Manganese oxidized sediments

In addition to effects on the concentration of anions, the redox potential can affect the oxidation state and solubility of the metal ion directly. The most important examples of this are the dissolution of iron and manganese under reducing conditions. The oxidized forms of these elements (Fe(III) and Mn(IV)) form very insoluble oxides and hydroxides, while the reduced forms (Fe(II) and Mn(II)) are orders of magnitude more soluble (in the absence of S( — II)). The oxidation or reduction of the metals, which can occur fairly rapidly at oxic-anoxic interfaces, has an important "domino" effect on the distribution of many other metals in the system due to the importance of iron and manganese oxides in adsorption reactions. In an interesting example of this, it has been suggested that arsenate accumulates in the upper, oxidized layers of some sediments by diffusion of As(III), Fe(II), and Mn(II) from the deeper, reduced zones. In the aerobic zone, the cations are oxidized by oxygen, and precipitate. The solids can then oxidize, as As(III) to As(V), which is subsequently immobilized by sorption onto other Fe or Mn oxyhydroxide particles (Takamatsu et al, 1985). 

Takamatsu, T., Kawashima, M. and Koyama, M. (1985). The role of Mn-rich hydrous manganese oxide in the accumulation of arsenic in lake sediments. Water Res. 19,1029-1032. 

Chao T. T. Selective dissolution of manganese oxides from soils and sediments with acidified hydroxylamine hydrochloride. Soil Sci Soc Am Proc 1972 36 704-768. 

Copper in livers and muscles of Weddell seals was positively correlated with manganese (Szefer et al. 1994). In general, manganese and copper are positively correlated in tissues of marine vertebrates (Eisler 1984). Uptake of copper from copper-contaminated freshwater sediments by annelid worms is related to the amount of reducible manganese oxide in the sediments (Diks and Allen 1983). 

In Limnodrilus sp., an oligochaete worm, copper bioavailability from surhcial freshwater sediments is associated with the amount of copper present in the manganese oxide fraction of the sediment. The redox potential and pH in the gut of Limnodrilus allows the dissolution of the manganese oxide coating, making copper and other metals available for uptake (Diks and Allen 1983). 

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... 

Leaching and desorption of As from its associated mineral surfaces such as iron, aluminum and manganese oxides under the influence of the aquifer complex geochemistry, largely take part in its transport from sediment to aquifer pore-water. Adsorption has widely been considered as the retardation of As transport (Smedley 2003). 

Several reactions between constituents in As-contaminated groundwater and oxic sediments controlled As mobility in the laboratory experiments. Adsorption was the primary mechanism for removing As from solution. The adsorption capacity of the oxic sediments was a function of the concentration and oxidation state of As, and the concentration of other solutes that competed for adsorption sites. Although As(lll) was the dominant oxidation state in contaminated groundwater, data from the laboratory experiments showed that As(lll) was oxidized to As(V) by manganese oxide minerals that are present in the oxic sediment. Phosphate in contaminated groundwater caused a substantial decrease in As(V) adsorption. Silica, bicarbonate and pH caused only a small decrease in As adsorption. 

Reactions between Fe(ll) in contaminated groundwater (5.8 mg/L) and oxic sediment also affected As mobility. Ferrous iron was oxidized by manganese oxides to ferric iron which precipitated as hydrous ferric oxide, creating additional sorption sites. Evidence for this reaction included an increase in ferric oxide concentrations in reacted column sediments and manganese concentrations in leachate that were greater than in the initial eluent. 

The first consideration was the speciation and distribution of the metal in the sediment and water. Benthic organisms are exposed to surface water, pore water and sediment via the epidermis and/or the alimentary tract. Common binding sites for the metals in the sediment are iron and manganese oxides, clays, silica often with a coating of organic carbon that usually accounts for ca. 2% w/w. In a reducing environment contaminant metals will be precipitated as their sulfides. There is not necessarily a direct relationship between bioavailability and bioaccumulation, as digestion affects the availability and transport of the metals in animals, in ways that differ from those in plants. 

The processes described and their kinetics is of importance in the accumulation of trace metals by calcite in sediments and lakes (Delaney and Boyle, 1987) but also of relevance in the transport and retention of trace metals in calcareous aquifers. Fuller and Davis (1987) investigated the sorption by calcareous aquifer sand they found that after 24 hours the rate of Cd2+ sorption was constant and controlled by the rate of surface precipitation. Clean grains of primary minerals, e.g., quartz and alumino silicates, sorbed less Cd2+ than grains which had surface patches of secondary minerals, e.g., carbonates, iron and manganese oxides. Fig. 6.11 gives data (time sequence) on electron spin resonance spectra of Mn2+ on FeC03(s). 

Adsorption may influence precipitation by means other than the processes mentioned above. Davies (Chapter 23) discusses the role of the surface as a catalyst for oxidation of adsorbed Mnz+. Redox reactions may contribute substantially to the formation of manganese oxide coatings on mineral surfaces in soils and sediments. 

Based upon thermodynamic data given in Table I, oxidant strength decreases in the order NijO > Mn02 > MnOOH > CoOOH > FeOOH. Rates of reductive dissolution in natural waters and sediments appear to follow a similar trend. When the reductant flux is increased and conditions turn anoxic, manganese oxides are reduced and dissolved earlier and more quickly than iron oxides (12, 13). No comparable information is available on release of dissolved cobalt and nickel. 

In the case of iron and manganese, most of these metals are removed from the hydrothermal fluids and converted to particulate form close to their point of entry. Some of these removals are in the form of sulfides, which fc>rm as the fluids emerge into the deep sea. The rest occurs as the fluids mix with cold, oxic, alkaline seawater, which promotes the oxidation of reduced metals. Thus, Fe (aq) and Mn (aq) are transformed into insoluble iron and manganese oxides, forming colloids and particles, the latter of which eventually settle onto the sediments. As described in the next chapter, at least some of these oxidation reactions are biologically mediated. Some of... 

Two types of metal-rich hydrogenous deposits are formed on the seafloor iron-manganese oxides and polymetallic sulfides. The iron-manganese oxides have been deposited as nodules, sediments, and crusts. They are enriched in various trace elements, such as manganese, iron, copper, cobalt, nickel, and zinc, making them a significant repository for some of these metals. Most of the metals in the polymetallic sulfides are of hydrothermal origin. These sulfides have been deposited as metalliferous sediments aroimd hydrothermal systems and as rocks that infill cracks within former... 

Table 18.1 Average Compositions of the Earth s Upper Continental Crust, Shale, Iron-Manganese Oxides, Phosphorite, and Various Types of Marine Sediments (All in Units of ppm. Unless Noted otherwise), along with Seawater and a Hydrothermal Vent Solution from the East Pacific Rise (both in Units of 10 g L ). 

Schematic representation of manganese nodule end-member morphologies. The size of the arrows Indicates the proportion and direction of metal supply, (a) Typical situation In the open ocean with the nodules lying on an oxidized sediment substrate dominant mode of formation Is hydrogenous, (b) Typical situation In nearshore and freshwater environments with nodules lying on a sediment substrate that Is partly reducing In character. Dominant supply of metals Is via Interstitial waters from below the substrate surface. Source From Chester, R. (2003). Marine Geochemistry, 2nd ed. Blackwell, p. 425.

Arsenic contaminants may be found in the aquatic and terrestrial environments as a result of anthropogenic inputs and weathering of primary materials. It is known (e.g., Oscarson et al. 1983 Tournassat et al. 2002) that in such environments, manganese oxides like birnessite (b-MnO ) directly and rapidly oxidize As(III) to As(V). However, As(III) oxidation can be inhibited in sediments when additional natural materials lead to coating of MnO by CaC03 (Oscarson et al. 1983). 

Precipitation can remove soluble nickel Ifom water. In aerobic waters, nickel ferrite is the most stable compound (Rai and Zachara 1984). Nickel may also be removed by coprecipitation with hydrous iron and manganese oxides. Nickel removed by precipitation and coprecipitation settles into the sediment. 

In discussing nickel exposure, it is important to consider what form of nickel a person is exposed to and its bioavailability. Such information is not often available. Although high concentrations of nickel may be found in contaminated soil and sediment, it may be embedded in a crystalline matrix or bound to hydrated iron, aluminum, and manganese oxides and, therefore, not bioavailable. 

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