Lepidocrocite y-FeOOH

First attempts to incorporate pre-formed magnetite colloids within alginate/silica nanocomposites via a spray-drying process have been described, but formation of lepidocrocite y-FeOOH and fayalite Fe2Si04 was observed, attributed to Fe2+ release during the aerosol thermal treatment [53],... 

Oxide composition and lattice structure influences the coordin-ative environment of surface sites, and should have an impact on rates of ligand substitution. Hematite (Fe203), goethite (a-FeOOH), and lepidocrocite (y-FeOOH), for example, are all Fe(III) oxide/ hydroxides, but may exhibit different rates of surface chemical... 

Mn(II) oxidation is enhanced in the presence of lepidocrocite (y-FeOOH). The oxidation of Mn(II) on y-FeOOH can be understood in terms of the coupling of surface coordination processes and redox reactions on the surface. Ca2+, Mg2+, Cl, S042-, phosphate, silicate, salicylate, and phthalate affect Mn(II) oxidation in the presence of y-FeOOH. These effects can be explained in terms of the influence these ions have on the binding of Mn(II) species to the surface. Extrapolation of the laboratory results to the conditions prevailing in natural waters predicts that the factors which most influence Mn(II) oxidation rates are pH, temperature, the amount of surface, ionic strength, and Mg2+ and Cl" concentrations. 

This paper discusses the oxidation of Mn(II) in the presence of lepidocrocite, y-FeOOH. This solid was chosen because earlier work (18, 26) had shown that it significantly enhanced the rate of Mn(II) oxidation. The influence of Ca2+, Mg2+, Cl", SO,2-, phosphate, silicate, salicylate, and phthalate on the kinetics of this reaction is also considered. These ions are either important constituents in natural waters or simple models for naturally occurring organics. To try to identify the factors that influence the rate of Mn(II) oxidation in natural waters the surface equilibrium and kinetic models developed using the laboratory results have been used to predict the... 

The orange coloured lepidocrocite, y-FeOOH, is named after its platy crystal shape (lepidos scale) and its orange colour (krokus = saffron). It occurs in rocks, soils, biota and rust and is often an oxidation product of Fe ". It has the boehmite (y-AlOOH) structure which is based on cubic close packing (ccp) of anions. 

Diakonov, G.G. (1998) Thermodynamic properties ofiron oxides and hydroxides. III. Surface and bulk thermodynamic properties of lepidocrocite (y-FeOOH) up to 500 K. Eur. J. Min. 10 31-41... 

A.I. Bordia, R.K. Korshin, G.V. Christensen T.H. (2000 a) Aging of iron (hydr)oxides by heat treatment and effects on heavy metal binding. Environ. Sci. Techn. 34 3991-4000 Sorensen, S. Thorling, L. (1991) Stimulation by lepidocrocite (y-FeOOH) of Fe(II)-depen-... 

Zhang, X. Zhang, F. Mao, D. (1999) Effect of iron plaque outside roots on nutrient uptake by rice Oryza sativa L.) Phosphate uptake. Plant and Soil 209 187-192 Zhang,Y Charlet, L. Schindler, P.W. (1992) Adsorption of protons, Fe(II) and Al(IIl) on lepidocrocite (y-FeOOH). Colloids Surfaces 63 259-268... 

Recently we presented (23) the results of an experimental study on the kinetics and mechanisms of the reaction of lepidocrocite (y-FeOOH) with H2S. With respect to the interaction between iron and sulfur, lepidocrocite merits special attention. It forms by reoxidation of ferrous iron under cir-cumneutral pH conditions (24), and it can therefore be classified as a reactive iron oxide (19). The concept of reactive iron was established by Canfield (19), who differentiated between a residual iron fraction and a reactive iron fraction (operationally defined as soluble in ammonium oxalate). The reactive iron fraction is rapidly reduced by sulfide or by microorganisms. 

Randall, S.R., Sherman, D.M. and Ragnarsdottir, K.V. (2001) Sorption of As(V) on green rust (Fe4(II)Fe2(III) (OH)i2S04.3H20) and lepidocrocite (y-FeOOH) surface complexes from EXAFS spectroscopy. Geochimica et Cosmochimica Acta, 65(7), 1015-23. 

In water logged soils radial oxygen loss from the root raises the redox potential in the rhizosphere as a consequence of which iron oxide plaques are seen to develop on root surfaces. Bacha and Hossner (1977) removed the coatings on rice roots growing under anaerobic conditions. The coatings were composed primarily of the iron oxide mineral lepidocrocite (y-FeOOH) as the only crystalline component. St-Cyr and Crowder (1990) studied the iron oxide plaque on roots of Phragmites and detected both Fe and Mn. The Fe Mn ratio of the plaque resembled the ratio of Fe Mn in substrate carbonates. The plaque material also contained Cu. 

Lepidocrocite (-y-FeOOH) has also been used as a catalyst for Fentonlike reactions [54]. First-order decomposition of hydrogen peroxide was observed in the presence of this catalyst. Peroxide decay at 20 g/L catalyst was found to be pseudo-first-order and pH-dependent, with rate constant values reported from 0.102 hr-1 at pH 3.3 to 0.326 hr-1 at pH 8.9. In this system benzoic acid degradation was fastest at the low pH value. Under these conditions, acid dissolution of the lepidocrocite was observed to produce... 

X-ray diffraction analysis indicates that boehmite y-AlOOH and lepidocrocite y-FeOOH crystallize in the space group Cmcm = n. 63 = D J, with Z = 4. However, such analysis does not reveal the position of the hydrogen atoms. Instead, vibrational spectroscopies can be used to obtain such information. The IR spectra are dominated by two well-split OH stretches (3305, 3090cm" for boehmite) and two OH deformations (1170 and 1074cm" ), see Figure 3.6. 

Lovley and Phillips, 1986). Minerals such as ferrihydrite and lepidocrocite (y-FeOOH) are generally reduced more rapidly than relatively stable minerals such as goethite and hematite (Postma, 1993). Amorphous manganese oxides such as vernadite are more easily reduced than strongly crystalline forms such as pyrolusite, but the overall influence of crystallinity on reduction kinetics appears to be weaker for manganese and iron oxides (Burdige et ai, 1992). 

Case Examples. The effects of various oxoanions on EDTA-pro-moted dissolution of lepidocrocite (y-FeOOH) have been studied by Bondietti et al. (33). EDTA was chosen as a reference system because it is dissolution-active over a relatively wide pH range. Phosphate, arsenate, and selenite markedly inhibit the dissolution at near-neutral pH values. At pH <5 phosphate, arsenate, and selenite accelerate the dissolution. It is presumed that the bi-nuclear surface complexes formed at near-neutral pH values by these oxoanions (Table II) inhibit the dissolution. Figure 8a displays data on the effect of selenite on EDTA-promoted dissolution, and Figure 8b shows that calculations on surface speciation by Sposito et al. (35) support the preponderance of binuclear selenite surface complexes in the neutral-pH range. Mononuclear surface species prevail at lower pH values. 

The kinetics of the photochemical reductive dissolution of lepidocrocite (y-FeOOH) with oxalate as the reductant depends strongly on pH both the rate and the overall rate constant, k> decrease with increasing pH. This behavior means that the pH dependence of the rate does not simply reflect the pH dependence of oxalate adsorption at the lepidocrocite surface. Between pH 3 and 5, the log k() values can be fitted with a straight line. The dependence of k on the concentration of surface protons, >FeOH2+, can be estimated from the slope of this line and from the protonation curve of lepidocrocite k0 >FeOHf I6. The value of 1.6, which can be considered only a rough estimate, is not too different from the theoretically expected value of 2 for the proton-catalyzed detachment of reduced surface iron centers (i.e., of surface metal centers with the formal oxidation state of II). 

Lepidocrocite y-FeOOH 38.7 to >40.6 Minor constituent in humid and temperate climate noncalcareous soils, especially where alternating reducing and oxidizing conditions in seasonally waterlogged soils. Favored by rapid oxr idation at low pH, low IFe, low T, and Fe(II])(aq) absent. 

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