57Fe mössbauer study of clinopyroxenes in the join CaFe3+ AlSiO6 - CaTiAl2O6

Synthetic clinopyroxenes of compositions between CaFe³⁺AlSiO₆ and CaFe _0.85 ³⁺ Ti_0.15Al_1.15Si_0.85O₆ have been studied by ⁵⁷Fe Mössbauer spectroscopy. The spectra consist of two doublets assigned to Fe³⁺ in M1 and T sites. From the area ratios of the doublets the site occupancies of Fe³⁺ and Al were determined. Si decreases from 1.00 to 0.85 and Al+Fe³⁺ increases from 1.00 to 1.15 per formula unit with increasing CaTiAl₂O₆ component of the clinopyroxene. The atomic ratio of Fe³⁺(T)/Fe³⁺(total) is 0.11–0.16; 4.5–7.5 percent of the T sites are occupied by Fe³⁺. Thus the presence of Si-O-Fe³⁺, Al-O-Fe³⁺, and Fe³⁺-O-Fe³⁺ bonds is expected in addition to Si-O-Si, Si-O-Al and Al-O-Al bonds. However, the possibility of the former bonds being present would be small, because the amount of Fe³⁺(T) is far less than that of Si and Al. The isomer shift of Fe³⁺(T) is one of the largest in the values found previously for Fe³⁺(T) in silicates. It increases with increasing CaTiAl₂O₆ component and seems to be correlated to the ionic character of the cation — anion bonds calculated from electronegativity. The quadrupole splittings of Fe³⁺(M1) and Fe³⁺(T) decrease with the substitution of Fe³⁺?Ti⁴⁺ in the M1 and of Si?Al in the T sites.     

A new Cu-rich variety of lyonsite from fumarolic sublimates of the Tolbachik volcano (Kamchatka, Russia) and its crystal structure

A new Cu-rich variety of lyonsite has been found from fumarolic sublimates of the Tolbachik volcano (Kamchatka, Russia). The empirical formula is Cu_4.33Fe _2.37 ³⁺ Ti_0.26Al_0.26Zn_0.07(V_5.85As_0.07Mo_0.07P_0.01S_0.01)O₂₄. The crystal structure was studied on single crystal using synchrotron radiation, R = 0.0514. The mineral is orthorhombic, Pnma, a = 5.1736(7), b =10.8929(12), c = 18.220(2) Å, V = 1026.8(2) ų, and Z = 2. The structural formula is (Cu_0.6Ti_0.3Al_0.3Fe _0.2 ³⁺ □_0.6)_Σ2Cu₂(Fe _2.2 ³⁺ Cu_1.8)_Σ4(V_5.8As_0.1Mo_0.1)_Σ6O₂₄. It is proposed to recast the simplified formula of lyonsite as Cu_3+x (Fe _4?2x ³⁺ Cu_2x )(VO₄)₆, where 0 ≤ x ≤ 1.     

A multi-analytical study of the crystal structure of unusual Ti–Zr–Cr-rich Andradite from the Maronia skarn, Rhodope massif, western Thrace, Greece

Unusual Ti–Cr–Zr-rich garnet crystals from high-temperature melilitic skarn of the Maronia area, western Thrace, Greece, were investigated by electron-microprobe analysis, powder and single-crystal X-ray diffraction, IR, Raman and Mössbauer spectroscopy. Chemical data showed that the garnets contain up to 8 wt.% TiO₂, 8 wt.% Cr₂O₃ and 4 wt.% ZrO₂, representing a solid solution of andradite (Ca₃Fe³⁺ ₂Si₃O₁₂ ≈46 mol%), uvarovite (Ca₃Cr₂Si₃O₁₂ ≈23 mol%), grossular (Ca₃Al₂Si₃O₁₂ ≈10 mol%), schorlomite (Ca₃Ti₂[Si,(Fe³⁺,Al³⁺)₂]O₁₂ ≈15 mol%), and kimzeyite (Ca₃Zr₂[Si,Al₂]₃O₁₂ ≈6 mol%). The Mössbauer analysis showed that the total Fe is ferric, preferentially located at the octahedral site and to a smaller extent at the tetrahedral site. Single-crystal XRD analysis, Raman and IR spectroscopy verified substitution of Si mainly by Al³⁺, Fe³⁺ and Ti⁴⁺. Cr³⁺ and Zr⁴⁺ are found at the octahedral site along with Fe³⁺, Al³⁺ and Ti⁴⁺. The measured H₂O content is 0.20 wt.%. The analytical data suggest that the structural formula of the Maronia garnet can be given as: (Ca_2.99Mg_0.03)_Σ=3.02(Fe³⁺ _0.67Cr_0.54Al_0.33Ti_0.29Zr_0.15)_Σ=1.98(Si_2.42Ti_0.24Fe_0.18Al_0.14)_Σ=2.98O₁₂OH_0.11. Ti-rich garnets are not common and their crystal chemistry is still under investigation. The present work presents new evidence that will enable the elucidation of the structural chemistry of Ti- and Cr-rich garnets.     

The Ti4+/Ti3+ ratio of magmatic melts: Application to the problem of the reduction of lunar basalts

Using published experimental data an expression was derived for the Ti⁴⁺/Ti³⁺ ratio as a function of temperature, oxygen fugacity, and melt composition. The equation can be used to estimate Ti³⁺ content in lunar basaltic melts. It was shown that the Ti³⁺ content in melts is probably no higher than the Fe3+ content even under the reduced conditions typical of lunar magmas. Trivalent Ti can lead to some decrease in $f_{O_2 }$ during melt cooling under closed-system conditions, but it cannot reduce Fe²⁺ in melt to metal, because it will be completely consumed by Fe³⁺ reduction to Fe²⁺. The presence of additional reducers, such as Cr²⁺, can be favorable for the formation of metal during melt cooling.     

Ti K-edge XANES study on the coordination number and oxidation state of Titanium in pyroxene,olivine, armalcolite,ilmenite, and silicate glass during mare basalt petrogenesis

Lunar mare basalts are a product of partial melting of the lunar mantle under more reducing conditions when compared to those expected for the Earth’s upper mantle. Alongside Fe, Ti can be a major redox sensitive element in lunar magmas, and it can be enriched by up to a factor of ten in lunar basaltic glasses when compared to their terrestrial counterparts. Therefore, to better constrain the oxidation state of Ti and its coordination chemistry during lunar magmatic processes, we report new X-ray absorption near edge structure (XANES) spectroscopy measurements for a wide range of minerals (pyroxene, olivine, Fe–Ti oxides) and basaltic melt compositions involved in partial melting of the lunar mantle. Experiments were conducted in 1 bar gas-mixing furnaces at temperatures between 1100 and 1300 °C and oxygen fugacities (fO₂) that ranged from air to two orders of magnitude below the Fe–FeO redox equilibrium. Run products were analysed via electron microprobe and XANES Ti K-edge. Typical run products had large (>?100 µm) crystals in equilibrium with quenched silicate glass. Ti K-edge XANES spectra show a clear shift in energy of the absorption edge features from oxidizing to reducing conditions and yield an average valence for Fe–Ti oxides (armalcolite and ilmenite) of 3.6, i.e., a 40% of the overall Ti is Ti³⁺ under fO₂ conditions relevant to lunar magmatism (IW ??1.5 to ??1.8). Pyroxenes and olivine have average Ti valence of 3.75 (i.e., 25% of the overall Ti is trivalent), while in silicate glasses Ti is exclusively tetravalent. Pre-edge peak intensities also indicate that the coordination number of Ti varies from an average V-fold in silicate glass to VI-fold in the Fe–Ti oxides and a mixture between IV and VI-fold coordination in the pyroxenes and olivine, with up to 82% ^[IV]Ti⁴⁺ in the pyroxene. In addition, our results can help to better constrain the Ti³⁺/∑Ti of the lunar mantle phases during magmatic processes and are applied to provide first insights into the mechanisms that may control Ti mass-dependent equilibrium isotope fractionation in lunar mare basalts.     

Isotopic fractionation of Mg(aq), Ca(aq), and Fe(aq) with carbonate minerals

Density-functional electronic structure calculations are used to compute the equilibrium constants for ²⁶Mg/²⁴Mg and ⁴⁴Ca/⁴⁰Ca isotope exchange between carbonate minerals and uncomplexed divalent aquo ions. The most reliable calculations at the B3LYP/6-311++G(2d,2p) level predict equilibrium constants K, reported as 10³ln (K) at 25 °C, of −5.3, −1.1, and +1.2 for ²⁶Mg/²⁴Mg exchange between calcite (CaCO₃), magnesite (MgCO₃), and dolomite (Ca_0.5Mg_0.5CO₃), respectively, and Mg²⁺(aq), with positive values indicating enrichment of the heavy isotope in the mineral phase. For ⁴⁴Ca/⁴⁰Ca exchange between calcite and Ca²⁺(aq) at 25 °C, the calculations predict values of +1.5 for Ca²⁺(aq) in 6-fold coordination and +4.1 for Ca²⁺(aq) in 7-fold coordination. We find that the reduced partition function ratios can be reliably computed from systems as small as and embedded in a set of fixed atoms representing the second-shell (and greater) coordination environment. We find that the aqueous cluster representing the aquo ion is much more sensitive to improvements in the basis set than the calculations on the mineral systems, and that fractionation factors should be computed using the best possible basis set for the aquo complex, even if the reduced partition function ratio calculated with the same basis set is not available for the mineral system. The new calculations show that the previous discrepancies between theory and experiment for Fe³⁺-hematite and Fe²⁺-siderite fractionations arise from an insufficiently accurate reduced partition function ratio for the Fe³⁺(aq) and Fe²⁺(aq) species.     

Optical spectroscopy study of natural Fe, Ti-bearing calcic amphiboles

Over thirty samples of natural Ti-bearing amphiboles with Ti- and Fe-contents ranging from 0.111 to 0.729 atom per formula unit (a.p.f.u.) and from 0.479 to 2.045 a.p.f.u., respectively, were studied by means of optical absorption spectroscopy and microprobe analysis. Thirteen samples were also studied by Mössbauer spectroscopy. A strong pleochroic absorption edge, causing the dark brown colours of Ti-bearing amphiboles, is attributed to ligand-metal and metal-metal charge transfer transitions involving both iron and titanium ions (O^2?→ Fe³⁺, Fe²⁺, O^2?→ Ti⁴⁺ and Fe²⁺ + Ti⁴⁺→ Fe³⁺ + Ti³⁺). A broad intense Y-polarized band ～22?000?cm^?1 (ν_1/2?≈?3700?cm^?1) in spectra of two low iron amphiboles with a relatively low Fe³⁺/Fe_total ratio, both from eclogite-like rocks in kimberlite xenoliths, was attributed to electronic Fe²⁺(M3) + Ti⁴⁺(M2)→Fe³⁺(M3)+Ti³⁺(M2) IVCT transitions. The IVCT bands of other possible ion pairs, involving Ti⁴⁺ and Fe²⁺ in M2 and M1, M4 sites, respectively, are presumed to be at higher energies, being obscured by the absorption edge.     

Li-bearing, disordered Mg-rich tourmaline from a pegmatite-marble contact in the Austroalpine basement units (Styria, Austria)

Pale-blue to pale-green tourmalines from the contact zone of Permian pegmatites to mica schists and marbles from different localities of the Austroalpine basement units (Rappold Complex) in Styria, Austria, are characterized. All these Mg-rich tourmalines have small but significant Li contents, up to 0.29 wt% Li₂O, and can be characterized as dravite, with FeO contents of ?~?0.9–2.7 wt%. Their chemical composition varies from ^X (Na_0.67Ca_0.19?K_0.02?_0.12) ^Y (Mg_1.26Al_0.97Fe²⁺ _0.36Li_0.19Ti⁴⁺ _0.06Zn_0.01?_0.15) ^Z (Al_5.31?Mg_0.69) (BO₃)₃ Si₆O₁₈ ^V (OH)₃? ^W [F_0.66(OH)_0.34], with a?=?15.9220(3), c?=?7.1732(2) Å to ^X (Na_0.67Ca_0.24?K_0.02?_0.07) ^Y (Mg_1.83Al_0.88Fe²⁺ _0.20Li_0.08Zn_0.01Ti⁴⁺ _0.01?_0.09) ^Z (Al_5.25?Mg_0.75) (BO₃)₃ Si₆O₁₈ ^V (OH)₃? ^W [F_0.87(OH)_0.13], with a?=?15.9354(4), c?=?7.1934(4) Å, and they show a significant Al-Mg disorder between the Y and the Z sites (R1?=?0.013–0.015). There is a positive correlation between the Ca content and?<?Y-O?>?distance for all investigated tourmalines (r?≈?1.00), which may reflect short-range order configurations including Ca and Fe²⁺, Mg, and Li. The tourmalines have X_Mg (X_Mg?=?Mg/Mg?+?Fe_total) values in the range 0.84–0.95. The REE patterns show more or less pronounced negative Eu and positive Yb anomalies. In comparison to tourmalines from highly-evolved pegmatites, the tourmaline samples from the border zone of the pegmatites of the Rappold Complex contain relatively low amounts of total REE (~8–36 ppm) and Th (0.1–1.8 ppm) and have low La_N/Yb_N ratios. There is a positive correlation (r?≈?0.91) between MgO of the tourmalines and the MgO contents of the surrounding mica schists. We conclude that the pegmatites formed by anatectic melting of mica schists and paragneisses in Permian time. The tourmalines crystallized from the pegmatitic melt, influenced by the metacarbonate and metapelitic host rocks.     

A reassessment of the role of iron in the 5,000–30,000 cm−1 region of the electronic absorption spectra of tourmaline

The E∥c and E ⊥ c polarized optical absorption spectra of a variety of blue/green tourmalines and a schorl were measured from room temperature down to helium temperatures. Heat treatments at 750–800° C in air and hydrogen were carried out on several green tourmalines. From the results obtained, absorptions at 7,900 and 13,800 cm^?1 in the E∥c spectra of tourmalines are assigned to Fe²⁺ in the b-site. In the same polarization, bands detected at 9,000 and 13,400 cm^?1 are attributed to Fe²⁺ in the smaller c position. In contrast to previous interpretations, the E ⊥ c polarized bands at 9,000 and 13,800 cm^?1 are not assigned to single ion transitions, but are largely associated with nearest neighbour Fe²⁺-Fe³⁺ pairs. Correlations between near-infrared band absorption coefficients and FeO concentration reinforce these assignments. The temperature dependence and the reaction to heat treatment of the strongly polarized (E⊥c?E∥c) band near 18,000 cm^?1 in blue and green tourmaline spectra are shown to be consistent with previous assignments of the band to Fe²⁺+Fe³⁺→Fe³⁺+Fe²⁺ charge transfer. Similar results are discussed for broad absorptions (also E⊥c?E∥c) found in the 22,000–25,000 cm^?1 region of the spectra of certain green and brown tourmalines. It is concluded that these absorptions are due to Fe²⁺+Ti⁴⁺→Fe³⁺+Ti³⁺ charge transfer. The proposal is made that the initial effect of heating green tourmalines in air and hydrogen is to reduce Fe³⁺ cations located in both b- and c-sites. Further heat treatment in air and hydrogen results in the oxidation of Fe²⁺→Fe³⁺ and leads to the generation of bands near 19,100 and 21,600 cm^?1. The newly formed bands are assigned to Fe³⁺-Fe³⁺ pairs.     

Uptake of uranium and trace elements in pyrite (FeS2) suspensions

Pyrite dissolution and interaction with Fe^(II), Co^(II), Eu^(III) and U^(VI) have been studied under anoxic conditions by solution chemistry and spectroscopic techniques. Aqueous data show a maximal cation uptake above pH 5.5. Iron (II) uptake can explain the non-stoichiometric [S]_aq/[Fe]_aq ratios often observed during dissolution experiments. Protonation data corrected for pyrite dissolution resulted in a proton site density of 9 ± 3 sites nm⁻². Concentration isotherms for Eu^(III) and U^(VI) sorption on pyrite indicate two different behaviours which can be related to the contrasted redox properties of these elements. For Eu^(III), sorption can be explained by the existence of a unique site with a saturation concentration of 1.25 × 10⁻⁶ mol g⁻¹. In the U^(VI) case, sorption seems to occur on two different sites with a total saturation concentration of 4.5 × 10⁻⁸ mol g⁻¹. At lower concentration, uranium reduction occurs, limiting the concentration of dissolved uranium to the solubility of UO₂(s).Scanning electron microscopy and micro-Raman spectrometry of U^(VI)-sorbed pyrite indicate a heterogeneous distribution of U at the pyrite surface and a close association with oxidized S. X-ray photoelectron spectroscopy confirms the partial reduction of U and the formation of a hyperstoichiometric UO_2+x(s). Our results are consistent with a chemistry of the pyrite surface governed not by Fe^(II)-bound hydroxyl groups, but by S groups which can either sorb cations and protons, or sorb and reduce redox-sensitive elements such as U^(VI).     

Fe-rich Li-bearing magnesionigerite-6N6S from Xianghualing tin-polymetallic orefield, Hunan Province, P.R. China

The Fe-rich Li-bearing magnesionigerite-6N6S occurs in the Xianghualing tin-polymetallic ore field, Linwu County, Hunan Province, Peoples Republic of China. It was found near the outer contact zone of the Laizhiling granite body and in the Middle-Upper Devonian carbonate rocks of Qiziqiao Formation. The mineral formed during the skarn stage. Its empirical formula is Sn_1.81Li_0.67(Fe_1.43Zn_1.19 Mn_0.41)_Σ3.03(Al_14.89Mg_1.46 Ti_0.11Si_0.01)_Σ16.47O₃₀(OH)₂. The structure for magnesionigerite-6N6S was solved and refined in space group R-3?m, with a?=?5.7144(8), c?=?55.446(11) Å, V?=?1568.0(4) ų, to R1?=?0.0528. Based on the structural refinement of single crystal diffraction data the formula of magnesionigerite-6N6S is Sn_1.80Li_0.97(Fe_1.89Zn_0.91) _Σ2.80 (Al_14.60Mg_1.63 Ti_0.20)_Σ16.43O₃₀(OH)₂ with Z?=?3. Fe-rich Li-bearing magnesionigerite-6N6S contains 0.74 wt.% Li₂O. The idealized charge-balanced composition of magnesionigerite-6N6S may be expressed by bivalent and trivalent cations: (Mg²⁺)₄(Al³⁺)₁₈O₃₀(OH)₂. The simplified general formula for the 6N6S polysomes in the nigerite and högbomite groups can be given as A _x B_18-x O₃₀(OH)₂, x?=?~4, where A?=?Mg²⁺, Fe²⁺, Zn²⁺; B?=?Al³⁺, Sn⁴⁺, Ti⁴⁺, Li⁺, □.     

Magnetization of Fe-Cr-Ti spinels

Magnetic properties are reported for the spinel series Fe_2.4—t Cr_0.6Ti _t O₄, 0≦t≦0.7, with t=0, 0.2, 0.4, 0.6 and Fe_2.1—t Cr_0.9Ti _t O₄, 0≦t≦0.55, with t=0, 0.2, 0.4, 0.45, 0.5. Magnetic moment data are compared with theoretical values derived from different ion distribution models. With increasing Ti concentration the compositions become hard magnetic spinels due to the increased number of Fe²⁺ ions on A- and B-sites of the spinel lattice.     

Hydroxamate siderophore-promoted reactions between iron(II) and nitroaromatic groundwater contaminants

Recent studies show that ferrous iron (Fe^II), which is often abundant in anaerobic soil and groundwater, is capable of abiotically reducing many subsurface contaminants. However, studies also demonstrate that Fe^II redox reactivity in geochemical systems is heavily dependent upon metal speciation. This contribution examines the influence of hydroxamate ligands, including the trihydroxamate siderophore desferrioxamine B (DFOB), on Fe^II reactions with nitroaromatic groundwater contaminants (NACs). Experimental results demonstrate that ring-substituted NACs are reduced to the corresponding aniline products in aqueous solutions containing Fe^II complexes with DFOB and two monohydroxamate ligands (acetohydroxamic acid and salicylhydroxamic acid). Reaction rates are heavily dependent upon solution conditions and the identities of both the Fe^II-complexing hydroxamate ligand and the target NAC. Trends in the observed pseudo-first-order rate constants for reduction of 4-chloronitrobenzene (k_obs, s⁻¹) are quantitatively linked to the formation of Fe^II species with standard one-electron reduction potentials, (Fe^III/Fe^II), below −0.3 V. Linear free energy relationships correlate reaction rates with the (Fe^III/Fe^II) values of different electron-donating Fe^II complexes and with the apparent one-electron reduction potentials of different electron-accepting NACs, (ArNO₂). Experiments describing a redox auto-decomposition mechanism for Fe^II-DFOB complexes that occurs at neutral pH and has implications for the stability of hydroxamate siderophores in anaerobic environments are also presented. Results from this study indicate that hydroxamates and other Fe^III-stabilizing organic ligands can form highly redox-active Fe^II complexes that may contribute to the natural attenuation and remediation of subsurface contaminants.     

Thermodynamic analysis of the system Fe2O3-FeTiO3

The cluster variation method, in the single prism approximation, is used to model phase relations in the system, Fe₂O₃-FeTiO₃. Ordering in FeTiO₃ is analyzed, and it is shown that the stabilization of FeTiO₃ (relative to mechanical mixing of Fe₂O₃ and Ti₂O₃) includes: (1) a contribution from the redox reaction, Fe³⁺+Ti³⁺→Fe²⁺+Ti⁴⁺ (ΔH _redox～?70kJ mole^?1); and (2) a contribution from ordering (ΔH _OD～?8kJ mole^?1). A theoretical phase diagram is presented and compared with available experimental data. Semiquantitative agreement between theory and experiment (on the location of phase boundaries) is achieved; but, owing to the paucity of experimental data on coexisting phases, these results may be fortuitous.     

Perrierite-(La), (La,Ce,Ca)4(Fe2+,Mn)(Ti,Fe3+,Al)4(Si2O7)2O8, a new mineral species from the Eifel volcanic district, Germany

Non-metamict perrierite-(La) discovered in the Dellen pumice quarry, near Mendig, in the Eifel volcanic district, Rheinland-Pfalz, Germany has been approved as a new mineral species (IMA no. 2010-089). The mineral was found in the late assemblage of sanidine, phlogopite, pyrophanite, zirconolite, members of the jacobsite-magnetite series, fluorcalciopyrochlore, and zircon. Perrierite-(La) occurs as isolated prismatic crystals up to 0.5 × 1 mm in size within cavities in sanidinite. The new mineral is black with brown streak; it is brittle, with the Mohs hardness of 6 and distinct cleavage parallel to (001). The calculated density is 4.791 g/cm³. The IR spectrum does not contain absorption bands that correspond to H₂O and OH groups. Perrierite-(La) is biaxial (-), α = 1.94(1), β = 2.020(15), γ = 2.040(15), 2V _meas = 50(10)°, 2V _calc = 51°. The chemical composition (electron microprobe, average of seven point analyses, the Fe²⁺/Fe³⁺ ratio determined from the X-ray structural data, wt %) is as follows: 3.26 CaO, 22.92 La₂O₃, 19.64 Ce₂O₃, 0.83 Pr₂O₂, 2.09 Nd₂O₃, 0.25 MgO, 2.25 MnO, 3.16 FeO, 5.28 Fe₂O₃, 2.59 Al₂O₃, 16.13 TiO₂, 0.75 Nb₂O₅, and 20.06 SiO₂, total is 99.21. The empirical formula is (La_1.70Ce_1.45Nd_0.15Pr_0.06Ca_0.70)_Σ4.06(Fe _0.53 ²⁺ Mn_0.38Mg_0.08)_Σ0.99(Ti_2.44Fe _0.80 ³⁺ Al_0.62Nb_0.07)_Σ3.93Si_4.04O₂₂. The simplified formula is (La,Ce,Ca)₄(Fe²⁺,Mn)(Ti,Fe³⁺,Al)₄(Si₂O₇)₂O₈. The crystal structure was determined by a single crystal. Perrierite-(La) is monoclinic, space group P2₁/a, and the unit-cell dimensions are as follows: a =13.668(1), b = 5.6601(6), c = 11.743(1) Å, β = 113.64(1)°; V = 832.2(2) ų, Z = 2. The strong reflections in the X-ray powder diffraction pattern are [d, Å (I, %) (hkl)]: 5.19 (40) (110), 3.53 (40) ( $\overline 3 $ 11), 2.96 (100) ( $\overline 3 $ 13, 311), 2.80 (50) (020), 2.14 (50) ( $\overline 4 $ 22, $\overline 3 $ 15, 313), 1.947 (50) (024, 223), 1.657 (40) ( $\overline 4 $ 07, $\overline 4 $ 33, 331). The holotype specimen of perrierite-(La) is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, Russia, with the registration number 4059/1.     

Titanian andradite in a metapyroxenite layer from the Malenco ultramafics (Italy): implications for Ti-mobility and low oxygen fugacity

Ti-andradite (melanite) has been found in a metapyroxenite layer in the upper part of the Malenco ultramafics(Italy), coexisting with clinochlore, diopside and magnetite. Field observations, as well as major and trace elementbulk-rock composition, strongly suggest a cumulate origin for the layer. Textural relationships indicate thatTi-andradite formed during two different metamorphic stages. Under peak metamorphic conditions (400–450°C, 5±2 kbar)Ti-andradite grew in an assemblage of diopside, clinochlore, magnetite and rare ilmenite and perovskite. Later, retrograde brittle deformationinduced formation of veins containing the paragenesis Ti-andradite, vesuvianite, diopside, chlinochlore, magnetite and accessory perovskite.The Ti-andradite varies considerably in TiO₂ (0.11–9.62 wt%), Fe₂O₃(14.3–30.5 wt%), Al₂O₃ (0.65–3.90 wt%), Cr₂O₃(>0.18–0.98 wt%) and SiO₂ (32.1–36.1 wt%); this is mostly, but not entirely, due to distinct zoning.Ti-andradite contains 0.32 to 0.66 wt% H₂O as determined by infrared spectroscopy and 0.83 to 1.76 wt% FeO. The CaO shows almost no variation (34.1±0.7 wt%) and Ca completely fills the dodecahedral site. Single crystal site refinements indicate that no tetrahedral Ti or Fe replaces Si. Titanium incorporation is attributed to similar degrees of substitution along the exchange vectors Ti³⁺ Fe³⁺, Ti⁴⁺ Al^IV Al _-1 ^VI Si_-1 and (Fe²⁺, Mn²⁺, Mg²⁺)Ti⁴⁺ 2Fe _-1 ³⁺ . The presence of mixed valence states of both Fe and Ti suggests a low oxygen fugacity during crystallization of Ti-andradite. Mass balance calculations indicate an isochemical origin of the first generation of Ti-andradite in the clinopyroxenite layer. Its occurrence is restricted to antigorite-free mineral assemblages containing clinochlore of 0.95X _Al>1.1. The hydrothermal crystallization of Ti-rich andradite in veins demonstrates Ti mobility in aqueous fluids under moderate P-T conditions. The zonation patterns indicate disequilibrium conditions during vein crystallization. As no fluorine-, carbonate- and phosphate-bearing minerals were found, OH^- is most probably the ligand complexing Ti.     

Single crystal absorption spectra of synthetic Ti,Fe-substituted pyropes

Synthetic pyrope crystals up to 0.5 mm in diameter, substituted by titanium or by titanium plus iron, were grown under defined conditions of P, T, $f_{O_2 }$ in the presence of water using a piston-cylinder device. The crystals were characterized by X-ray and microprobe techniques. Their single-crystal optical absorption spectra were measured by means of a microscope-spectrometer. Two absorption bands at 16100 and 22300 cm{cm-1} in the spectra of pale-blue Fe-free Ti-bearing pyropes, grown under reduced conditions, were identified as originating from spin-allowed transitions, derived from ² T _2g → ² E _g of octahedral Ti³⁺ ions. The splitting value of the excited ²E _g state, 6200 cm^-1, and the crystal field parameter of Ti³⁺ in pyrope Δ ₀ = 19 200 cm^-1 are both in agreement with literature data. In spectra of brown Fe, Ti-bearing garnets, a broad band at 23000 cm^-1 was interpreted as a Fe^2+[8] → Ti^4+[6] charge-transfer band. The spectral position and width of this band agree with those observed for a FeTi charge transfer band in natural garnets. Fe, Ti-containing garnets synthesized at relatively high oxygen fugacity (10^-11,0 atm), which permits a fraction of Fe³⁺ to enter the garnet, show an additional Fe^2+[8] → Fe^3+[6] charge transfer band at 19800 cm^-1.     

Electron delocalization in ilvaite,a reinterpretation of its 57Fe Mössbauer spectrum

The Mössbauer spectra of ilvaite CaFe ₂ ²⁺ Fe³⁺[Si₂O₇/O/OH] and their temperature dependence between 298 K and 455 K can be satisfactorily least-squares fitted by a superposition of the resonances for Fe²⁺(8d), Fe³⁺(8d) and Fe²⁺(4c). The relative areas under the three resonances are nearly equal and vary only weakly with temperature. No additional resonances or line broadenings have to be introduced, if we assume that the hyperfine interactions of Fe²⁺(8d) and Fe³⁺(8d) fluctuate between their values due to electron hopping between the iron ions at the 8d sites. Hopping can be assumed to occur homogeneously among nearly equivalent sites. The fluctuation rate is described by an Arrhenius law with a pre-exponent of about 9 × 10⁸ s^?1 and an activation energy of 0.11 eV indicating non-adiabatic hopping. In addition to the intersite hopping process, the strong decrease of the quadrupole splitting and the isomer shift of Fe²⁺(8d) between 298 K and 360 K suggests the occurrence of intrinsic charge delocalization from Fe²⁺(8d) which does not involve the neighbouring Fe³⁺(8d) ions.     

Concentration of Mn and separation from Fe in sediments—I. Kinetics and stoichiometry of the reaction between birnessite and dissolved Fe(II) at 10°C

Redox reactions between Fe²⁺ in solution and Mn-oxides are proposed as a mechanism for concentration of Mn in sediments both during weathering and diagenesis in marine sediments, e.g. the formation of Mn-nodules.If such a mechanism is to be effective, then reaction rates between Fe²⁺ and Mn-oxides should be fast. The kinetics and stoichiometry of the reaction between dissolved Fe²⁺ and synthetically prepared birnessite (Mn₇O₁₃·5H₂O) were studied experimentally in the pH range 3–6.Results show a stoichiometry which at pH < 4 conforms to a simple reaction between Fe²⁺ and birnessite, releasing Mn²⁺ and Fe³⁺ to the solution. At pH > 4 FeOOH is precipitated and excess Fe²⁺ consumption compared to the theoretical stoichiometry is observed. The excess Fe²⁺ consumption is not due to a formation of a quantitative MnOOH layer but rather to adsorption.Reaction kinetics are very fast at pH < 4 and change at pH 4 to a slower mechanism. At pH > 4 the reaction is fast initially until 17% of the bimessite has dissolved and changes then to a slower stage. The later stage can be described by the equation: $\text{J = km}{}_0\text{(H}{}^{\mathrm{+}}\text{)}{}^{\mathrm{?0.45}}\text{[Fe}{}^{\mathrm{2+}}\text{]}{}^{\mathrm{\gamma }}\text{(}\text{m}\text{m}{}_0\text{)}{}^{\mathrm{\beta }}$ where J is the overall rate of Mn²⁺ release, m₀ and m the mass of birnessite at time t = 0 and t > 0, β = 6.76?0.94 pH and γ has values of 0.76 at pH 5 and 0.39 at pH 6. The rate constant k is 7.2·10^?7 moles s^?1 g^?1 (moles/1)^?0.31 at pH 5 and 9.6·10^?8 moles s^?1 g^?1 (moles/1)^0.06 at pH 6.Diffusion calculations show that the rate is controlled by surface reaction and it is tentatively proposed that the availability of vacancies in octahedral [MnO₆]sheets of the birnessite surface could be rate controlling. It is concluded that reactions between Fe(II) and birnessite, and probably other Mn-oxides, are fast enough to be important in natural environments at the earth surface.     

Magnetic behavior of trioctahedral micas with different octahedral Fe ordering

This contribution is finalized at the discussion of the magnetic structure of two samples, belonging to phlogopite–annite [sample TK, chemical composition ^IV(Si_2.76Al_1.24) ^VI(Al_0.64Mg_0.72 $ {\text{Fe}}_{1.45}^{2 + } $ Mn_0.03Ti_0.15) (K_0.96Na_0.05) O_10.67 (OH)_1.31 Cl_0.02] and polylithionite–siderophyllite joints [sample PPB, chemical composition ^IV(Si_3.14Al_0.86)^VI(Al_0.75Mg_0.01 $ {\text{Fe}}_{1.03}^{2 + } $ $ {\text{Fe}}_{1.03}^{3 + } $ Mn_0.01Ti_0.01Li_1.09) (K_0.99Na_0.01) O_10.00 (OH)_0.65F_1.35]. Samples differ for Fe ordering in octahedral sites, Fe²⁺/(Fe²⁺?+?Fe³⁺) ratio, octahedral composition, defining a different environment around Fe cations, and layer symmetry. Spin-glass behavior was detected for both samples, as evidenced by the dependency of the temperature giving the peak in the susceptibility curve from the frequency of the applied alternating current magnetic field. The crystal chemical features are associated to the different temperature at which the maximum in magnetic susceptibility is observed: 6?K in TK, where Fe is disordered in all octahedral sites, and 8?K in PPB sample, showing a smaller and more regular coordination polyhedron for Fe, which is ordered in the trans-site and in one of the two cis-sites.