Redox properties of iron-bearing mineral surfaces may play an important role in controlling the transport and transformation of pollutants into ground waters. Suspensions of seven iron-bearing minerals were reacted with pH and redox indicators under anaerobic conditions at the pH of the natural suspension. The responses of the indicators to the mineral surfaces were monitored by UV-visible spectroscopy using a scattered transmission technique. The Hammett surface acidity function (Hs) and the surface redox potential (Ehs) of these iron-bearing minerals were measured. These measured values were used to calculate Eh values for the seven minerals: goethite = +293 mV; chlorite = +290 mV; hematite = +290 mV; almandite = +282 mV; ferruginous smectite = +275 mV; pyrite = +235 mV; and Na-vermiculite = +223 mV. Calculated surface redox potentials of minerals are different from their potentials measured by platinum electrode in bulk suspensions. UV-visible spectroscopy provides a quick and non-destructive way of monitoring organic probe response at the mineral surface.

The evolution of Fe-containing phases of carbonaceous chondrites heated under various oxidation-reduction conditions was investigated by means of Mössbauer spectroscopy. Heating of the lower petrological types of chondrites (CM2) released gases which initially produced oxidizing conditions (∼450°C) and then reducing conditions (> 700°C Phase transformation occurred rapidly (during 1–5 minutes) at all temperatures. During heating the Fe-bearing phyllosilicate phases in CM2-chondrite converted to Fe-bearing olivine, metallic iron and troilite (pentlandite). These phases resemble those of CO3, CV3 and EH-chondrites. Iron distribution resembling that of ordinary chondrites (some additional Fe2+ in pyroxene) was obtained only by heating a mixture of oxidized matter (CM2) with reduced matter (EH).

A phase transition discovered at 1050°C is probably the temperature boundary between conditions of formation of the two main components of ordinary chondrites: matrix and chondrules. Chondrules of ordinary chondrites may be formed at temperatures > 1050°C while the matrix forms at temperatures < 1050°C For the carbonaceous chondrite Kainzas (CO3) these temperatures are approximately 1000°C and < 900°C The experimental conditions determined for the evolution of chondrites do not contradict the theoretical two-component model of Wood-Anders-Ringwood and may further its development.

A simple general equation is presented for estimating the Fe3+ concentrations in ferromagnesian oxide and silicate minerals from microprobe analyses. The equation has been derived using stoichiometric criteria assuming that iron is the only element present with variable valency and that oxygen is the only anion. In general, the number of Fe3+ ions per X oxygens in the mineral formula, F, is given by;

where T is the ideal number of cations per formula unit, and S is the observed cation total per X oxygens calculated assuming all iron to be Fe2+. Minerals for which this equation is appropriate include pyralspite and ugrandite garnet, aluminate spinel, magnetite, pyroxene, sapphirine and ilmenite. The equation cannot be used for minerals with cation vacancies (e.g. micas, maghemite) unless, as in the case of amphiboles, the number of ions of a subset of elements in the formula can be fixed. Variants of the above equation are presented for some of the numerous published schemes for the recalculation of amphibole formulae. The equation is also inappropriate for minerals showing Si4+ = 4H+ substitution (e.g. staurolite, hydrogarnet), minerals containing an unknown proportion of an unanalysed element other than oxygen (e.g. boron-bearing kornerupine) and minerals containing two or more elements with variable valency.

Geological disposal facilities (GDF) are intended to isolate and contain radioactive waste within multiple protective barriers, deep underground, to ensure that no harmful quantities of radioactivity reach the surface environment. The last line of defense in a multi-barrier GDF is the geosphere, where iron is present in the host rock mineralogy as either Fe(II) or Fe(III), and in groundwater as Fe(II) under reducing conditions. The mobility of risk-driving radionuclides, including uranium and technetium, in the environment is affected significantly by their valence state. Due to its low redox potential, Fe(II) can mediate reduction of these radionuclides from their oxidized, highly mobile, soluble state to their reduced, insoluble state, preventing them from reaching the biosphere. Here a study of five types of potential host rocks, two granitoids, an andesite, a mudstone and a clay-rich carbonate, is reported. The bulk rocks and their minerals were analysed for iron content, Fe(II/III) ratio, and for the speciation and fine-grained nature of alteration product minerals that might have important controls on groundwater interaction. Total iron content varies between 0.9% in clays to 5.6% in the andesite. X-ray absorption spectroscopy reveals that Fe in the granitoids and andesite is predominantly Fe(II), and in mudstones, argillaceous limestone and terrestrial sandstone is predominantly Fe(III). The redox reactivity of the potential host rocks both in the presence and absence of Fe(II)-containing 'model' groundwater was investigated using an azo dye as a probe molecule. Reduction rates as determined by reactivity with the azo dye were correlated with the ability of the rocks to uptake Fe(II) from groundwater rather than with initial Fe(II) content. Potential GDF host rocks must be characterized in terms of mineralogy, texture, grain size and bulk geochemistry to assess how they might interact with groundwater. This study highlights the importance of redox reactivity, not just total iron and Fe(II)/(III) ratio, when considering the host rock performance as a barrier material to limit transport of radionuclides from the GDF.