Thermal diffusivity of natural and synthetic garnet solid solution series

Knowledge of heat transport properties as a function of mineral- and rock-composition and temperature is of major relevance to understand and model heat transfer in the Earth’s interior. A systematic study on 13 natural and 4 synthetic garnets was carried out in an attempt to obtain a better systematic understanding of the processes that affect the heat transport in minerals, especially the effect of chemical substitution in solid solution series. It is found that substitution significantly lowers the thermal diffusivity from end-member values for both synthetic and natural garnets with a minimum of thermal diffusivity at an intermediate composition. The thermal diffusivity as a function of the degree of substitution can be described by the approach of Padture and Klemens (J Am Ceram Soc 80 (4):1018–1020, 1997). With increasing temperature the thermal diffusivity decreases due to phonon-phonon-scattering effects. A quantitative analysis of the high-temperature behaviour was carried out by using the model of Roufosse and Klemens (J Geophys Res 79 (5):703–705, 1974), which takes a lower limit of thermal diffusivity at elevated temperatures into account. The model allows for an extrapolation of the deduced room temperature thermal diffusivities to higher temperatures. Furthermore, the model was modified to determine the high temperature limit of the thermal diffusivity for all investigated natural garnets D _min to be 0.64 ± 0.03 mm²/s.     

Long-range atmospheric transport of trace metals: the need for geoscience perspectives

 The scientific literature of the past 25 years indicates a lack of consensus over the relative significance of anthropogenic and natural sources of metals in rural and remote ecosystems, meaning areas located several hundred to several thousand kilometers from industrial point sources. Geoscience perspectives are needed to address the critical information gaps associated with this issue, particularly where information on the significance and variability of naturally occurring metals is required. Uncertainties in source apportionment need to be addressed by improving methods of fingerprinting sources of airborne particles, and establishing identities of individual particles on the basis of characteristic morphologies and chemical composition. Further research is required to obtain robust estimates of total metal emissions to the atmosphere and to the oceans in order to determine the relative contribution from anthropogenic sources. Such research must involve a systematic attempt to obtain spatially and temporally representative data on the natural release of metals at the global scale. Moreover, a clear understanding of all local natural and anthropogenic loadings to an ecosystem is required before firm conclusions can be drawn about the relative importance of long-range atmospheric transport. Received: 31 October 1996 · Accepted: 27 May 1997     

Testing the ability of bentonite-amended natural zeolite (clinoptinolite) to remove heavy metals from liquid waste

 The design of environmentally sound liquid waste containment structures has become a crucial task in engineering applications due to ever increasing groundwater contamination from such sites. Construction of such structures usually requires a bottom liner of low hydraulic conductivity as part of the design. In order to reduce the hazards associated with liquid wastes including landfill leachate, bentonite-amended natural zeolite is proposed as an alternative to conventional earthen liners. Among many contaminants associated with liquid wastes, heavy metals are the most dangerous ones. This paper deals with determining the ability of natural zeolite to remove heavy metals from aqueous waste. For this purpose, crushed natural zeolite (clinoptinolite) is amended with commercial powdered bentonite to yield a soil mixture low in permeability and high in ion-exchange capacity. Leachate from a conventional landfill is used as the percolation fluid. Concentrations of certain heavy metals in the effluent fluid percolated through the bentonite-zeolite mixture are compared with that of initial leachate. The conclusion is reached that certain metals are efficiently removed from the influent solution by the soil matrix whereas some ions do not show significant reduction in concentration. This is attributed to high hydraulic conductivity of the bentonite-zeolite mixture.     

Microclimatic characterization of a karstic cave: human impact on microenvironmental parameters of a prehistoric rock art cave (Candamo Cave, northern Spain)

The Candamo Cave contains an important group of paleolithic paintings which have been seriously deteriorated due to mass tourism. In this work, an analysis was carried out of different climatic parameters (CO₂, temperature, humidity, ²²²Rn) during annual cycles with the cave closed to the public and during an experimental period of controlled visits. The effect of visits on the geochemical characteristics of karstic water was also analyzed together with the cave ventilation. The natural variations in the cave air CO₂ were above 3000 ppm, the increase produced through visits was only 100–110 ppm and since the humidity is almost permanently at saturation point, the critical parameter which limits the visitor capacity becomes air temperature. The temperature changes during the annual cycle are of the order of 1  °C in the external part and less than 0.5  °C in the internal part of the cave and a maximum increase of 0.13  °C was observed during the period of the visits. The ²²²Rn and CO₂ concentration minimums in the summer period (July–October) show that this is the most propitious time for visits, since the greatest ventilation is produced in the cave at this time and, therefore, the greatest capacity for recovery. The geochemistry of the water, on the other hand, indicated that this is the period of the year in which processes of wall corrosion can be most easily introduced, although this would be of limited magnitude. The visitor capacity calculated was 29 visitors/day. Received: 29 August 1996 · Accepted: 23 June 1997     

Study of the electron density in MgO, (Mg0.963Fe0.037)O and Cu2O by the maximum entropy method and multipole refinements: comparison between methods

 The electron densities determined by the maximum entropy method and by the multipole refinement approach are compared with each other, in terms of some topological properties according to the Bader formalism (Laplacian and eigenvalues of the Hessian matrix of the electron density at the critical points). The cases of MgO, (Mg,Fe)O and Cu₂O are examined. The best agreement is observed for the critical points along the Mg–O, (Mg,Fe)–O and Cu–O directions, whereas larger discrepancies occur at the other critical points. Plots of the electron densities generated by the maximum entropy method and the multipole formalism along the most representative crystallographic directions contribute to elucidating the comparison between approaches. Received: 3 July 2001 / Accepted: 7 March 2002     

Assessment of natural attenuation of aromatic hydrocarbons in groundwater near a former manufactured-gas plant, South Carolina, USA

 Shallow, anaerobic groundwater near a former manufactured-gas plant (MGP) in Charleston, South Carolina, USA, contains mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs, respectively). Between 1994 and 1997, a combination of field, laboratory, and numerical-flow and transport-model investigations were made to assess natural attenuation processes affecting MAH and PAH distributions. This assessment included determination of adsorption coefficients (K _ad ) and first-order biodegradation rate constants (K _bio ) using aquifer material from the MGP site and adjacent properties. Naphthalene adsorption (K _ad =1.35×10^–7 m³/mg) to aquifer sediments was higher than toluene adsorption (K _ad =9.34×10^–10 m³/mg), suggesting preferential toluene transport relative to naphthalene. However, toluene and benzene distributions measured in January 1994 were smaller than the naphthalene distribution. This scenario can be explained, in part, by the differences between biodegradation rates of the compounds. Aerobic first-order rate constants of ¹⁴C-toluene, ¹⁴C-benzene, and ¹⁴C-naphthalene degradation were similar (–0.84, –0.03, and 0.88 day^–1, respectively), but anaerobic rate constants were higher for toluene and benzene (–0.002 and –0.00014 day^–1, respectively) than for naphthalene (–0.000046 day^–1). Both areal and cross-sectional numerical simulations were used to test the hypothesis suggested by these rate differences that MAH compounds will be contained relative to PAHs. Predictive simulations indicated that the distributions of toluene and benzene reach steady-state conditions before groundwater flow lines discharge to an adjacent surface-water body, but do discharge low concentrations of naphthalene. Numerical predictions were "audited" by measuring concentrations of naphthalene, toluene, and benzene at the site in early 1997. Measured naphthalene and toluene concentrations were substantially reduced and the areal extent of contamination smaller than was both observed in January 1994 and predicted for 1997. Measured 1997 benzene concentrations and distribution were shown to be relatively unchanged from those measured in 1994, and similar to predictions for 1997. Received: 26 June 1997 · Accepted: 25 August 1997     

Weathering process at the natural fission reactor of Bangombé

 The uranium deposits in the basin of Franceville (Gabon) host the only natural fission reactors known in the world. Unique geological conditions favoured a natural fission reaction 2 Ga ago. This was detected by anomalous isotopic compositions of uranium and rare earth elements (REE), which are produced by the fission reaction. In total, 16 reactor zones were found. Most of them are mined out. The reactor zone of Bangombé, is only 10–11 m below the surface. This site has been influenced by surface weathering processes. Six drill cores have been sampled at the site of the reactor zone of Bangombé during the course of the study and only one drill core (BAX 08) hit the core of the reactor. From these data and previous drilling campaigns, the reactor size is estimated to be 10 cm thick, 2–3 m wide and 4–6 m long. The migration of fission products can be traced by the anomalous isotope ratios of REE because of the fission process. The ¹⁴⁹Sm/¹⁴⁷Sm ratio close to the reactor zone is only 0.28 (normal: 0.92) because of the intense neutron capture of ¹⁴⁹Sm and subsequent transmutation, whereas ¹⁴⁷Sm is enriched by the fission reaction. Similar changes in isotopic patterns are detectable on other REE. The isotope ratios of Sm and Nd of whole rock and fracture samples surrounding the reactor indicate that fission-genic REE migrated only a few decimetres above and mainly below the reactor zone. Organic matter (bitumen) seems to act as a trap for fission-genic REE. Additional REE-patterns show less intense weathering with increasing depth in the log profile and support a simple weathering model. Received: 26 November 1999 · Accepted: 2 May 2000     

Sources and pathways of natural and anthropogenic hydrocarbons into the natural dump Arkona Basin (southern Baltic Sea)

 Surface sediments, suspended particulate matter and fluffy-layer material, collected in the Arkona Basin and the Pomeranian Bay during 1995–1997, as well as air particulate matter, collected on the island of Rügen during August 1995, were analysed for total organic carbon content, saturated and polycyclic aromatic hydrocarbons (PAH). The resulting concentrations and distributions of these compounds and molecular PAH ratios are discussed in terms of matrix, origin of the organic matter and seasonal variations. The data show that the Oder river can be identified as a major source for PAH transported into the southern part of the Arkona Basin. A strong atmospheric input of PAH is noted for the central and northern part of the basin. In general, anthropogenic and bacterially degraded hydrocarbons bound to organic carbon-rich and small particles are mainly deposited in the basin center, whereas their natural counterparts accumulate mainly on the basin flanks covered by coarser grained sediments. Received: 2 March 1999 · Accepted: 8 June 1999     

Electron density distributions and bonded interactions for the fibrous zeolites natrolite, mesolite and scolecite and related materials

 For the fibrous zeolites natrolite, Na₂[Al₂Si₃O₁₀]·2H₂O, mesolite, Na₂Ca₂[Al₂Si₃O₁₀]₃·8H₂O, and scolecite, Ca[Al₂Si₃O₁₀]·3H₂O, with topologically identical aluminosilicate framework structures, accurate single-crystal X-ray diffraction data have been analyzed by least-squares refinements using generalized scattering factor (GSF) models. The final agreement indices were R(F ) = 0.0061, 0.0165, and 0.0073, respectively. Ensuing calculations of static deformation [Δρ(r)], and total, [ρ(r)], model electron density distributions served to study chemical bonding, in particular by topological electron density analyses yielding bond critical point (bcp) properties and in situ cation electronegativities. The results for 32 SiO, 24 AlO, 14 CaO, and 12 NaO unique bonds are compiled and analyzed in terms of both mean values and correlations between bond lengths, bonded oxygen radii, bcp densities, curvatures at the bcps, and electronegativities. Comparison with recent literature data obtained from both experimental electron density studies on minerals and model calculations for geometry-optimized molecules shows that the majority of the present findings conforms well with chemical expectation and with the trends observed from molecular modeling. For the SiO bond, the shared interaction is indicated to increase with decreasing bond length, whereas the AlO bond is of distinctly more polar nature, as is the NaO bond compared to CaO. Also, the observed ranges of the Si and Al in situ electronegativities and their mean electronegativities agree well with both Pauling's values and model calculation results, and statistically significant correlations are obtained which are consistent with trends described for oxide and nitride molecules. Received: 10 May 1999 / Revised, accepted: 14 September 1999     

Synchrotron X-ray powder diffraction study of natural P2 /n-omphacites at high-pressure conditions

 Synchrotron X-ray powder diffraction experiments at high pressure conditions (0.0001–13 GPa) were performed at ESRF (Grenoble-F), on the beamline ID9, to investigate the bulk elastic properties of natural P2/n-omphacites, with quasi-ideal composition. The monoclinic cell parameters a, b, c and β were determined as a function of pressure, and their compressibility coefficients are 0.00277(7), 0.00313(8), 0.00292(5) and 0.00116(4) GPa⁻¹, respectively. The third-order Birch-Murnaghan equation of state was used to interpolate the experimental P−V data, obtaining K ₀=116.6(±2.5) GPa and K′₀=6.03(±0.60). K ₀ was also determined by means of the axial and angular compressibilities [122.5(±1.7) GPa], and of the finite Lagrangian strain theory [121.5(±1.0) GPa]. The discrepancies on K ₀ are discussed in the light of a comparison between techniques to determine the bulk modulus of crystalline materials from static compression diffraction data. Received: 22 February 2000 / Accepted: 10 July 2000     

Investigation of groundwater flow in karst areas using component separation of natural potential measurements

 The natural (electrical) potential (NP) method – also known as self-potential, spontaneous potential and streaming potential (SP) – has been used to locate areas of groundwater flow in karst terrane. NP is the naturally occurring voltage at the ground surface resulting from ambient electrical currents within the earth. The measurement of NP can be used to characterize groundwater flow in karst terrane because electrical potential gradients are generated by the horizontal flow of water along fractures or conduits and the vertical infiltration of water into fractures or shafts. NP data from a site on the Mitchell Plain of southern Indiana, USA, revealed that NP data can be decomposed into three components: topographic effect, residual NP and noise. At this site, NP was inversely proportional to elevation, but the correlation varied with time. The topographic correction factor varied from –2.5 to –1.2 mV/m (NP change per unit elevation increase), with an average linear correlation coefficient (R) of 0.95. Because the site slopes toward an adjacent creek that is the local groundwater discharge zone, one possible explanation for this effect is a streaming-potential mechanism generated by groundwater movement toward the creek. The residual NP data revealed three negative anomalies at the survey area. Two of them coincide with sinkholes. A part of the third anomaly is coincident with a small valley, and concentrated infiltration does occur at this elevation in other valleys at the site, as evidenced by the existence of sinkholes. However, the dispersed, low-magnitude nature of the third anomaly does not prove the existence of concentrated groundwater recharge activity. Received: 18 March 1998 · Accepted: 27 April 1998     

Calculation of thermodynamic properties of hydrated borates by group contribution method

 General equations to correlate and predict the thermodynamic properties of hydrated borates were developed based on the experimental results according to their structural types. The thermodynamic properties (ΔH _f ⁰ and ΔG _f ⁰) of a hydrated borate phase are the sum of the contributions of the cations in aqueous solution, the borate polyanions, and the structural water to the corresponding thermodynamic properties. This method is called the group contribution method, and it is extensively used to calculate the thermodynamic properties of many kinds of inorganic compounds, such as silicates and clay minerals. Received: 23 November 1998 / Accepted: 11 October 1999     

Characterization of a natural magnetite

Single crystals of a rock magnetite were separated from steatite cobbles collected in a geological site near the city of Serro (18° 36′ 47′′ S 43° 22′ 46′′ W), Minas Gerais, Brazil. A typically well-shaped magnetite single crystal was characterized by chemical analysis, ⁵⁷Fe Mössbauer spectrometry at 300, 77 and 4 K and under an applied magnetic field of 6 T at 10 K, magnetization measurements and electronic microprobe. From Mössbauer data, the sample is stoichiometric with a tetrahedral and octahedral site occupancy ratio of 1:2. Elemental chemical analysis and point-to-point electron microscope probing show some inclusions of lamellar ilmenite (≤ 1 mass%) randomly distributed throughout the magnetite matrix, and also that the magnetite matrix is constituted only by Fe²⁺ and Fe³⁺, with no isomorphic substitution. Results are discussed on the basis of the magnetization curve and of the temperature dependence of the AC magnetic susceptibility. The Verwey transition occurs in the temperature range of 100–115 K, observed by a sudden change in the temperature dependence of the magnetization.     

The crystal chemistry of birefringent natural uvarovites. Part III. Application of the superposition model of crystal fields with a characterization of synthetic cubic uvarovite

Synthetic, flux-grown uvarovite, Ca₃Cr₂ [SiO₄]₃, was investigated by optical methods, electron microprobe analysis, UV-VIS-IR microspectrometry, and luminescence spectroscopy. The crystal structure was refined using single-crystal X-ray CCD diffraction data. Synthetic uvarovite is optically isotropic and crystallizes in the “usual” cubic garnet space group Ia3¯d [a=11.9973 Å, Z=8; 21524 reflections, R1=2.31% for 454 unique data and 18 variables; Cr–O=1.9942(6), Si–O=1.6447(6), Ca–O_a=2.3504(6), Ca–O_b= 2.4971(6) Å]. The structure of Ca₃Cr₂[SiO₄]₃ complies with crystal-chemical expectations for ugrandite group garnets in general as well as with predictions drawn from “cubically averaged” data of non-cubic uvarovite–grossular solid solutions (Wildner and Andrut 2001). The electronic absorption spectra of Cr³⁺ in trigonally distorted octahedra of synthetic uvarovite were analyzed in terms of the superposition model (SM) of crystal fields. The resulting SM and interelectronic repulsion parameters are =9532 cm^?1, =4650 cm^?1, power law exponent t ₄=6.7, Racah B₃₅=703 cm^?1 at 290 K (reference distance R ₀=1.995 Å; fixed power law exponent t ₂=3 and spin-orbit parameter ζ=135 cm^?1). The interelectronic repulsion parameters Racah B ₅₅=714 cm^?1 and C=3165 cm^?1 were extracted from spin-forbidden transitions. This set of SM parameters was subsequently applied to previously well-characterized natural uvarovite–grossular solid solutions (Andrut and Wildner 2001a; Wildner and Andrut 2001) using their extrapolated Cr–O bond lengths to calculate the energies of the spin-allowed bands. These results are in very good agreement with the experimentally determined band positions and indicate the applicability of the superposition model to natural 3d ^N prevailing systems in geosciences. Single-crystal IR absorption spectra of synthetic uvarovite in the region of the OH-stretching vibration exhibit one isotropic absorption band at 3508 cm^?1 at ambient conditions, which shifts to 3510 cm^?1 at 77 K. This band is caused by structurally incorporated hydroxyl groups via the (O₄H₄)-hydrogarnet substitution. The water content, calculated using an integral extinction coefficient ?=60417 cm^?2 l mol^?1, is c _H2O=33 ppm.     

Mie scattering and charge transfer phenomena as causes of the UV edge in the absorption spectra of natural and synthetic almandine garnets

 The UV edge in the electronic absorption spectra of minerals, in many cases influencing their colour, is generally interpreted as the low-energy wing of very strong UV bands caused by ligand–metal charge transfer (CT) transitions (e.g. Burns 1993). However, Mie scattering theory shows that the presence of randomly distributed submicroscopic inclusions with narrow size distribution and a refractive index n _i in a matrix with different refractive index n _m may give rise to a λ-dependent, band-like scattering (e.g. Kortüm 1969). Such scattering bands have so far not been considered as contributing to the UV edge. Single-crystal electronic absorption spectra of eight natural almandine-rich garnets (Alm₆₀–Alm₈₈), two synthetic almandine samples (Alm₁₀₀), all of different colours, and synthetic spessartine were studied by means of a Zeiss microscope-spectrometer in the range 40 000–20 000 cm⁻¹. Special techniques of spectral measurements with crossed analyzer and polarizer, which enable the registration of the scattering effect directly, were used as well. Four of the above garnets were also investigated using transmission electron microscopy. Different types of inclusions, from 10 to several 100 nm in size, were observed in the garnet matrices. They are abundant in cores of synthetic garnets, but very rare in most natural almandines studied. Electronic absorption spectra of the natural almandine garnets show largely varying UV edge position and, hence, intensity at a given wavenumber which correlates with the intensities of spin-forbidden dd bands of Fe³⁺ ions at 27 000 and 28 000 cm⁻¹, superimposed on the long energy slope of the UV absorption. There are also positive correlations between Ti⁴⁺ and Fe³⁺ content, the latter recalculated on the basis of garnet stoichiometry, and UV edge intensity. Thus, the presence of Ti⁴⁺ and Fe³⁺ ions in octahedra, even in very low concentrations (0.0n at. pfu), leads to CT phenomena, that probably involve Fe²⁺ ions in edge-shared dodecahedral position and intensifies ligand- to-metal CT. The different colours of natural almandine garnets with similar Fe²⁺ contents studied here are caused by this effect. Consistent with the absence of inclusions in most natural garnets studied, λ-dependent scattering plays no role in their UV absorption. In contrast, in synthetic almandine and spessartine crystals, a different intensity of UV absorption was observed in inclusion-free rims and inclusion-enriched cores. Some of the latter demonstrate typical scattering patterns when measured at crossed polarizers. Received: 10 April 2001 / Accepted: 27 September 2001     

Thermodynamic data of the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite)

 Calorimetric and P–V–T data for the high-pressure phase Mg₅Al₅Si₆O₂₁(OH)₇ (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B₂O₃) at T=700 ^∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets; they range from −221.1 to −259.4 kJ mol⁻¹ (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol⁻¹ (formation from the elements). The heat capacity of Mg₅Al₅Si₆O₂₁(OH)₇ has been measured from T=50 ^∘C to T=500 ^∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents the heat capacity over the entire temperature range to within the experimental uncertainty: C _P (Mg-sursassite) =(1571.104 −10560.89×T ^−0.5−26217890.0 ×T ⁻²+1798861000.0×T ⁻³) J K⁻¹ mol⁻¹ (T in K). The P V T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ^∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the bulk modulus was determined as 116.0±1.3 GPa, (K ^′=4), V _T,0 =446.49 ³ exp[∫(0.33±0.05) × 10⁻⁴ + (0.65±0.85)×10⁻⁸ T dT], (K _T/T) _P  = −0.011± 0.004 GPa K⁻¹. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg 1998); the best agreement was obtained with Δ_f H ⁰ ₂₉₈ (Mg-sursassite) = −13901.33 kJ mol⁻¹, and S ⁰ ₂₉₈ (Mg-sursassite) = 614.61 J K⁻¹ mol⁻¹. Received: 21 September 2000 / Accepted: 26 February 2001     

The spa Deutsch-Altenburg and the hydrogeology of the Vienna basin (Austria)

 Some years ago the thermal water wells of the spa Deutsch-Altenburg were considered the result of a local water circulation. Extensive measurements of the water chemistry, trace elements, and environmental isotopes combined with drillings in the river bed of the Danube resulted in the indication of a key position of the mineral thermal wells of Deutsch-Altenburg for the groundwater circulation in the entire Vienna basin. The proof of this fact demanded the inclusion of the complicated geological position of the basin into the argumentation. The historical background of Bad Deutsch-Altenburg is the Roman municipium Carnuntum. During the reign of the Roman emperor Marc Aurel (161-180 A.C.) Carnuntum became the largest Roman municipium northeast of Rome with about 50 000 inhabitants covering the areas of present-day villages Petronell and Deutsch-Altenburg due to its strategic and trade position. The town was totally destroyed during the era of "migration of nations." The land surface was farmland or meadows. The first document concerning the thermal water of Deutsch-Altenburg is an expertise of the medical faculty of the University of Vienna (1548). During the siege of Vienna by the Turkish army under Kara Mustafa (1683–84) Deutsch-Altenburg was again, destroyed. It was only at the end of the 19th century that the modern installation of the spa began. The healing thermal water with the highest content of sulfur in Austria made Deutsch-Altenburg one of the most well-known spas in the country. The archaeological excavation of Carnuntum is the largest in Austria. Received: 6 October 1995 · Accepted: 13 November 1995     

Crystal chemistry of ferric iron in (Mg,Fe)(Si,Al)O<Subscript>3</Subscript> majorite with implications for the transition zone

Fifteen samples of (Mg,Fe)SiO₃ majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O₃ majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe³⁺ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe²⁺–Fe³⁺ charge transfer, where band intensity increases with increasing Fe³⁺ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe³⁺ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO₃ majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe³⁺ concentration of (Mg,Fe)(Si,Al)O₃ majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O₃ perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.