustrine sediments , 1990 .

[33]  U. Schwertmann,et al.  Effect of pH on the Formation of Goethite and Hematite from Ferrihydrite , 1983 .