ALBERT

Notes: Abstract Single-crystal X-ray and neutron structure refinements carried out on neptunite (KNa2Li(Fe, Mg, Mn)2Ti2Si8O24) from San Benito, California at various temperatures (neutrons: 15 K and 293 K; X-rays: 110 K, 293 K and 493 K) indicate that this mineral crystallizes in the acentric space group Cc (T=293K: a=16.427 Å, b=12.478 Å, c=9.975 Å, β= 115.56°, Z=4, V=1844.53 Å3) due to ordering of octahedrally coordinated metals (Ti, Fe, Mn, Mg). In the neptunite structure, Ti and (Fe, Mn, Mg) octahedra share edges to form chains that run along [110] and [110]. These chains are, in turn, linked through shared corners along [001]. The resulting octahedral framework is interwoven by a similar [Si8O22] tetrahedral framework. Li, Na and K occupy 6-, 8- and 10- coordinated sites within the framework. The metal-containing polyhedra show strong distortions at all temperatures. In particular, Ti exhibits a strong off-center displacement (≈0.25 Å) within its octahedron, leading to four Ti-O distances of 2.0 Å, one of 2.2 Å and one of 1.7 Å. The displaced Ti position is in good agreement with a position that minimizes differences between ionic bond strengths and is interpreted as an energy minimum in an ionic potential model. Mössbauer spectra collected at 77 K, 293 K and 400 K indicate all Fe to be present as octahedral Fe2+. Although two distinct Fe positions were found in the structure, 77 K and 293 K spectra display only one quadrupole doublet. Two Fe sites can only be resolved in the 400 K spectrum. It is suggested that the temperature dependence of octahedral edge distortions is responsible for the separation of the Mössbauer doublets.

Notes: Abstract  Mössbauer measurements on neptunite (KNa2Li(Fe,Mn,Mg)2Ti2Si8O24) at 400 K reveal the distribution of Fe-ions on the crystallographic sites in agreement with neutron diffraction results published elsewhere. Even the previously postulated small amount of Fe-ions on the Ti(2) site has been detected, combined with a charge transfer which is in agreement with optical absorption investigations by other authors. A qualitative site occupation model is able to explain the different features of our observations. Single crystal Mössbauer measurements with the k-vector of incident γ-rays parallel to the crystallographic b-axis (space group Cc) of neptunite at different temperatures yield the angle β between the main component of the electric field gradient (EFG), V zz and b. This angle is in close accordance with a calculated value of β for the Fe(1) position from electron density maps. The latter also reveal an absolute value of V zz which is in satisfactory agreement with V zz derived from Mössbauer spectroscopy.

Notes: Abstract  The reaction-displacement technique was applied to the end-member reaction annite = sanidine + magnetite + H2 in order to determine the activity of the annite component (a Ann) in iron biotites with variable degrees of the Tschermak's substitution ([6]Fe + [4]Si = [6]Al + [4]Al). Based on the simplified relation a Ann = f H 2/foH2 (foH2 = hydrogen fugacity of the end-member reaction at P, T), two types of experiments were performed at 700°C / 2 kbar: Type I used Fe-Al biotites of known starting composition together with sanidine + magnetite + H2O. This assemblage was exposed to various f H 2 conditions (f H 2 〈 foH2) produced in the pressure vessel either by using different ratios of water/oil as pressure medium (f H 2 in this case was measured by the hydrogen sensor technique), or by the Ni′NiO buffer. The composition of the Fe-Al biotites changed through incorporation or release of the annite component in response to the externally imposed f H 2. By using opposite biotite starting compositions, the equilibrium composition as a function of f H2 was bracketed. For type II, f H 2 in equilibrium with a specific combination of fine-grained Fe-Al biotite (+ sanidine + magnetite + H2O) was measured internally by application of the hydrogen sensor technique. Both type I and type II experiments yield consistent results demonstrating that a fine-grained assemblage of Fe-Al biotite (+ sanidine + magnetite + H2O) is able to act as a sliding-scale buffer. The final chemical composition of the Fe-Al biotite after the experiments was determined by electron microprobe and Mössbauer spectroscopy. The [4]Al and [6]Al in the biotites are coupled according to the Tschermak's substitution. In the tetrahedral sheet 0.1 Al-atoms per formula unit are present in excess to the amount required to balance [6]Al, and all Fe-Al biotites contain 8–10% Fe3+. Therefore, they are not members of the pure annite - siderophyllite join, but have an almost constant amount (15 Mol%) of two additional Fe3+-bearing components (ferri-siderophyllite and a vacancy end-member). The volume - composition relationship obtained does not indicate excess molar volumes of mixing for the annite (Ann) - siderophyllite (Sid) binary. The data are consistent with a molar volume of annite of 15.46 ± 0.02 Jbar–1 and of 15.06 ± 0.02 Jbar–1 for siderophyllite. The experimentally determined activity - composition relation shows that biotites on the join annite - siderophyllite deviate negatively from ideality. A symmetric interaction parameter WAnnSid is sufficient to represent the data within error. This was constrained as: W AnnSid = –29 ± 4 kJmol–1. This is in contradiction to empirical interaction parameters derived from natural assemblages for this binary that predict positive deviation from ideality. Reasons for this discrepancy are discussed.

Notes: Abstract The valence and distribution of iron in vivianite, lazulite, babingtonite, rockbridgeite, acmite, aegirine-augite, hedenbergite, and ilvaite were studied with optical and Mössbauer spectroscopy. Optically activated intervalence charge transfer between Fe2+ and Fe3+ in neighboring sites through common edges or faces is observed in all these minerals irrespective of the polymerization of the iron-oxygen polyhedra ranging from finite clusters to infinite structural units. However, a distinct decrease occurs in the energy of the corresponding optical absorption band with increasing number of Fe2+ and Fe3+ ions involved in the charge transfer process. Thermally activated electron delocalization between Fe2+ and Fe3+ occurs only if Fe2+ and Fe3+ occupy crystallographically equivalent or geometrically very similar neighboring sites which share common edges to form extended structural units such as the ribbon in ilvaite. If the Fe-O polyhedra form finite clusters of two, three, or four polyhedra (e.g., in vivianite, lazulite, and babingtonite, respectively) no thermally-activated mixed-valence states of iron are observed. In aegirine, extended regions of the M1 chain are statistically occupied by Fe2+ and Fe3+ giving rise to thermally-activated electron delocalization in addition to the intervalence band in the optical absorption spectrum. The intensity of the optical intervalence absorption has been measured in a number of systems: ɛ values range from 60 to 210.