Effects of Ca-Mg substitution in C2/c pyroxene structure on natural clinopyroxenes from spinel peridotite nodules (Pico Cabugi,Brazil)

X-ray crystal structure refinements and microprobe analyses of clinopyroxenes from two suites of spinel-peridotite nodules are compared for an understanding of the structural response to a decrease in Ca content. The kinking of the tetrahedral chain (O3-O3-O3 angle) of the C2/c structure associated with decreased Ca content shows behavior similar to that observed for the A-tetrahedral chain of the P2₁/c structure. Contemporaneously the occupancy of the M2′ split site increases. In addition, as a consequence of the low Ca content, the M2 polyhedron dominates the structural rearrangement of the clinopyroxenes considered here.     

Crystal-chemistry of clinopyroxenes from potassic and ultrapotassic rocks in central Italy: implications on their genesis

The clinopyroxenes mentioned have been investigated by single crystal X-ray diffraction combined with electron microprobe analysis. The aim of this study was to characterize the crystal-chemical variations of clinopyroxenes in order to delineate the intracrystalline constraints which are characteristic of specific magmatic environments. Clinopyroxenes (cpx) crystallized from peralkaline ultrapotassic melt with kamafugitic and lamproitic affinities are characterized by high Si contents, which are insensitive to variations in silica abundance and silica saturation of the melt. The high Si occupancy in clinopyroxenes from kamafugitic magma is coupled to large M1 (i.e. Mg and Fe²⁺) and M2 (high Ca occupancy) sites, whereas in clinopyroxenes from magmas with lamproitic affinity, high Si content is combined with large M1 but small M2 sites. Clinopyroxenes from Romantype alkaline potassic and ultrapostassic rocks are characterized by an expanded tetrahedron (high ^IVA1 content) and small M1 site which is combined with small M2 polyhedron in clinopyroxenes from the potassic rocks and large M2 site in those from the ultrapotassic rocks.     

Mg,Fe2+ site occupancies in coexisting pyroxenes

The separate distributions for MgSiO₃ and FeSiO₃ in coexisting pyroxenes from the Skaergaard and Bushveld intrusions and charnockites, which were introduced in an earlier communication, indicate directly that significant amounts of both Fe²⁺ and Mg were present in the M(2) site of the Ca-rich pyroxene at the temperature of final intercrystalline equilibration. The calculated Fe²⁺ M(2) site occupancy in the Ca-rich pyroxene increases markedly with decrease in total MgSiO₃ content but the corresponding Mg site occupancy appears largely independent of MgSiO₃. The mean value of the distribution constant for intracrystalline exchange in the Ca-rich pyroxene decreases, away from unity, with decreasing temperature of equilibration. Occupancy of Mg and Fe²⁺ in the M (2) site of the Ca-rich pyroxene effectively compensates for the expected variation in K _D with composition resulting from intracrystalline partition in Ca-poor pyroxene, and this largely accounts for the difference in K _D between igneous and metamorphic pyroxenes. The variation of the augite limb of the pyroxene solvus within the pyroxene quadrilateral is developed as a possible geothermometer.     

Crystal Chemistry and Site Configuration of the Clinopyroxene from Leucite-bearing Rocks and Related Genetic Significance: the Sabatini Lavas, Roman Region, Italy

A clinopyroxene suite from leucite–bearing lavas locatedin the Sabatini district of the Roman Volcanic Region has beeninvestigated by single–crystal X–ray diffractionmethods combined with electron probe microanalysis. The main aim of the study was to obtain crystallographic datanecessary to evaluate intracrystaUine order–disorder relationshipsin natural clinopyroxenes and related equilibria–disequilibriaphenomena in different host–rock types. Generally, the polyhedral site configurations of the clinopyroxenesinvestigated are interdependent and follow specific variationtrends related to specific host–rock types. The majorvariations are found in the tetrahedron and the octahedron;while the polyhedron M2 is essentially unchanged and occupiedby(Ca+Na). The degree of Mg–Fe²⁺; ordering in M1–M2, respectively,depends on the configuration of these sites, particularly M2,and is generally lower in late–crystallized (rim) clinopyroxenesthan in the corresponding higher–temperature (core) fromthe same crystals. This is' attributed to configuration relationshipsunfavourable to the Mg–Fe²⁺ ordering and largely dependingon the occupancy of M2. Polygenetic, early–crystallized clinopyroxenes, occasionallywith resorbed margins, indicate crystal-liquid disequilibriarelated to crystal and–or magma mixing processes.     

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.     

Influence of magma composition and oxygen fugacity on the crystal structure of C2/c clinopyroxenes from a basalt-pantellerite suite

The crystallochemical variations of clinopyroxene in response to changes in f_{O 2} and melt composition have been determined for a basalt-pantellerite suite (Boseti Complex, Main Ethiopian Rift) by crystal structure refinement and microprobe analysis. The pyroxene evolutionary trend has both a “Ca-minimum” and late iron enrichment. During crystallization from basalts to trachytes, clinopyroxene geometry depends mainly on the relationships between T and M2 sites; for example, high SiO₂ activity in the magma causes high Si occupancy in T site, which in turn requires low Ca occupancy in M2 site in order to fulfill the local charge balance requirements. In contrast, clinopyroxene crystallized from acid melts is characterized by high Fe²⁺ (M1) content and therefore by a very large M1 site. Longer 〈M1-O1〉 and M1-O2 bond lengths require shorter T-O1 and T-O2 bond lengths and high Si occupancy in T site. It is concluded that the “Ca-minimum” in the clinopyroxene structure is regarded as the lowest value at which the charge balance requirements are satisfied in a C2/c clinopyroxene structure.     

多硅白云母中Fe2+的高压有序效应

21个多硅白云母来自4个低温高压变质带。用电子探针、X射线粉末衍射及穆斯堡尔谱测定其化学成分、b0值及Fe²⁺占位。建立Fe²⁺(M1)/Fe²⁺(M2)对b0值相关图,发现Fe²⁺在八面体晶位有序化并解释其有序机理。     

The crystal chemistry of lithium and Fe3+ in synthetic orthopyroxene

Lithian ferrian enstatite with Li₂O = 1.39 wt% and Fe₂O₃ 7.54 wt% was synthesised in the (MgO–Li₂O–FeO–SiO₂–H₂O) system at P = 0.3 GPa, T = 1,000°C, fO₂ = +2 Pbca, and a = 18.2113(7), b = 8.8172(3), c = 5.2050(2) Å, V = 835.79(9) Å³. The composition of the orthopyroxene was determined combining EMP, LA-ICP-MS and single-crystal XRD analysis, yielding the unit formula ^M2(Mg_0.59Fe _0.21 ²⁺ Li_0.20) ^M1(Mg_0.74Fe _0.20 ³⁺ Fe _0.06 ²⁺ ) Si₂O₆. Structure refinements done on crystals obtained from synthesis runs with variable Mg-content show that the orthopyroxene is virtually constant in composition and hence in structure, whereas coexisting clinopyroxenes occurring both as individual grains or thin rims around the orthopyroxene crystals have variable amounts of Li, Fe³⁺ and Mg contents. Structure refinement shows that Li is ordered at the M2 site and Fe³⁺ is ordered at the M1 site of the orthopyroxene, whereas Mg (and Fe²⁺) distributes over both octahedral sites. The main geometrical variations observed for Li-rich samples are actually due to the presence of Fe³⁺, which affects significantly the geometry of the M1 site; changes in the geometry of the M2 site due to the lower coordination of Li are likely to affect both the degree and the kinetics of the non-convergent Fe²⁺-Mg ordering process in octahedral sites.     

Distinctive crystal chemistry and site configuration of the clinopyroxene from alkali basaltic rocks

A crystal chemical investigation of clinopyroxenes from a suite of nepheline-bearing lavas located in the Nyambeni Range of Kenya has delineated the polyhedral site configurations and related intracrystalline relationships. These are distinct from those determined for the clinopyroxene in an analogous suite of leucite-bearing lavas from the Sabatini volcanoes in the Roman Region of Italy (Dal Negro et al. 1985).The Nyambeni clinopyroxene, varying from salite to hedenbergite, preferentially accepts Na in the M2 site to balance increasing Fe²⁺ and Si, respectively, whereas the Sabatini clinopyroxene is confined within the salite field and preferentially accepts Al^iv to balance the effect of increasing (Fe³⁺+Ti⁴⁺+Al^vi+Cr³⁺)_M1.The Fe²⁺/Fe³⁺ and K/Na ratios of the host rocks emerge as significant factors in determining the different polyhedral configurations and evolutions of the clinopyroxene from the two lava suites, respectively. The resulting Mg-Fe²⁺ order-disorder relationships in M1–M2 are also distinct in the two clinopyroxenes. A high degree of MgFe²⁺ order in M1–M2 corresponds to the largest configurational, hence energetic, difference between M1 and M2 in the Nyambeni clinopyroxene, whereas the converse applies to the Sabatini clinopyroxene.In view of the significant crystal chemical differences and distinct evolution trends, it is proposed that salites from alkali volcanic rocks may be referred to as Nyambeni-type or Sabatini-type, respectively.     

An EXAFS study of Gd,Er and Lu site location in the epidote structure

L _III edge extended X-ray absorption fine structure (EXAFS) spectra of Gd, Er and Lu environments in synthetic epidotes of composition CaLa_0.9 X _0.1Al₂MgSi₃O₁₃H (X=Gd or Er or Lu) were recorded using synchrotron radiation. The Fourier transforms of the Gd-, Er- and Lu-EXAFS are clearly different from one another indicating wholly or partially different site occupancy. Model fitting of the Fourier-filtered partial EXAFS and comparison of pair distribution functions with those calculated for natural epidote leads to the conclusion that three different sites are probably involved in the accommodation of these elements in the epidote structure, and that site preference is a function of the rare earth ionic size. Gd is located in A2-type sites, whereas the local atomic environment of Er is consistent with A1 site occupancy and the Lu environment has been modelled on an M3-type octahedral site.     

Strong site preference of Co2+ in olivine,Co1.10Mg0.90SiO4

The crystal structure and site preference of Co²⁺ in a synthetic Co_1.10Mg_0.90SiO₄ olivine have been determined from single crystal X-ray diffraction data collected on an automatic diffractometer. The R factor is 0.044 for 612 reflections. The site occupancies are: Ml site: Co 0.730±0.006; Mg 0.270; M2 site: Co 0.370, Mg 0.630. The Gibbs free energy change, ΔG° for the ion-exchange reaction between M1 and M2 sites is ?4.06 kcals/mole, assuming ideal mixing at each set of sites. This energy may be called ‘site preference energy’ of Co²⁺ in olivine. The strong preference of Co²⁺ for the M1 site can be quantitatively explained by two competing forces: preference of ions larger than Mg²⁺ for the M2 site and stronger covalent bonding of transition metal ions at the M1 site. For Fe²⁺, Mg²⁺, these two effects nearly neutralize each other, explaining the lack of considerable cation-ordering in Fe-Mg olivines.     

Crystal-chemistry of high-pressure clinopyroxene from spinel lherzolite nodules Mts. Leura and Noorat Suites,Victoria, Australia

Summary The clinopyroxene suites from lherzolite nodules from Mts. Leura and Noorat (Victoria, Australia) have been investigated by X-ray diffraction and electron probe microanalyses (Dal Negro et al., 1984; Cundari et al., 1986).The evolution of the host nodule is shown by general depletion of AlIv, AVI, Ti⁴⁺, Fe²⁺ and enrichment of Si, Mgm,, Fe³⁺, Cr³⁺, Ca, while Na depletion occurs only in the clinopyroxenes from Mt. Noorat. Different mechanisms of cation substitution are thus involved in the two clinopyroxene suites, suggesting different total pressures of equilibration in the stability field of spinel.Modifications involving the M1 octahedron are mainly ascribed to variable amounts of trivalent cations, the volume of the M 1 site increasing with decreasing content of trivalent cations in each suite. The differences in M 1 site configuration between the Mt. Leura and Mt. Noorat clinopyroxene suites are ascribed to the different amounts of A1v1 and FeM,.The volume of the T tetrahedral site is generally related to A1Iv in each suite. An increase in T site volume from Mt. Leura to Mt. Noorat clinopyroxenes was found however, due to lengthening of the T-O_brg bond lengths, for similar AIIv contents. The volume of the M2 site, generally related to Ca content, was generally higher in the Noorat clinopyroxenes for similar Ca (and Ca + Na) contents, due to the longer M₂-O₃C₁ bond length, strongly related to Na content. Cell volume is linearly correlated to M 1 volume in each suite, but is definitely higher in the Noorat clinopyroxenes for similar M 1 volume. All the structural data show that the total pressure of equilibration in the Noorat clinopyroxenes was lower than that in the Leura clinopyroxenes, as suggested by chemical data.

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Die Kristallchemie von hochdruck-klinopyroxenen aus spinell-lherzolithknollen von Mt. Leura und Mt. Noorat, Victoria, Australien

Zusammenfassung Die Klinopyroxenparagenesen aus Lherzolitheinschlüssen von Mt. Leura und Mt. Noorat (Victoria, Australien) wurden mittels Röntgendiffraktometrie und Elektronenmikrosonde untersucht (Dal Negro et al., 1984; Cundari et al., 1986). Die Lherzolitheinschlüsse zeigen generell eine Abnahme von Al^IV, Al^VI, Ti⁴⁺, Fe _MI ²⁺ und eine Zunahme von Si, Mgm,, Fe³⁺, Cr³⁺ und Ca. Eine Abnahme von Na tritt nur in Klinopyroxenen von Mt. Noorat auf. Verschiedene Substitutions-Mechanismen der Kationen weisen auf verschiedene Equilibrationsdrucke im Stabilitätsbereich der Spinelle hin und sind daher in den beiden Klinopyroxenserien zu berücksichtigen. Modifikationen in der oktaedrischen M1-Position wurden vor allem dem wechselnden Anteil an dreiwertigen Kationen zugeschrieben, wobei in jeder der beiden Serien das Volumen der Ml-Position mit abnehmenden Gehalten dreiwertiger Kationen zunimmt. Die unterschiedliche Konfiguration der M1-Position der Klinopyroxene von Mt. Leura und Mt. Noorat wird mit unterschiedlichen Gehalten an Al^VI und Fe _MI ²⁺ , in Zusammenhang gebracht.Das Volumen der tetraedrischen T-Position ist normalerweise mit den Gehalten an All^IV in jeder Serie verknüpft. Ein Vergleich der Klinopyroxene von Mt. Leura und Mt. Noorat zeigte jedoch, daß bei gleichen Gehalten an Al^VI das Volumen der tetraedrischen Position infolge einer Aufwertung der T-O_brg.-Bindungen zunimmt. Das Volumen der M2-Position, üblicherweise mit dem Ca-Gehalt korreliert, ist in den Klinopyroxenen von Mt. Noorat bei ähnlichen Ca (und Ca f Na) Gehalten infolge größerer M2--O₃C₁-Abstände größer. Sie stehen also mit den Na-Gehalten in Verbindung.Das Volumen der Elementarzelle korreliert mit dem der M1-Position in jeder Serie; es ist aber in den Klinopyroxenen von Mt. Noorat deutlich höher. Die Ergebnisse der Strukturuntersuchungen zeigen-wie auch die chemischen Daten-, daß die genannten Equilibrationsdrucke für die Klinopyroxene von Mt. Noorat niedriger waren als für die von Mt. Leura.

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With 2 Figures     

莱河矿的超结构和低温穆斯堡尔谱的对比研究

本文进行了莱河矿3C超结构和4.2K穆斯堡尔谱的对比研究。研究表明。莱河矿的非等效位置M2A+M2C,M2B,M1B,M1A和VB能够分别与Kan等(1985)测定的莱河矿穆斯堡尔谱的吸收双峰A,B,C,D和E对应,不仅解决了超结构位置和吸收双峰之间的对应,而且圆满解释了吸收双峰A:B和C:D的强度比为2:1的关系。另外,还利用莱河矿超结构的资料讨论了莱河矿的反铁磁性内部作用。     

Clinopyroxene geobarometry of magmatic rocks Part 1: An expanded structural geobarometer for anhydrous and hydrous, basic and ultrabasic systems

Crystal-structure modeling of experimental Ca-rich clinopyroxenes [Ca + Na > 0.5 apfu; Mg/(Mg + Fe²⁺) > 0.7] coexisting with basic and ultrabasic melts was utilized for calibration of geobarometers based on unit-cell volume (V_cell) vs M1-site volume (V_M1). The clinopyroxene database includes over one hundred experiments from literature and sixteen previously unpublished experiments on basanite and picrobasalt starting materials. The coexisting melts span a wide range of petrologically relevant anhydrous and hydrous compositions (from quartz-normative basalt to nephelinite, excluding high-Al basalts and melts coexisting with garnet or melilite) at pressure conditions pertinent to the earth's crust and uppermost mantle (P= 0–24 kbar) in a variety of fO ₂ conditions (from CCO-buffered to air-buffered) and mineral assemblages (Cpx ± Opx ± Pig ± Ol ± Plag ± Lc ± Ne ± Spl ± Amp ± Ilm). As previously found for near-liquidus products of basaltic melts, the experimental clinopyroxenes follow two distinct trends: (i) at a given P, V_cell is linearly and negatively correlated with V_M1. This corresponds with the extent of Tschermak-type substitutions, which depends strongly on aSiO₂ and a _CaO; (ii) for a fixed melt composition, V_cell and V_M1 decrease linearly as P increases, due to a combination of M₁, M₂ and T site exchanges. Despite the chemical complexity of these relationships, P could be modeled as a linear function of V_cell and V_M1. A simplified solution for anhydrous magmas reproduced the experimental pressures with an uncertainty of 1.75 kbar (=1 ; max. dev. = 5.5 kbar; N = 135). An expanded T-dependent solution capable of recovering the measured pressures of both anhydrous and hydrous experiments with an uncertainty of 1.70 kbar (=1 ; max. dev. = 5.4 kbar; N = 157) was obtained by correcting unit-cell and M1-site volumes for thermal expansivity and compressibility. The corrected formulation is more resistant to the effects of temperature variations and is therefore recommended. Nevertheless, it requires an independent, accurate estimate of crystallization T. Underestimating T by 20 °C propagates into a 1-kbar increase of calculated P. The applicability of the T-dependent formulation was tested on hydrous ultramafic to gabbroic rocks of the southern Adamello batholith for which P-T evolution could independently be constrained by field observation, petrography and experimentally determined phase relations. The pressure estimates obtained by clinopyroxene structural geobarometry closely matched those predicted by phase equilibria of a picrobasaltic melt parental to the investigated magmatic rocks. To facilitate application of the present geobarometers, both anhydrous and corrected solutions were implemented as MS-DOS^® and UNIX^® software programs (CpxBar) designed to permit retrieval of the pressure of crystallization directly from a chemical analysis or from uncorrected unit-cell and M1-site volume X-ray data.     

Calculations of activity-composition relations in multi-site solid solutions: the example of AB2O4 spinels

A model to calculate activities in multisite solutions like spinels, from a general expression of the Gibbs free energy is developped. The free energy is written as that of a solution with ideal mixing of cations on each sublattice corrected by any suitable higher order terms. It is shown that activities of i^th end-member can be simply written: $${\text{act (}}i{\text{) = (}}\gamma _i {\text{/}}\gamma _i^{\text{0}} {\text{)}}\mathop \prod \limits_j (N_j /N_j^0 )^{P(j,{\text{ }}i)} .$$ N _j are site occupancy fractions; the γ _i are equal to one for the ideal multisite model and depend only on the higher order corrections to this model; ⁰ indicate values for the i ^th end member. The exponents in the matrix P are integers and constants. The activities cannot be expressed explicitly as function of the macroscopic composition. The site occupancy fractions which minimize the Gibbs free energy must be calculated first solving a set of non linear equations which define the internal equilibrium conditions. The (Fe²⁺, Mg) (Al, Cr, Fe³⁺) spinel are used to illustrate these calculations. For multicomponent AB₂O₄ spinels activity expressions derived for the reference ideal multisite mixing model are: $${\text{act (AB}}_{\text{2}} {\text{O}}_{\text{4}} {\text{) = }}\frac{{({\text{A}})[{\text{B}}]^2 }}{{({\text{A}})_0 [{\text{B}}]_0^2 }}$$ (A): fraction of tetrahedral sites occupied by A²⁺; [B]: fraction of octahedral sites occupied by B³⁺. Because the site occupancy fractions at equilibrium are not independent (but related by the internal equilibrium relations) many equivalent expressions of the activities can be obtained. Finally approximations proposed in the literature to obtain simple explicit activity-concentration relationships are discussed.     

Use of ultrasonically modulated electron resonance to study S-state ions in mineral crystals: Mn2+, Fe3+, in tremolite

The use of ultrasonically modulated electron resonance (UMER) to study S-state ions in substitutional sites of mineral single crystals is discussed. Mn²⁺ and Fe³⁺ in natural single crystals of tremolite are used as examples. Combined electron paramagnetic resonance (EPR) and UMER measurements establish almost certainly that Mn²⁺ enters predominantly into the distorted M4 sites occupied by Ca²⁺ in the ideal tremolite structure and only to a minor extent into the M1, M2 and M3 sites normally occupied by Mg²⁺. Fe³⁺ in tremolite gives rise to the well known high spin resonance with g _eff?4.3 but there is considerable uncertainty as to the site of the impurity ion.     

Multiple origins of clinopyroxenes in alkali basaltic rocks

Geochemical and textural data on clinopyroxenes in individual alkali basaltic flows from provinces in eastern Australia and the Massif Central can be used to differentiate four different modes of origin (three at high pressure) for these clinopyroxenes. Many single flows from the two provinces contain clinopyroxenes of three, or even four, of these origins. Rare flows contain core clinopyroxene with overgrowths of clinopyroxenes of two distinct generation. Each of the overgrowth is compositionally analogous to clinopyroxenes occurring in xenoliths or as discrete crystals in the same host lava. Such rimming relationships provide evidence that the host magma has undergone high pressure crystallisation and confirm that some xenoliths and megacrysts are cognate. With decreasing pressure the major changes in clinopyroxene chemistry are an increase in the ratio Al^lv/Al^vi, a linear increase of atomic proportions of Ti and Al with decreasing Si, and an increase in the Ti: (100 Mg/(Mg + Σ Fe)) ratio of the pyroxenes. Al₂O₂ wt, % is an unreliable potential geobarometric indicator; consideration of tetrahedral and octahedral site occupancies by Al (Al^lv/Al^vl ratio) is necessary. High-pressure fractionation dominated by clinopyroxene is postulated for some basaltic-composition, resulting in SiO₂ depletion, alkali enrichment and decrease in the Mg/(Mg + Fe²⁺) value of the host magma.     

Some clinopyroxenes from ultramafic inclusions in Dreiser Weiher,Eifel

Eight clinopyroxenes from wehrlites and clinopyroxenites and three clinopyroxenes of crystal lapilli in tuff of Dreiser Weiher in Eifel, Germany, have been separated and chemically analysed. One hornblende and two phlogopites from a wehrlite and clinopyroxenites have also been analysed. The rocks enclosing these inclusions are alkali basalts of basanite composition. The analysed clinopyroxenes contain considerable amounts of Al₂O₃ (3.87–10.84 wt%). The calculated Tschermak's component ranges from 5.9 to 18.4 mol per cent. All of the analysed clinopyroxenes are clearly different from chromian diopsides in lherzolite inclusions in basaltic rocks in Dreiser Weiher and other localities; the former has higher contents of total FeO, CaO and TiO₂ and lower contents of MgO and Cr₂O₃ than the latter. Two clinopyroxenes separated from apatite-bearing clinopyroxenites show high contents of Fe₂O₃ with about 2 per cent of Na₂O, indicating the presence of considerable amounts of acmite component in addition to Tschermak's component. The relative proportions of Al in the tetrahedral site and that in the octahedral site in the analysed clinopyroxenes are clearly different from those of the common igneous clinopyroxenes and eclogites, and similar to those of the clinopyroxenes from other inclusions in basaltic rocks and granulites. It is suggested that all the analysed clinopyroxenes and their host inclusions have crystallized from alkali basalt magmas in relatively deep levels of the continental crust.     

Ca−Sr substitution in clinopyroxenes along the join CaMgSi2O6−SrMgSi2O6

Summary In order to define the limits of expansion of the M2 polyhedron in theC2/c clinopyroxenes of formulaX ^M2Mg^M1 [Si₂O₆] as the mean ionic radius in the M2 site increases, the join CaMgSi₂O₆–SrMgSi₂O₆ (Di–SrPx) has been investigated atP=1 atm and between 1090°C and 1350°C. The extent of the clinopyroxene solid solutions is limited to the compositional range Di₁₀₀–Di₇₀SrPx₃₀. Within this range the unit-cell parameters of the clinopyroxenes show a linear variation with the increase of Sr content. The comparison of the variations caused in the unit-cell dimensions by the increase of the mean ionic radius in the M2 site (Di–SrPx series) with those caused by the decrease of the mean ionic radius in M2 (Di–En series) displays a different trend ofb in the two series. This different trend ofb suggests a different mechanism of the structure deformation in the two solid solution series. The narrow extent of the Di–SrPx solid solutions atT=1200°C shows that the increase of the mean ionic radius in the M2 site is restricted to the range 1.12–1.16 Å.

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La substitution Ca–Sr dans les clinopyroxènes le long du joint CaMgSi₂O₆–SrMgSi₂O₆

Résumé Le joint CaMgSi₂O₆–SrMgSi₂O₆ (Di–SrPx) a été étudié entre 1090°C et 1350°C à 1 atm dans le but d'établir quelles sont les limites de l'expansibilité du polyhèdre M2 dans les clinopyroxènesX ^M2Mg^M1 [Si₂O₆] (group spatialC2/c) avec l'augmentation du rayon jonique moyen dans le site M2. La solution solide est limitée à l'intervalle de composition Di₁₀₀–Di₇₀ SrPx₃₀. Dans ce domaine les paramètres de la maille varient d'une façon linéaire avec la teneur croissante de Sr. Si on compare les variations de la maille, déterminées par le rayon jonique moyen croissant dans le site M2 (série Di–SrPx), avec celles causées par la diminution du rayon jonique moyen dans le site M2 (série Di–En), on observe une tendance différente du paramètreb dans les deux séries. Ceci indique un mécanisme différent de la déformation structuralle dans les deux séries de solutions solides. Puisque àT=1200°C le domaine des solutions solides Di–SrPx est étroit, l'augmentation du rayon ionique moyen dans le site M2 est bornée à l'intervalle 1.12–1.16 Å.

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With 5 Figures     

H T -XRD study of synthetic ferrian magnesian spodumene: the effect of site dimension on the P 21/ c → C 2/ c phase transition

 Ferrian magnesian spodumene was synthesized in the MLFSH system at P=0.4 GPa, T=700 °C, fO₂=NNO+2.3. The space group at room T is P2₁/c [a=9.638(3) ?, b=8.709(2) ?, c=5.258(2) ?, β=109.83(3)^∘, V=415.2 ?³]. The structure is topologically equivalent to that of ferrian spodumene, LiFeSi₂O₆, and has two symmetrically independent tetrahedral chains, A and B, and two independent octahedral sites, M1 and M2. The crystal-chemical composition was determined combining EMP, SIMS and single-crystal XRD analysis, yielding ^M2(Li_0.85Mg_0.09Fe²⁺ _0.06) ^M1(Fe³⁺ _0.85Mg_0.15)Si₂O₆. Li is ordered at the M2 site and Fe³⁺ is ordered at the M1 site, whereas Mg (and Fe²⁺) distribute over both octahedral sites. Structure refinements done at different temperatures (25, 70, 95, 125, 150 and 200 °C) allowed characterization of a reversible displacive P2₁/c→C2/c transition at 106 °C. Previous HT-XRD studies of Li-clinopyroxenes had shown that the transition temperature is inversely related to the size of the M1 cation. For the crystal of this work, the aggregate ionic radius at M1 is longer than that of ferrian spodumene, for which the transition temperature is −44 °C. The higher transition temperature observed can only be explained on the basis of the shorter aggregate radius at the M2 site (due to the presence of Mg substituting after Li), in keeping with the results obtained for ferromagnesian P2₁/c pyroxenes. The effects of all the chemical substitutions must be considered when modelling transition temperatures and thermodynamic behaviour in clinopyroxenes. Received: 7 May 2002 / Accepted: 23 October 2002