Ferrous iron-containing minerals

Sorption on Granite and Ferrous-Iron-Containing Minerals under Anoxic Conditions... 

Table V. Ferrous-Iron-Containing Minerals used in Technetium Sorption Studies...

As pointed out by Seal et al. (2000), many studies of ancient hydrothermal systems have utilized equilibrium sulfate-sulfide sulfur isotope fractionation models, but these should be applied with great caution. As shown in Figure 9, seafloor hydrothermal vent fluid 5" Sh2S values do not conform to simple equilibrium fractionation models. Shanks et al. (1981) first showed experimentally that sulfate in seawater-basalt systems is quantitatively reduced at temperatures above 250°C when ferrous minerals like the fayalitic olivine are present. When magnetite is the only ferrous iron-bearing mineral in the system, sulfate-reduction proceeds to sulfate-sulfide equilibrium, but natural basalts contain ferrous iron-bearing olivine, pyroxene, titanomagnetite, and iron-monosulfide solid-solution (mss) (approximately pyrrhotite). It is the anhydrite precipitation step... 

Since ferrous iron usually colors minerals green, and ferric iron yellow or brown, it may seem rather remarkable that the presence of both together should give rise to a blue color, as in the case of vivianite. It may be pointed out, however, that this is by no means a unique instance of such an effect. Even apart from the artificial substances, Prussian and Turnbull s blues, which are complex cyanides containing both ferric and ferrous iron, there are several blue minerals in which the color seems explainable only on this basis. The most noteworthy of these are crocidolite and related amphiboles iolite and the blue tourmaline or indicolite. Other instances may perhaps be discovered, should this subject ever be investigated as it deserves to be . 

The main alteration minerals surrounding Kuroko ore body are K-mica, K-feldspar, kaolinite, albite, chlorite, quartz, gypsum, anhydrite, and carbonates (dolomite, calcite, magnesite-siderite solid solution), hematite, pyrite and magnetite. Epidote is rarely found in the altered basalt (Shikazono et al., 1995). It contains higher amounts of ferrous iron (Fe203 content) than that from midoceanic ridges (Shikazono, 1984). 

First, we read in the dataset of complexation reactions and specify that the initial mass balance calculations should include the sorbed as well as aqueous species. We disable the ferric-ferrous redox couple (since we are not interested in ferrous iron), and specify that the system contains 1 g of sorbing mineral. 

Figure 2 is a combined E -pH diagram for technetium and iron and shows that, under certain conditions, technetium can be reduced by ferrous iron. To study the role of ferrous iron in the removal of technetium from solution, experiments were carried out with crystalline rock and ferrous minerals and TcO -containing solutions, under both anoxic and oxic conditions. 

The autoradiographs of the rock and mineral thin sections (Figures 4 to 6) also confirm the importance of iron oxides although biotite.(K(Mg,Fe Si AlCLQ(0H) ) and hornblende ((Na,Ca2)(Mg,Fe )(Al,Fe )(Si AlO OH ) contain ferrous iron, sorption appears to take place solely on the small opaque (iron-oxide) inclusions. In the case of biotite, these oxides are located between the basal planes, and are randomly distributed in the hornblende. Similar distributions are observed for olivine, pyroxene, and epidote. The results for pyroxene further confirm the low sorption results obtained with gabbro, where it is one of the major minerals. 

Trivalent iron is an effective activator when it is free of the effects of ferrous iron. Because of the larger value of Dq, the emission is shifted to 700 - 750 nm in the deep red when Fe + is present on tetrahedral sites. Fe + in octahedral coordination is predicted to emit in the near infrared at about 900 to 1000 nm but is rarely observed and is thus indicated by a dashed line in Figure 5. Fe luminescence in minerals is mainly observed when Fe + substitutes for Al3+ in tetrahedral sites in aluminosilicates. Observations on feldspars (15) provide the transition sketched on Figure 5. In the orthoclase structure the Stokes shift is 1500 wavenumbers. Trivalent iron is the most likely activator for luminescence seen in many terrestrial feldspars and feldspar-containing rocks. The characteristic 700-750 nm band is weak or absent in lunar feldspars (16,17). 

In general, minerals in sedimentary and meta-morphic rocks contain ferrous iron (Velde, 1985) which is destined to become iron oxide under conditions of weathering. Oxidation under surface conditions has a tendency to produce iron in the ferric state. Most often the process takes iron out of the silicates and puts it into an oxide phase. In the uppermost layers of mature soils, iron oxide and various silicates, usually non-iron-bearing, are produced. In silicates containing iron, the majority is in the ferric state. The extent of the transformation of iron oxidation state is a rough measure of the maturity of the soil. In the extremely weathered soils one finds only ferric iron and aluminum oxides and hydroxides. These soils are typically red. 

The investigations of Landesman et al. (1966a, b) clarify the effects of the various conditions controlling the optimum oxidation rates of ferrous iron, sulfur and reduced sulfur compounds by T. ferrooxidans. Experiments on soluble iron, sulfur and iron-containing sulfide minerals (chalcopyrite, CuFeS2, bornite, CUsFeS4, and pyrite) established that iron and sulfur can be oxidized simultaneously. With a mixed iron-sulfur substrate a rate of oxidation, equal to that of the sum of the maximum rates of oxidation of the two substrates individually was observed with both S-adapted and Fe-adapted cells. Subsequently, Duncan et al. (1967) established the differential susceptibility of the bacterial oxidation of ferrous iron and sulfur to N-ethyl maleimide and sodium azide, and determined the effect of these inhibitors on pyrite and chalcopyrite oxidation. Decreased rates... 

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