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     

Heat of formation of petalite, LiAlSi4O10

The enthalpy of formation of petalite, LiAlSi₄O₁₀, has been measured using high-temperature solution calorimetry. The measurements were carried out in a Calvet-type twin micro calorimeter at 728?°C. A 2PbO?·?B₂O₃ melt was used as a solvent. Tabulated heats of formation of the components and tabulated heat capacities of the reactants and the product (Robie and Hemingway 1995) were used to calculate the standard heat of formation of petalite from the measured heats of solution. The calculations yielded a mean value of Δ _f H ^pet _298.15=?4872±5.4 kJ mol^?1. This value may be compared to the heat of formation of Δ _f H ^pet _298.15= ?4886.5±6.3 kJ mol^?1 determined by the HF solution calorimetry by Bennington et?al. (1980). Faßhauer et?al. (1998) combined thermodynamic data with phase-equilibrium results to obtain best-fit thermodynamic results using the Bayes method, in order to derive an internally consistent dataset for phases in the NaAlSiO₄– LiAlSiO₄–Al₂O₃–SiO₂–H₂O system. They determined ?4865.6?±?0.8?kJ?mol^?1 as the enthalpy of formation of petalite, a value that is appreciably closer to the enthalpy found in this work.     

Cation ordering in BaAl2Ge2O8-feldspar: implications for the phase transition in anorthite

BaAl₂Ge₂O₈-Feldspar undergoes an order-disorder phase transition I2/c↔C2/m at T _tr ≈1690 K. The thermodynamics of the Al,Ge cation ordering process is described in terms of the compressible Ising model in mean field approximation. The mean field potential predicts a first order character of the phase transition. This is compared to antiferromagnetic ordering in a two-dimensional square Ising model with NN-pair interactions and four-spin interactions on alternating squares. Calculated order parameters and short range ordering are in good agreement with the corresponding properties observed in BaAl₂Ge₂O₈-feldspar by means of X-ray diffraction, hard mode infrared spectroscopy and TEM. Using known calorimetric data a similar model is postulated for Al,Si ordering in anorthite, CaAl₂Si₂O₈, for which the derived potential describes a transition with slightly stronger first order character at T _tr ≈1928 K. Received: 30 January 1998 / Revised, accepted: 29 August 1998     

Phase transition of synthetic zinc ferrite spinel (ZnFe2O4) at high pressure, from synchrotron X-ray powder diffraction

 Synthetic Zn-ferrite (ideally ZnFe₂O₄; mineral name: franklinite) was studied up to 37 GPa, by X-ray powder diffraction at ESRF (Grenoble, France), on the ID9 beamline; high pressure was achieved by means of a DAC. The P-V equation of state of franklinite was investigated using the Birch-Murnaghan function, and the elastic properties thus inferred [K₀ = 166.4(±3.0) GPa K₀ ^′ = 9.3(±0.6) K₀ ^″ = −0.22 GPa⁻¹] are compared with earlier determinations for MgAl-spinel and magnetite. The structural behaviour of Zn-ferrite as a function of pressure was studied by Rietveld refinements, and interpreted in the light of a phase transition from spinel to either CaTi₂O₄- or MnFe₂O₄-like structure; this transformation occurs above 24 GPa. Received: 15 March 1999 / Accepted: 22 April 2000     

The crystal and magnetic structure of Li-aegirine LiFe3+Si2O6: a temperature-dependent study

Single crystals of Li-aegirine LiFe³⁺Si₂O₆ were synthesized at 1573?K and 3?GPa, and a polycrystalline sample suitable for neutron diffraction was produced by ceramic sintering at 1223?K. LiFe³⁺Si₂O₆ is monoclinic, space group C2/c, a=9.6641(2)?Å, b= 8.6612(3)?Å, c=5.2924(2)?Å, β=110.12(1)^° at 300?K as refined from powder neutron data. At 229?K Li-aegirine undergoes a phase transition from C2/c to P2₁ /c. This is indicated by strong discontinuities in the temperature variation of the lattice parameters, especially for the monoclinic angle β and by the appearance of Bragg reflections (hkl) with h+k≠2n. In the low-temperature form two non-equivalent Si-sites with 〈SiA–O〉=1.622?Å and 〈SiB–O〉=1.624?Å at 100?K are present. The bridging angles of the SiO₄ tetrahedra O3–O3–O3 are 192.55(8)° and 160.02(9)° at 100?K in the two independent tetrahedral chains in space group P2₁ /c, whereas it is 180.83(9)° at 300?K in the high-temperature C2/c phase, i.e. the chains are nearly fully expanded. Upon the phase transition the Li-coordination changes from six to five. At 100?K four Li–O bond lengths lie within 2.072(4)–2.172(3)?Å, the fifth Li–O bond length is 2.356(4)?Å, whereas the Li–O3?A bond lengths amount to 2.796(4)?Å. From ⁵⁷Fe Mössbauer spectroscopic measurements between 80 and 500?K the structural phase transition is characterized by a small discontinuity of the quadrupole splitting. Temperature-dependent neutron powder diffraction experiments show first occurrence of magnetic reflections at 16.5?K in good agreement with the point of inflection in the temperature-dependent magnetization of LiFe³⁺Si₂O₆. Distinct preordering phenomena can be observed up to 35?K. At the magnetic phase transition the unit cell parameters exhibit a pronounced magneto-striction of the lattice. Below T _N Li-aegirine shows a collinear antiferromagnetic structure. From our neutron powder diffraction experiments we extract a collinear antiferromagnetic spin arrangement within the a–c plane.     

In situ X-ray observations of phase transitions in MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel to 40 GPa using multianvil apparatus with sintered diamond anvils

 Phase transitions in MgAl₂O₄ spinel have been studied at pressures 22–38 GPa, and at temperatures up to 1600 °C, using a combination of synchrotron radiation and a multianvil apparatus with sintered diamond anvils. Spinel dissociated into a mixture of MgO plus Al₂O₃ at pressures to 25 GPa, while it transformed to the CaFe₂O₄ (calcium ferrite) structure at higher pressures via the metastably formed oxide mixture upon increasing temperature. Neither the e-phase nor the CaTi₂O₄-type MgAl₂O₄, which were reported in earlier studies using the diamond-anvil cell, were observed in the present pressure and temperature range. The zero-pressure bulk modulus of the calcium-ferrite-type MgAl₂O₄ was calculated as K=213 (3) GPa, which is significantly lower than that reported by Yutani et al. (1997), but is consistent with a more recent result by Funamori et al. (1998) and that estimated by an ab initio calculation by Catti (2001). Received: 2 April 2002 / Accepted: 29 July 2002 Acknowledgements The authors thank Y. Higo, Y. Sueda, T.␣Ueda, Y. Tanimoto, A. Fukuyama, K. Ochi, F. Kurio and T. Kawahara for help in the in situ X-ray observations at SPring-8 (No: 2000A0061-CD-np and 2000B0093-ND-np). We also thank W.␣Utsumi, J. Ando and O. Shimomura for advice and encouragement during this study, and N. Funamori and an anonymous reviwer for comments on the article. The present study is partly supported by the grant-in-aid for Scientific Research (A) of the Ministry of Education, Science, Sport and Culture of the Japanese government (no: 11694088).     

Structure and compressibility of synthetic ZnAl2O4 (gahnite) under high-pressure conditions, from synchrotron X-ray powder diffraction

 The structural behavior of synthetic gahnite (ZnAl₂O₄) has been investigated by X-ray powder diffraction at high pressure (0–43 GPa) and room temperature, on the ID9 beamline at ESRF. The equation of state of gahnite has been derived using the models of Birch–Murnaghan, Vinet and Poirier–Tarantola, and the results have been mutually compared (the elastic bulk modulus and its derivatives versus P determined by the third-order Birch–Murnaghan equation of state are K ₀=201.7(±0.9) GPa, K ^′ ₀=7.62(±0.09) and K ^″ ₀=−0.1022 GPa⁻¹ (implied value). The compressibilities of the tetrahedral and octahedral bond lengths [0.00188(8) and 0.00142(5) GPa⁻¹ at P=0, respectively], and the␣polyhedral volume compressibilities of the four-␣and␣sixfold coordination sites [0.0057(2) and 0.0041(2) GPa⁻¹ at P=0, respectively] are discussed. Received: 15 January 2001 / Accepted: 23 April 2001     

Simulation of structural phase transition in NaNO3 and CaCO3

 The order-disorder phase transitions in NaNO₃ and CaCO₃ are simulated by molecular dynamics. The simulations are based on the potentials calculated from the Gordon–Kim modified electron gas formalism extended to molecular ions. We successfully reproduced the transition temperature T _c and the abnormally large c axis thermal expansion observed in experiment. The phase transitions in NaNO₃ and CaCO₃ were found to be initiated by ±60 and ±180° reorientation of the NO₃ and CO₃ ions about the c axis. The orientations of NO₃ and CO₃ ions are continuous with six preferred calcite-type orientations above the phase-transition temperature. Received: 30 January 2001 / Accepted: 11 May 2001     

Phosphorus oxynitride PON, a silica analogue: structure and compression of the cristobalite-like phase; P –T phase diagram

 The structure of the cristobalite-like polymorph of phosphorus oxynitride PON has been refined using neutron powder diffraction data. It is tetragonal, space group I&4macr;2d, Z=4. The four P–(O,N) distances are equal but the tetrahedron is compressed along c. In AX₂ or ABX₄ compounds, the tetragonal I&4macr;2d or I&4macr; structure is obtained when the average ratio of the cation to anion radius is below 1.186, whereas the tetragonal P4₁2₁2 or orthorhombic C222₁ structure is obtained at low temperatures for larger ratios. The cell parameters of this PON polymorph have been determined as a function of hydrostatic pressure by in situ angle dispersive X-ray powder diffraction in a diamond-anvil cell. Under truly hydrostatic pressure, a strong anisotropic behavior is observed with the c parameter being nearly incompressible. Very slight anisotropic stress strongly modifies the high-pressure behavior. According to the pressure-temperature conditions of treatment, three phases, cristobalite-, moganite-, and quartz-like, have been obtained by quenching experiments, and the P–T phase diagram of PON was derived. The high-pressure behavior of the α-quartz, moganite, and cristobalite-like polymorphs of PON and SiO₂ is discussed. Received: 7 August 2000 / Accepted: 21 January 2001     

Thermal expansion and structural transformations of stuffed derivatives of quartz along the LiAlSiO4–SiO2 join: a variable-temperature powder synchrotron XRD study

 The structural behavior of stuffed derivatives of quartz within the Li_{1− x} Al_{1− x} Si_{1+ x} O₄ system (0 ≤ x ≤ 1) has been studied in the temperature range 20 to 873 K using high-resolution powder synchrotron X-ray diffraction (XRD). Rietveld analysis reveals three distinct regimes whose boundaries are defined by an Al/Si order-disorder transition at x=∼0.3 and a β–α displacive transformation at x=∼0.65. Compounds that are topologically identical to β-quartz (0 ≤ x < ∼0.65) expand within the (0 0 1) plane and contract along c with increasing temperature; however, this thermal anisotropy is significantly higher for structures within the regime 0 ≤ x < ∼0.3 than for those with compositions ∼0.3 ≤ x < ∼0.65. We attribute this disparity to a tetrahedral tilting mechanism that occurs only in the ordered structures (0 ≤ x < ∼0.3). The phases with ∼0.65 ≤ x ≤ 1 adopt the α-quartz structure at room temperature, and they display positive thermal expansion along both a and c from 20 K to their α–β transition temperatures. This behavior arises mainly from a rotation of rigid Si(Al)-tetrahedra about the <100> axes. Landau analysis provides quantitative evidence that the charge-coupled substitution of Li+Al for Si in quartz dampens the α–β transition. With increasing Li+Al content, the low-temperature modifications exhibit a marked decrease in spontaneous strain; this behavior reflects a weakening of the first-order character of the transition. In addition, we observe a linear decrease in the α–β critical temperature from 846 K to near 0 K as the Li+Al content increases from x=0 to x=∼0.5. Received: 26 June 2000 / Accepted: 1 December 2000     

Polysomatism and modules of gehlenite composition and structure in the Hanic phase (Ca5Al6MgSiO17)

 Discrete, well-ordered, single-phase crystals (the Hanic phase) form when powders the bulk composition of Ca₅Al₆MgSiO₁₇ are allowed to react in the absence of a melt. If, on the other hand, either the powders or crystals of Ca₅Al₆MgSiO₁₇ are molten and then cooled, complex intergrowths form. These intergrowths consist of modules having the composition and structure of Ca₃Al₄MgO₁₀ and gehlenite (Ca₂Al₂SiO₇), forming a polysomatic series in which the modules occur in varied proportions. High-resolution transmission electron microscope (HRTEM) images reveal the details of these intergrowths. Mass balance is achieved by the formation of this polysomatic series together with Mg-substituted mayenite (Ca_12−xMg_xAl₁₄O₃₃). The tetrahedral sheets in gehlenite have close structural similarities to those of Ca₅Al₆O₁₄. Based on our HRTEM images, we hypothesize chemical substitutions between gehlenite and Ca₅Al₆O₁₄, resulting in gehlenite-like modules that are depleted in Si and correspondingly enriched in Al and Ca. Received: 2 August 2000 / Accepted: 18 January 2001     

Microsommite: crystal chemistry, phase transitions, Ising model and Monte Carlo simulations

Microsommite, ideal formula [Na₄K₂(SO₄)] [Ca₂Cl₂][Si₆Al₆O₂₄], is a rare feldspathoid that occurs in volcanic products of Vesuvius. It belongs to the cancrinite–davyne group of minerals, presenting an ABAB… stacking sequence of layers that contain six-membered rings of tetrahedra, with Si and Al cations regularly alternating in the tetrahedral sites. The structure was refined in space group P6₃ to R=0.053 by means of single-crystal X-ray diffraction data. The cell parameters are a=22.161?Å=√3a _dav, c=5.358?Å=c _dav; Z=3. The superstructure arises due to the long-range ordering of extra-framework ions within the channels of the structure. This ordering progressively decreases with rising temperature until it is completely lost and microsommite transforms into davyne. The order–disorder transformation has been monitored in several crystals by means of X-ray superstructure reflections and the critical parameters T _c?≈?750?°C and β?≈?0.12 were obtained. The kinetics of the ordering process were followed at different temperatures and the activation energy was determined to be about 125?kJ?mol^?1. The continuous order–disorder phase transition in microsommite has been discussed on the basis of a two-dimensional Ising model in a triangular lattice with nn (nearest neighbours) and nnn (next-nearest neighbours) interactions. Such a model was simulated using a Monte Carlo technique. The theoretical model well matches the experimental data; two phase transitions were indicated by the simulated runs: at low temperature only one of the three sublattices begins to disorder, whereas the second transition involves all three sublattices.     

Heating-induced phase transformation in zeolite brewsterite: new 4- and 5-coordinated (Si,Al) sites

The dehydration-rehydration processes and phase transformations of brewsterite (space group P2₁/m, ideal formula (Sr,Ba)Al₂Si₆O₁₆·5H₂O) were studied by single crystal X-ray diffraction on two samples heated in an evacuated capillary for 24 h at 280°C and 330°C, respectively, and then cooled to room temperature. After the data collection, the capillary of the crystal heated at 280°C was broken, the sample was kept at room conditions for one month, and diffraction data were recollected. Brewsterite heated in vacuum at 280°C shows a strong decrease of the unit cell volume (about 10%) and the statistical breaking of the T1-O7-T2 bridge of the 4-ring of the 4²5⁴ PBU. T1 cation, in 31% of cases, migrates to a new tetrahedral site, which shares three vertices with the previously occupied one; the fourth vertex is on the mirror plane, and joins two adjacent layers. T2 cation, in 20% of cases, migrates to a new site, which is characterized by a 5-fold coordination. This coordination polyhedron shares three vertices with the previously occupied tetrahedron; the fourth vertex is on the mirror plane, and joins two adjacent layers; the fifth one is unshared. The formation of these new T-O-T bridges prevents the re-expansion and rehydration of the heated brewsterite; as a consequence, the crystal brought back to room conditions does not show any noticeable structural difference with respect to that heated at 280°C. The exchangeable cations, which occupy only one extraframework site in the untreated brewsterite, spread over several sites. The sample heated at 330°C shows a further decrease in the unit cell volume of about 2% with respect to the sample heated at 280°C, and an increase in the migration percentage of T1 and T2 cations to the new sites. Received: 11 November 1997 / Revised, accepted: 26 June 1998     

High-pressure phase transition and behavior of protons in brucite Mg(OH)2: a high-pressure–temperature study using IR synchrotron radiation

 Infrared absorption spectra of brucite Mg (OH)₂ were measured under high pressure and high temperature from 0.1 MPa 25 °C to 16 GPa 360 °C using infrared synchrotron radiation at BL43IR of Spring-8 and a high-temperature diamond-anvil cell. Brucite originally has an absorption peak at 3700 cm⁻¹, which is due to the OH dipole at ambient pressure. Over 3 GPa, brucite shows a pressure-induced absorption peak at 3650 cm⁻¹. The pressure-induced peak can be assigned to a new OH dipole under pressure. The new peak indicates that brucite has a new proton site under pressure and undergoes a high-pressure phase transition. From observations of the pressure-induced peak under various P–T condition, a stable region of the high-pressure phase was determined. The original peak shifts to lower wavenumber at −0.25 cm⁻¹ GPa⁻¹, while the pressure-induced peak shifts at −5.1 cm⁻¹ GPa⁻¹. These negative dependences of original and pressure-induced peak shifts against pressure result from enhanced hydrogen bond by shortened O–H···O distance, and the two dependences must result from the differences of hydrogen bond types of the original and pressure-induced peaks, most likely from trifurcated and bent types, respectively. Under high pressure and high temperature, the pressure-induced peak disappears, but a broad absorption band between 3300 and 3500 cm⁻¹ was observed. The broad absorption band may suggest free proton, and the possibility of proton conduction in brucite under high pressure and temperature. Received: 16 July 2001 / Accepted: 25 December 2001     

Geochemical evolution of high-pressure mafic granulites from the Bacariza formation (Cabo Ortegal complex, NW Spain): an example of a heterogeneous lower crust

 The Cabo Ortegal complex (northwestern Iberian massif) is a klippen formed of several structural units stacked during the Hercynian collision. All these units include ultramafic rocks, metabasites and quartz-feldspathic gneisses affected by different metamorphic conditions. The Bacariza formation is heterogeneous showing a conspicuous layering mainly defined by alternate high-pressure ultrabasic-to-basic granulites, retrogressed garnet amphibolites of intermediate composition and rare acid rocks forming garnet trondhjemitic gneisses. This layering is inherited from a gabbroic protolith showing a composition rich in Fe and Ti. Major and trace elements of these rocks can be correlated to continental tholeiitic series of extensional settings. These high-pressure granulites are situated in normal contact between±serpentinised ultramafic rocks and other high-grade metabasites with lessevolved and more-depleted composition comparable to T-type and N-type MORB. It is suggested that the layered gabbro-type protolith was part of a continuous mafic crust. This crust was initially formed during Early Ordovician in a continental extensional setting and progressively evolved to oceanic spreading. Received: 9 February 1996/Accepted: 10 February 1997     

Assessment of mercury contamination and human exposure associated with coastal disposal of waste from a cinnabar mining operation, Palawan, Philippines

 An integrated geochemical and toxicological assessment of environmental mercury contamination and attendant human exposure in Honda Bay, Palawan was undertaken in 1995 following a nationally reported pollution scare centered on a coastal jetty, Sitio Honda Bay, constructed using approximately 1 million tons of tailings and beneficiation waste from a cinnabar mine. Mercury (Hg) data for marine and fluvial sediments, fish tissues and human hair indicate that the toxicological hazard is considerably lower than initially reported by state environment and health officials. Typical Hg concentrations in surficial Honda Bay sediments were found to lie within the global background range (<60 μg/kg). Downcore profiles provide no evidence of enhanced Hg fluxes coincident with the onset of mining and/or coastal tailings disposal. The mean and median Hg concentrations recorded in tissues of six species of Honda Bay fish are compliant with thresholds established by the US Environmental Protection Agency (US-EPA) for marketable stocks. Earlier reports of 'Minamata range' Hg concentrations in fish and shellfish from Honda Bay remain unsubstantiated. Geochemical analyses of samples of the Sitio Honda Bay substrate have confirmed the prevalence of solid-phase Hg concentrations to ca. 340 mg/kg. The speciation of Hg is, however, dominated by secondary oxides of low bioavailability. The mean Hg concentration in hair from Sitio Honda Bay residents (4.41 mg/kg) was found to be statistically analogous to that for a neighbouring coastal community unimpacted by the coastal disposal of mine waste. A negligible residential exposure factor is thus inferred for the former. Relatively high hair Hg burdens prevail throughout the coastal Honda Bay population, consistent with significant methyl Hg ingestion through daily fish consumption. The data presented provide no environmental or toxicological justification for immediate remedial action. Received: 14 May 1998/Accepted: 1 September 1998     

Analysis of groundwater discharge with a lumped-parameter model, using a case study from Tajikistan

 A lumped-parameter model of groundwater balance is proposed that permits an estimate of discharge variability in comparison with the variability of recharge, by taking into account the influence of aquifer parameters. Recharge–discharge relationships are analysed with the model for cases of deterministic and stochastic recharge time-series variations. The model is applied to study the temporal variability of groundwater discharge in a river valley in the territory of Tajikistan, an independent republic in Central Asia. Received, April 1996 Revised, August 1997 Accepted, March 1998     

Magnetic phase diagrams of Mg-, Fe-, (Cu + Ti)- and Cu-substituted braunite Mn<Superscript>2+</Superscript>Mn<Subscript>6</Subscript><Superscript>3+</Superscript>SiO<Subscript>12</Subscript>

 The magnetic behavior of the Jahn-Teller structure braunite, (Mn²⁺ _1−yM _y )(Mn³⁺ _{6− x} M_x)SiO₁₂, is strongly influenced by the incorporation of elements substituting manganese. Magnetic properties of well-defined synthetic samples were investigated in dependence on the composition. The final results are presented in magnetic phase diagrams. To derive the necessary data, ac susceptibility and magnetization of braunites with the substitutional elements M = Mg, Fe, (Cu+Ti) and Cu were measured. Whereas the antiferromagnetic ordering temperature, T _N , of pure braunite is hardly affected by the substitution of nonmagnetic Mg, it is rapidly suppressed by the substitution of magnetic atoms at the Mn positions. Typically for a concentration (x, y) ≥ 0.7 of the substituted elements, a spin glass phase occurs in the magnetic phase diagrams. Additionally, for the braunite system with Fe³⁺ substitutions, we observe in the concentration range 0.2 < x< 0.7 a double transition from the paramagnetic state, first to the antiferromagnetic state, followed by a transition to a spin glass state at lower temperatures. The unusual change of the magnetic properties with magnetic substitution at the Mn positions is attributed to the peculiar antiferromagnetic structure of braunite, which has been resolved recently. Received: 19 April 2001 / Accepted: 6 September 2001