Hydrous oxides of iron and manganese

Bound to hydrous oxides of iron and manganese (HOx/NH4Ox)... 

Industrial waste to the Saale River (Germany) resulted in zinc concentrations at Rubolstadt of several thousand milligrams per liter which decreased by a factor of 10 within 6 to 8 miles downstream. Surficial sediment in front of a dam 7.4 miles downstream had a zinc content of 0.86%, whereas similar sediment 21.8 miles further downstream had only 0.36% zinc (91), Since the hydrous oxides of iron and manganese are ubiquitous in surficial stream sediments, it is suggested that the zinc decontamination of the Saale River in this case may have been caused by the scavenging ability of the hydrous oxides. 

In addition to the soluble chemical species and possible solid phase species described in the previous sections no discussion on speciation can be complete without the consideration of surface species. These include the inorganic and organic ions adsorbed on the surface of particles. Natural systems such as soils, sediments and waters abound with colloids such as the hydrous oxides of iron, aluminium, manganese and silicon which have the potential to form surface complexes with the various cationic and anionic dissolved species (Evans, 1989). 

Phosphorus extracted from sediment by NaOH has been related to non-occluded, surface-exchangeable, bioavailable forms (22). Hydrochloric acid extraction yields occluded phosphorus incorporated in hydrous metal oxides, carbonate and phosphate minerals of sediment. Hydroxylamine reagent specifically removes hydrous manganese oxides, while amorphous hydrous oxides of iron and aluminijm are removed by the oxalate reagent. Total available sediment phosphorus analyses includes sediment organic phosphorus components in addition to the inorganic portion determined by the selective extraction procedures. 

Inorganic phosphorus Incorporated with easily reducible hydrous manganese oxides is typically less than that found for the hydrous oxides of iron and aluminum. 

Finally, finely divided hydrous oxides of iron, aluminum, manganese, and silicon are the dominant sorbents in nature because they are common in soils and rivers, where they tend to coat other particles. This is the reason why numerous laboratory researchers have been studying the uptake of trace elements by adsorption on hydrous oxides (Dzomback and Morel, 1990). Partition coefficients (concentration in solid/concentration in the solution) for a number of trace elements and a great variety of surfaces have been determined. The comparison of these experimental with natural values should give information on the nature of the material on which trace elements adsorb in namral systems and allow quantitative modeling. 

In Skirmer, H.G.W. Fitzpatrick, R.W. (eds.) Biomineralization processes of iron and manganese. Catena Verlag, Cremhngen-Destedt, Catena Suppl. 21 75—99 Ghoneimy, H.F. Morcos.T.N. Misak, N.Z. (1997) Adsorption of Co and Zn ions on hydrous Fe(lll), Sn(lV) and mixed Fe(lll)/ Sn(IV) oxides. Part 1. Characteristics of the hydrous oxides, apparent capacity and some equilibria measurements. Colloids Surfaces A. 122 13-26... 

Surface Complex Formation. Metal ions form both outer and inner sphere complexes with solid surfaces, e.g. hydrous oxides of iron, manganese, and aluminium. In addition, metal ions, attracted to charged surfaces, may be held in a diffuse layer, which, depending upon ionic strength, extends several nanometres from the surface into solution. 

The most commonly reported solid forms of iron and manganese oxides in marine sediments and ferromanganese nodules are goethite (aFeOOH) and hydrous manganese dioxide (bimessite, todorokite and 6Mn02) (, . The surface chemistry of... 

Reprecipitation A drastic but effective way to minimize the effects of adsorption is reprecipitation. In this process, the filtered solid is redissolved and reprecipitated. The first precipitate ordinarily carries down only a fraction of the contaminant present in the original solvent. Thus, the solution containing the redissolved precipitate has a significantly lower contaminant concentration than the original, and even less adsorption occurs during the second precipitation. Reprecipitation adds substantially to the time required for an analysis but is often necessary for such precipitates as the hydrous oxides of iron(III) and aluminum, which have extraordinary tendencies to adsorb the hydroxides of heavy-metal cations such as zinc, cadmium, and manganese. 

Iron and manganese transformations are another redox potential-pH regulated process in sediment-water systems, which can affect heavy metal availability (see Chapter 10). The reduced forms of iron and manganese, when oxidized, form amorphous hydrous oxides with large surface... 

Most of the zinc introduced into aquatic environments is sorbed onto hydrous iron and manganese oxides, clay minerals, and organic materials, and eventually is partitioned into the sediments (USEPA 1987). Zinc is present in sediments as precipitated zinc hydroxide, ferric and manganic... 

Trivedi, P. Axe, L. (1999) A comparison of strontium sorption to hydrous aluminum, iron, and manganese oxides. J. Coll. Interf. Sd. 218 554-563... 

Samples of the red clay having uniform physical and chemical characteristics were provided by G. R. Heath of the University of Rhode Island. The samples were obtained from core LLUU-GPC-2, collected on October 11, 1976, at 30° 20.9 n, 157° 50.85 w, water depth 5821 meters, and are representative of the smectite-rich region of the red clays which occurs in the sediment at depths below about ten meters. In this region, the sediment appears to contain about five to six percent by weight leachable iron and manganese in the form of hydrous oxides. The remaining material appears to be dominated by iron-rich smectite and lesser, varying amounts of phillipsite (2). The results of a semi-quantitative (precision in data is within a factor of 2) elemental analysis... 

For each nuclide studied, the sorption distribution coefficients appeared to result from a minimum of two separate mechanisms. In all cases, one mechanism appears to be an ion-exchange phenomena associated with the silicate phases and appears to have a relatively much larger sorption capacity than the other mechanism. In the case of cesium (and probably rubidium) the second mechanism appears to also be related to the silicate phases and may or may not be an ion-exchange phenomena. However, for the other elements studied, the second mechanism appears to be related to the hydrous iron and manganese oxides and again may or may not be an ion-exchange process. 

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