Crystal chemistry of a clinopyroxene series in ultrafemic xenoliths from North-Eastern Brazil

A series of clinopyroxenes (Cpx) in peridotitic spinel nodules from Rio Grande do Norte, North-Eastern Brazil, was investigated by X-ray diffraction and electron microprobe analyses and compared with an analogous series from spinel peridotite nodules from Mt. Leura, Victoria, Australia. The examined Cpx series is mainly characterized by increasing Mg/(Mg+Fe²⁺) ratio (i.e. increase of refractory character of the host nodules), by the substitutions of Al^vi vs Mg in the M1 site and Na vs (Ca+Mg) in the M2 site, whereas Al^iv in the T site remains substantially constant. The strong Na depletion in the Brazilian Cpx causes a different charge balance from that in the Australian Cpx, in which Na remains quite constant. This feature, associated with the differences in polyhedral and cell volumes which are significantly higher in the Brazilian Cpx than in those of the Australian Cpx, suggests that the Brazilian Cpx crystal chemistry may be related to a lower pressure regime, compared with that of the Australian Cpx series.     

Luminescence excitation spectra of Mn2+ in synthetic forsterite

Detailed ligand-field spectra of Mn²⁺ in both microcrystalline and single-crystal synthetic forsterite are obtained using the technique of luminescence excitation spectroscopy. It is shown that Mn²⁺ has an almost exclusive preference for one particular cation site which is most probably the M2 site. Low temperature measurements reveal a no-phonon (purely electronic) transition at 16,260 cm^?1 (615 nm) which is the energy of the lowest split component of the ⁴ T ₁(G) state above the ground state. Phonon replicas of this transition are evident showing that a particular phonon mode (180 cm^?1) is dominantly involved. An analysis of the polarized spectra of Mn²⁺ in single-crystal forsterite shows the choice of C _2v (C ₂, σ _d ) pseudosymmetry for the M2 site yields the best agreement with the polarization dependence of the transitions between the ligand-field states of the Mn²⁺ ion in this site.     

Mn3+ in garnets III. Absence of Jahn-Teller distorition in synthetic Mn3+-bearing garnet

Physics and Chemistry of Minerals - The crystal structure of a ternary Mn3+-bearing garnet, close to the composition Gross34 Spess26 CaMnGt40 has been refined to a weighted R-value of 0.051 for 440...     

An EPR study of Mn2+ and Fe3+ in dolomites

Electron paramagnetic resonance (EPR) measurements on dolomites from 9 different localities revealed contents of Mn²⁺ on two axial sites in all of them. The center with largerzero-field splitting (ZFS) was always present in much higher concentrations, except for a sample from Oberdorf it amounted to 95 percent or more of the total. This dolomite was the only one with a considerable content of Fe³⁺ on one axial site, almost certainly substituting for Mg²⁺. With X-ray irradiation the concentration of Fe³⁺ increased by about 30 percent showing that at least some of the divalent iron also substitutes for Mg. The ZFSs for Fe³⁺ and Mn²⁺ with larger ZFS increase with decreasing temperature in the same manner. The previous assignment of this Mn²⁺ to Mg sites is thus confirmed. An almost regular increase of the trigonal distortions at the divalent ions in different carbonates with increasing ionic radius is indicated by their crystal structure data. The very small ZFS for Mn²⁺ on Ca sites in dolomite must thus result from a strong local relaxation in the direction of a more regular octahedral arrangement. It is difficult to explain the different distribution ratios of Mn²⁺ on Ca and Mg sites with differences in growth and/or annealing temperatures alone. Thus different supply of Mg²⁺ and Ca²⁺ in the growth solutions may also contribute.     

High pressure single-crystal synthesis, structure and compressibility of the garnet Mn2+ 3Mn3+ 2[SiO4]3

Single crystals of the garnet Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ and coesite were synthesised from MnO₂-SiO₂ oxide mixtures at 1000°C and 9 GPa in a multianvil press. The crystal structure of the garnet [space group Ia3¯d, a=11.801(2) Å] was refined at room temperature and 100 K from single-crystal X-ray data to R1=2.36% and R1=2.71%, respectively. In contrast to tetragonal Ca₃Mn³⁺ ₂[GeO₄]₃ (space group I4₁/a), the high-pressure garnet is cubic and does not display an ordered Jahn-Teller distortion of octahedral Mn³⁺. A disordered Jahn-Teller distortion either dynamic or static is evidenced by unusual high anisotropic displacement parameters. The room temperature structure is characterised by following bond lengths: Si-O=1.636(4) Å (tetrahedron), Mn³⁺-O=1.995 (4) Å (octahedron), Mn²⁺-O=2.280(5) and 2.409(4) Å (dodecahedron). The cubic structure was preserved upon cooling to 100 K [a=11.788(2) Å] and upon compressing up to 11.8 GPa in a diamond-anvil cell. Pressure variation of the unit cell parameter expressed by a third-order Birch-Murnaghan equation of state led to a bulk modulus K ₀=151.6(8) GPa and its pressure derivatives K′=6.38(19). The peak positions of the Raman spectrum recorded for Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ were assigned based on a calderite Mn²⁺ ₃Fe³⁺ ₂[SiO₄]₃ model extrapolated from andradite and grossular literature data.     

Time-resolved luminescence of Fe3+ and Mn2+ ions in hydrous volcanic glasses

 Time-resolved luminescence spectra of natural and synthetic hydrous volcanic glasses with different colors and different Fe, Mn, and H₂O content were measured, and the implications for the glass structure are discussed. Three luminescence ranges are observed at about 380–460, 500–560, and 700–760 nm. The very short-living (lifetimes less than 40 ns) blue band (380–460 nm) is most probably due to the ⁴T₂(⁴D) →⁶A₁(⁶S) and ⁴A₁(⁴G) →⁶A₁(⁶S) ligand field transitions of Fe³⁺. The green luminescence (500–560 nm) arises from the Mn²⁺ transition ⁴T₁(⁴G) →⁶A₁(⁶S). It shows weak vibronic structure, short lifetimes less than 250 μs, and indicates that Mn²⁺ is tetrahedrally coordinated, occupying sites with similar distortions and ion–oxygen interactions in all samples studied. The red luminescence (700–760 nm) arising from the ⁴T₁(⁴G) →⁶A₁(⁶S) transition of Fe³⁺ has much longer lifetimes of the order of several ms, and indicates that ferric iron is also mainly tetrahedrally coordinated. Increasing the total water content of the glasses leads to quenching of the red luminescence and decrease of the distortions of the Fe³⁺ polyhedra. Received: 30 July 2001 / Accepted: 15 November 2001     

Structural control of polyhedral compression in synthetic braunite, Mn2+Mn3+ 6O8SiO4

The compression of synthetic braunite, Mn²⁺Mn³⁺ ₆O₈SiO₄, was studied by high-pressure single-crystal X-ray diffraction carried out in a diamond-anvil cell. The equation of state at room temperature (third-order Birch-Murnaghan equation of state: V ₀=1661.15(8) ų, K _0,298=180.7±0.9 GPa, K′=6.5±0.3) was determined from unit-cell volume data to 9.18 GPa. Crystal structures were determined at 6 different pressures to 7.69 GPa. Compression of the structure (space group I4₁/acd) was found to be slightly anisotropic (a ₀=9.4262(4) Å, K _a =499±4 GPa, K _a ′=19.7±0.9; c ₀=18.6964(6) Å, K _c =657±6 GPa, K _c ′=15.7±1.4) which can be attributed to the fact that the Mn³⁺-O bonds, which are the most compressible bonds, are aligned closer to the (001) plane than to the c axis. The large bulk modulus is the result of the structural topology in which 2/3 and 1/2 of the edges of the Mn²⁺O₈ and Mn³⁺O₆ polyhedra share edges with other polyhedra. The Mn²⁺O₈ polyhedra were found to compress isotropically, whereas anisotropic compressional behaviour was observed for all three Mn³⁺O₆ octahedra. Although the polyhedral geometry of all three crystallographically independent Mn³⁺ sites shows the same type of uniaxially elongated distortion, the compression of the individual octahedral configurations was found to be strongly dependent upon both the geometry of the polyhedron itself and the types of, and the connectivity to, the neighbouring polyhedra. The differences in the configuration of the different oxygen atoms, and therefore the structural topology, is one of the major factors determining the type and degree of the pressure-induced distortion, while the Jahn-Teller effect plays a subordinate role.     

Crystal structure refinement and reflectance measurements of hausmannite,Mn3O4

Summary The crystal structure of hausmannite from Langbån, Sweden, was refined with 462 independent X-ray diffraction data toR = 0.036 (R_W = 0.034). The Jahn-Teller distortion of the Mn³⁺O6 octahedron is relatively strong: Mn³⁺ -O = 1.930 (1) Å (4 x), 2.282 (1) Å (2 x), and the anisotropies of the thermal vibrations of Mn^3- and O differ clearly from those of the corresponding atoms in cubic spinels. It is shown that, from a stereochemical point of view, the hausmannite structure-type is not the only geometrically possible Jahn-Teller distortion of the spinel-type. The reflectance of hausmannite was measured on an oriented cut plate with polarized light (k = 400–700 nm) in air and in oil immersion, and the refractive indices and absorption coefficients were derived.

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Kristallstrukturverfeinerung und reflexionsmessungen am Hausmannit, Mn₃O₄

Zusammenfassung Die Kristallstruktur eines Hausmannits von Langbån, Schweden, wurde an Hand von 462 unabhängigen Einkristall-Röntgendiffraktometerdaten zu einemR = 0.036 (R _w = 0.034) verfeinert. Die Jahn-Teller-Verzerrung des Mn3+O_6-Oktaeders ist relativ stark: Mn^3--O = 1.930 (1) Å (4 x); 2.282 (1) Å (2 x), und die Anisotropien der thermischen Schwingungen von Mn3 und O unterscheiden sich deutlich von denen analoger Atome in kubischen Spinellen. Es wird gezeigt, daß aus einer stereochemischen Sicht der Strukturtyp des Hausmannits nicht die einzig geometrisch mögliche JahnTeller-Verzerrung des Spinell-Typs ist. Das Reflexionsvermögen des Hausmannits wurde an einer orientiert geschnittenen Platte mit polarisiertem Licht ( = 400–700 nm) in Luft und in Ölimmersion gemessen und Brechungsindizes und Absorptionskoeffizienten wurden bestimmt.

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With 2 Figures     

The effect of “A” site occupancy upon the hydroxyl stretching frequency in clinoamphiboles

The electric field arising from K⁺ or Na⁺ in the A sites of synthetic hydroxyamphiboles of the richterite-tremolite series raises the stretching frequency of adjacent OH groups by about 60 cm^–1. In natural amphiboles, however, the increase in frequency is generally only 20–40 cm^–1, due, probably, to the effects of such substitutions as F for OH and Al for Si.     

Mn2+和Fe3+的致色作用:来自意大利白垩纪远洋红色灰岩的启示

本文首先详细研究了含Mn2 和Fe3 的致色矿物菱锰矿、鲕状赤铁矿、云母赤铁矿和镜铁矿的可见光吸收光谱及其一阶导数谱,鲕状赤铁矿、云母赤铁矿和镜铁矿的可见光吸收一阶导数谱的红光区的吸收谷的位置的变化表明随赤铁矿结晶度的降低,吸收谷由586.4nm移至577.4nm,而菱锰矿展示出了Mn2 的因电子跃迁产生的四个典型吸收及其一阶导数谱上577nm的吸收谷的强度比赤铁矿相应谷的强度低一个数量级,表明其电子跃迁的致色机理与赤铁矿的染色机理完全不同。依据赤铁矿的结晶度和鲕状赤铁矿与大洋红层中赤铁矿的沉积成因相似的原则遴选出鲕状赤铁矿为含Fe3 致色矿物,依据菱锰矿是和方解石具有相似结构且为红色的原则选取菱锰矿为含锰致色矿物,并佐以化学纯氧化镁为基体配制了一系列的含菱锰矿、鲕状赤铁矿和菱锰矿及鲕状赤铁矿的两相或三相混合物。详细研究了三类混合物的可见光吸收光谱的一阶导数谱,发现含菱锰矿和含鲕状赤铁矿在573nm附近均存在一吸收谷,鲕状赤铁矿的重量分数低至0.05%时仍可见一明显吸收谷且该吸收谷移至565nm附近,菱锰矿在低至0.50%时也可见这一吸收且在低至0.11%时仍可显示出菱锰矿的信息,其575nm的吸收峰未见偏移;混合物可见光一阶导数吸收谱上鲕状赤铁矿的575nm附近的吸收谷的强度随鲕状赤铁矿的重量分数的升高而增强,而所有的配制混合物中该吸收谷的位置低于577.4nm的事实也表明为使致色矿物和氧化镁混合均匀的研磨降低了赤铁矿的结晶度。本研究表明Mn2 的电子跃迁激发和细小、结晶差的赤铁矿的染色共同造就了意大利白垩纪远洋红色灰岩的红色。     

Characterization and origin of two Fe3+ EPR spectra in kaolinite

The electron paramagnetic resonance (EPR) spectra of Fe³⁺ in a well cristallized kaolinite from Decazeville in France are well resolved. It is shown that in this sample there are mainly two slightly different spectra, well separated at low temperature and characterized at -150° C by the constants B ₂ ⁰ = 0.112 cm^?1, B ₂ ² = 0.0688 cm^?1 for one and B ₂ ⁰ = 0.116 cm^?1, B ₂ ² = 0.0766 cm^?1 for the second. These two spectra arise from Fe³⁺ substituted for Al³⁺ at the two octahedral positions in equal amounts. The temperature dependence of EPR spectra was studied and was explained by a modification of the octahedral sites.     

Partitioning of Hf,Lu, Ti,and Mn between olivine,clinopyroxene and basaltic liquid

The crystal/liquid partition coefficients of Lu, Hf, Ti, Mn and Ca have been measured between olivine, clinopyroxene and basaltic melt. The Ti, Mn, and Ca partition coefficients were determined at natural abundance levels. The Lu and Hf partition coefficients were determined at doping levels ranging from 0.5 to 1.5 wt% “trace element” as oxide in order to allow analysis by electron microprobe. Olivine/liquid partition coefficients for Lu, Hf, Ti, Mn, and Ca were determined at 1 bar and temperatures from 1150 to 1177° C. Clinopyroxene/liquid partition coefficients were determined for Lu, Hf, Ti, and Mn at pressures of 10, 15, and 20 kbars and temperatures from 1250 to 1290° C. The olivine/liquid partition coefficients of Hf, Lu, Ti, and Ca are small. D(Hf-ol) is zero within the analytical uncertainty. Both D(Lu-ol) and D(Mn-ol) decrease with increasing temperature, but D(Ti-ol) and D(Ca-ol) are constant over the narrow temperature range studied. The partition coefficient results are summarized below.

Electronic absorption spectra of Cr3+ ions in natural clinopyroxenes

The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr₂O₃), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr³⁺ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C ₂ or C _2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C _3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D _q increases from diopside (1542 cm^?1) through omphacite (1552 cm^?1), jadeite (1574 cm^?1) to spodumene (1592 cm^?1). The parameter B which is a measure of covalency for Cr³⁺-O bonds at M1 sites in clinopyroxene depends on the Cr³⁺ concentration and the cations at M2 sites.     

Crystal chemistry and evolution of the clinopyroxene in a suite of high pressure ultramafic nodules from the Newer Volcanics of Victoria,Australia

A clinopyroxene suite from lherzolite inclusions associated with the Victorian (Australia) “Newer Volcanics” has been investigated with the aim of understanding the clinopyroxene crystal-chemical response to increasing temperature (e.g. a melting model and/or crystallization processes prevailing at high pressure). The M1 clinopyroxene polyhedron dominates the intracrystalline physical-chemical variations, essentially given by the triple substitution Al^VIFe _M1 ² Ti⁴⁺⇌Cr³⁺ Fe³⁺Mg _M1 ²⁺ corresponding to an increase in the volume of M1 with increasing Mg/Mg+Fe²⁺ (mg) for the clinopyroxene. A relative Ca²⁺ increase in M2 ensures the necessary charge balance. However, Na⁺ occupancy of M2 persists to the highest mg values, i.e. maximum thermal stability, where the volume of M2 is the largest due to Fe _M2 ²⁺ depletion. The variations of M1 and M2 volumes are greater than, and opposite to, the variations in the volume of T (tetrahedron) by factors of ca. 3 and 1.5, respectively. Inclusions with relatively low clinopyroxene content (Mt. Porndon specimens) show distinct intracrystalline variations, essentially reflecting lower Al^VI, i.e. higher volume of M1, and implying a lower pressure regime compared to clinopyroxene-rich analogues (Mt. Leura specimens). The intracrystalline relationships of the Mt. Porndon clinopyroxene suggest that the host peridotite inclusions survived larger degree of mantle melting at shallower depths relative to the Leura analogues.     

Absorption spectra of Cr3+ in Al2O3 under shock compression

Unpolarized absorption spectra of single crystals of Cr³⁺ doped Al₂O₃ (synthetic ruby) have measured using a new, time-resolving, dispersive, streak photographic system over the range ～350 to ～700 nm during a series of shock loading experiments. The crystal field absorptions assigned to the transition ⁴ A _2g→⁴ T _2g were observed to shift in a series of experiments from 555±1 nm at atmospheric pressure to 503±5 nm at 46 GPa. In a single experiment at 32 GPa the ⁴ A _2g→⁴ T _1g transition was observed to shift from 405±1 to 386±5 nm. The present data extrapolate downwards in compression toward the 10 GPa data of Stephens and Drickamer (1961) although both crystal field absorption energies increase considerably less with compression than predicted by the simple ionic point charge model. The single datum observed for the Racah parameter B, 588±38 cm^?1 at 32 GPa, is consistant with previous results to 10 GPa and the trend of decreasing B, with compression expected from the divergence of the data from the point charge model due to increasing covalancy.     

Polarized electronic absorption spectra of 3d3-configurated tetravalent manganese in octahedral fields of Mn(SeO3)2

Polarized optical absorption spectra of Mn(IV) in octahedral crystal fields of Mn(SeO₃)₂ have been studied by means of microscope-spectrometry in the range 40000-4000 cm^?1 and at temperatures between 113 K and 293 K. Intense charge-transfer absorptions (linear absorption coefficient α ? 30000 cm^?1) completely mask the d-d transitions in the UV and VIS region above ≈23000 cm^?1. The optical electronegativity χ _opt of Mn(IV) in Mn(SeO₃)₂ is estimated to be 2.7. In accordance with the d ₃ configuration of tetravalent manganese three d-d bands observed at ambient temperatures at 13250, 14137 (α≈50 cm^?1) and ≈18500 cm^?1 (α≈500–800 cm^?1) are assigned to the spin forbidden ⁴ A _2g →² E _g and ⁴ A _2g →² T _1g transitions as well as to the first spin allowed ⁴ A _2g →⁴ T ^2g transition, respectively. These assignments allow the calculation of the following ligand field parameters: Dq ≈ 1850 cm^?1, B ₅₅ = 869 cm^?1 (β ₅₅ = 0.82), and C = 2346 cm^?1 (293 K).     

Miscibility and compatibility of braunite,Mn2+Mn 6 3+ O8/SiO4, in the system Mn-Si-O at 1 atm in air

Experimental investigations between 800 ° to 1,100 ° C yielded no evidence for extensive substitution of Mn²⁺+Si⁴⁺2Mn³⁺ in braunite, leading to a complete solid solution series between partridgeite (Mn₂O₃) and braunites with silica contents up to 40 wt. % as proposed by Muan (1959a, b). In the presence of excess manganese braunite of nearly ideal composition coexists at 800 ° C with partridgeite and at T1,000 ° C with hausmannite (Mn₃O₄). At 800 ° C and 1,000 ° C braunite coexists, in the presence of excess silica, with a SiO₂-polymorph and at 1,100 ° C with rhodonite (MnSiO₃). Quantitative analysis of the X-ray patterns of coexisting cristobalite and braunite confirms a maximum silica-excess in braunite of only about 2 wt.% over the ideal composition, Mn²⁺Mn ₆ ³⁺ SiO₁₂.     

雷州英峰岭玄武岩中单斜辉石巨晶的地球化学和地幔交代作用

雷州半岛英峰岭火山岩中单斜辉石巨晶以低Mg^#值(0．62—0．47)、贫重稀土(HREE)和富Al2O3、TiO2、Na2O和中稀土(MREE)为特征，并具有明显的成分变化。随着Mg^#降低，单斜辉石的Al：O，(11．58～6．97％，)、TiO，(2．28～1．06％)和HREE逐渐降低。这种变化特征不同于世界上大多数辉石巨晶的变化规律。随着演化辉石巨晶的大多数不相容元素，如Nb、Sr、Zr、Hf和LREE—MREE逐渐增加。低的Mg^#值和Ni、Co、Cr含量指示巨晶母岩浆是一种强烈演化的残余岩浆(Mg^#=0．27～0．35)。分离结晶模拟表明本研究最富镁的巨晶(Lz-54)的母岩浆很可能是由拉斑玄武质岩浆经70～80％，以单斜辉石为主的结晶分异后形成。而本研究的其它辉石巨晶是该母岩浆在不同演化阶段(25～80％)分离结晶的产物。分离矿物中除了单斜辉石还包含了大量的石榴子石、斜长石和钛铁矿。温压计算表明英峰岭巨晶是高温岩浆在56～60km深的上地幔的结晶产物(r=1290℃～1130℃，P=1.73～1．83GPa)，这一深度有利于石榴子石结晶。对比不同地区辉石巨晶的成分特征和形成条件，作者指出不同地区单斜辉石巨晶各种元素的不同变化规律主要受母岩浆成分和结晶条件控制。巨晶母岩浆在地幔结晶时对围岩橄榄岩进行了不同程度的交代作用。早期贫流体的岩浆对橄榄岩的交代作用较弱，只有Sr，La等强活动性元素被明显改变；晚期富流体(F，P，H2O)岩浆对橄榄岩的交代作用强烈，大多数元素被明显改变。因此，可以推断交代熔体中流体的含量是影响地幔橄榄岩交代作用的关键。     

The effect of Ca-Tschermaks component on trace element partitioning between clinopyroxene and silicate melt

We have studied the influence of Ca-Tschermaks (Calcium Tschermaks or CaTs) content of clinopyroxene on the partitioning of trace elements between this phase and silicate melt at fixed temperature and pressure. Ion probe analyses of experiments carried out in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂, at 0.1 MPa and 1218°C, produced crystal-melt partition coefficients (D) of 36 trace elements (Li, Cl, Sc, Ti, V, Cr, Fe, Co, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta and W), for clinopyroxene compositions between 10 and 32 mol% CaTs. Partition coefficients for 2+ to 5+ cations show, for each charge, a near parabolic dependence of log D on ionic radius of the substituting cation, for partitioning into both the M1 and M2 sites of clinopyroxene. Fitting the results to the elastic strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372, 452–454] we obtain results for the strain-free partition coefficients of theoretical cations (D₀), with site radius r₀, and for the site's Young's Modulus (E).

In agreement with earlier data our results show that increasing ^ivAl concentration in cpx is matched by increasing D, E_M1, E_M2 and D₀ for tri-, tetra- and pentavalent cations. The degree of fractionation between chemically similar elements (i.e. Ta/Nb, Zr/Hf) also increases. In contrast, D values for mono-, di- and hexavalent cations decrease with increasing ^ivAl in the cpx. The large suite of trace elements used has allowed us to study the effects of cation charge on D₀, r₀ and E. We have found that D₀ and r₀ decrease with increasing cation charge, e.g. r₀=0.66 Å for 4+ cations and 0.59 Å for 5+ cations substituting into M1. Values of E_M1 and E_M2 increase with cation charge as well as with increasing ^ivAl content. The increase in E_M2 is linear and close to the trend set by Hazen and Finger [Hazen, R.M., Finger, L.W., 1979. Bulk modulus-volume relationship for cation–anion polyhedra. J. Geophys. Res. 84 (10) 6723–6728] for oxides. E_M1 values are much higher and do not fit the trend predicted by the Hazen and Finger relationship.