Thermodynamics of multicomponent pyroxenes: III. Calibration of Fe2+(Mg)-1, TiAl2(MgSi2)-1, TiFe 2 3+ (MgSi2)-1, AlFe3+(MgSi)-1, NaAl(CaMg)-1, Al2(MgSi)-1 and Ca(Mg)-1 exchange reactions between pyroxenes and silicate melts

A thermodynamic model for the Gibbs free energy of igneous pyroxenes with the general formula [Na, Ca, Fe²⁺, Mg]^M2[Fe²⁺, Mg, Ti, Al, Fe³⁺]^M1[Al, Fe³⁺, Si]^TetSiO₆ is calibrated from experimentally determined compositions of coexisting pyroxene and silicate melt. The model is based upon the general formulation, and relies upon the calibration of the “quadrilateral” subsystem, previously published by the present authors. The calibration database of pyroxene-liquid equilibria spans a broad spectrum of temperature, pressure and oxygen fugacity conditions, ranging from 1000°–1600°C, 0.001–30 kbar and iron-wüstite to air. Chemical potentials of endmember pyroxene components as well as exchange potentials between pyroxenes and coexisting liquids are defined utilizing the present authors' thermodynamic melt model. Model parameters are extracted from these relations by regression analysis. The resulting model and derivative endmember properties are internally consistent with an existing standard state thermodynamic database. The success of the model and its applicability to igneous petrogenesis are demonstrated by comparing calculated and experimentally determined liquidus compositions, temperatures and symmetry states for pyroxenes crystallizing from a variety of silicate melts, ranging in composition from tholeiites and angrites through rhyolites to potash ankaratrites.     

Mineralogy,petrology, and phase relations of glaucophane-lawsonite zone blueschists from the Tavşanli Region,Northwest Turkey

Glaucophane-lawsonite facies blueschists representing a metamorphosed sequence of basic igneous rocks, cherts and shales have been investigated northeast of the district of Tav?anli in Northwest Turkey. Sodic amphiboles are rich in magnesium reflecting the generally high oxidation states of the blueschists. Lawsonite has a very uniform composition with up to 2.5 wt.% Fe₂O₃. Sodic pyroxenes show an extensive range of compositions with all the end-members represented. Chlorites are uniform in their Al/(Al+Fe+Mg) ratio but show variable Fe/ (Fe+Mg) ratios. Garnets from metacherts are rich in spessartine (>50%) whereas those from metabasites are largely almandine. Pistacite rich epidote is found in metacherts coexisting with lawsonite. Phengites are distinctly higher in their Fe, Mg and Si contents than those from greenschist facies. Hematites with low TiO₂ are ubiquitous in metacherts. Fe²⁺/Mg partitioning between chlorite and sodic amphibole is strongly controlled by the calcium content of the sodic amphibole and ranges from 1.1 for low calcium substitution to 0.8 for higher calcium substitution. The Al/Fe³⁺ partition coefficient between sodic amphibole and sodic pyroxene is 2.1. A model system has been constructed involving projections from lawsonite, iron-oxide and quartz onto a tetrahedron with Na, Al, Fe²⁺ and Mg at its apices. Calcite is treated as an indifferent phase. The model system illustrates the incompatibility of the sodic pyroxene with chlorite in the glaucophanelawsonite facies; this assemblage is represented by sodic amphibole. Sodic amphibole compositions are plotted in terms of coexisting ferromagnesian minerals. Five major areas on the sodic amphibole compositional field are delineated, each associated with one of the following minerals: chlorite, stilpnomelane, talc, almandine, deerite.     

Coexisting hornblendes and biotites from Precambrian gneisses of the south coast of Western Australia

The compositions of coexisting hornblendes and biotites from amphibolite and granulite facies gneisses from the south coast of Western Australia were controlled by host rock composition, paragenesis, metamophic grade, pressure, and oxygen fugacity. The Mg/(Mg + Fe²⁺) and Mn/Fe²⁺ ratios in both minerals and possibly the Al^vi contents of the hornblendes are related to host rock compositions. Metamorphic grade appears to influence, perhaps only indirectly, the Ti, Mn, and Fe³⁺ contents of both minerals and possibly the hornblende Ca content. The higher Ti and lower Mn contents of the granulite facies hornblendes and biotites are attributed to their coexistence with pyroxenes, whereas their lower Fe³⁺/(Fe²⁺ + Fe³⁺) ratios are probably due to lower oxygen fugacity in the granulite facies environment. Grade-related colour variations in both minerals were controlled by their Ti/Fe²⁺ and Fe³⁺/(Fe²⁺ + Fe³⁺ ratios. The relatively low Al^vi contents of the hornblendes suggest low- to moderate-pressure metamorphism.Variations in element distribution coefficients are related to variations in mineral compositions rather than metamorphic grade. Thus K_{D(Al^iv ?Si)} is related to the Al^iv andedenite alkali contents of the hornblendes, K_{D(Fe²⁺ ?Mg)} to the distributions of Al^iv ?Si and Al^vi + Ti + Fe³⁺, K_D(Mn) to the Mn contents of both minerals, and K_D(Al^vi) to the Al^vi contents of the biotites.     

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.     

Micas from the Khaluta carbonatite deposit,western Transbaikal region

The Khaluta carbonatite deposit located in the western Transbaikal region was formed during the Late Mesozoic rifting in the southern framework of the Siberian Craton. Carbonatite is associated with shonkinite and syenite and is accompanied by fenitization. The composition of mica in more than 160 samples of country rocks, carbonatites, silicate rocks, and fenites was studied. The Fe³⁺ and Fe²⁺ contents, as well as oxygen isotopic composition, were determined. The Mg and Fe contents increase, whereas the Ti and Al contents decrease in micas when passing from silicate rocks and fenites to carbonatites. Micas from carbonatites are depleted in Al, enriched in Fe³⁺, and distinguished by high Si and F contents. According to our calculations, in some cases Al replaces Si in the tetrahedral site instead of replacement of Fe³⁺ as is characteristic of tetraferriphlogopite. Formally, the mica from carbonatites falls within the tetraferriphlogopite field, but typical inverse pleochroism is not always observable. The δ¹⁸O values of micas from carbonatite, shonkinite, syenite, and fenite are similar to those of mantle-derived silicate minerals. The δ¹⁸O values in the minerals coexisting with phlogopite testify to their isotopic equilibrium and make it possible to calculate the crystallization temperature of carbonatite.     

Partition of Mg and Fe2+ in coexisting pyroxenes

A general theory for the partition of elements between coexisting, multicomponent phases is outlined and applied to data for Ca-rich pyroxene (Cap) — Ca-poor pyroxene (Op) assemblages from the Skaergaard and Bushveld intrusions and from charnockites. The intercrystalline partition of Mg and Fe²⁺ are studied separately rather than through the exchange reaction, MgSiO ₃ ^Cap +FeSiO ₃ ^Op FeSiO ₃ ^Cap +MgSiO ₃ ^Op .The separate distributions for x_MgSiO3> and x_FeSiO3> are quite distinct and demonstrate directly that solutions of both Mg and Fe²⁺ in the two pyroxenes are nonideal.     

Clinoenstatite in volcanic rocks from the Bonin Islands

Multiply-twinned clinoenstatite has been found in andesitic rocks from Chichi-jima and Mukojima in the Bonin Islands.The clinoenstatite occurs as (1) reaction rims around olivine, (2) composite crystals with bronzite, and (3) anhedral phenocrysts rimmed or included by bronzite.The clinoenstatite is chemically characterized by low contents of Ca (less than 0.5 wt.% oxide), Fs (9.2–11.5) and Al (less than 0.6 wt.% oxide) relative to the coexisting bronzite. The partition coefficient, K _{D op} ^cp =(Mg/Fe²⁺)^cp/(Mg/Fe²⁺)^op between coexisting clinoenstatite and bronzite, ranges from 1.02 to 1.32 (average 1.17). The Fe²⁺/Mg+Fe²⁺ ratios of coexisting clinoenstatite and bronzite are different in different rock types, which suggests variable inversion temperatures of protoenstatite to orthopyroxene in boninite.Bronzite phenocrysts in a specimen, ranging from Fs15 to Fs30, coexist with augite phenocrysts, whereas those in the other specimens, ranging from Fs12 to Fs18, do not coexist with augite phenocrysts. These differences in petrographical nature and mineral chemistry among the specimens examined may be due to variations in their quenching stages.The boninite clinoenstatite and bronzite are relatively rich in Ca and Mg, compared with the Papuan and Mariana pyroxenes, which seems to depend upon the rock chemistry.     

Fractionation of chromium,nickel, cobalt and copper in a differentiated dolerite‐granophyre sequence at Red Hill,Tasmania

Fractionation of tholeiitic magma in the Red Hill intrusion produced a gradational series of rocks ranging from dolerite to granophyre (McDougall, 1962). Granophyres are enriched in Fe, Si and alkalies, and impoverished in Mg, Ca and Al. With fractionation the magma was depleted rapidly in Cr and Ni owing to their removal in early crystallizing pyroxene and iron oxides. Cobalt decreases gradually from chilled dolerite to silicic dolerite, followed by a significant maximum in the most Fe‐enriched rocks, and finally decreases markedly in the granophyres. Cobalt follows Fe²+ closely and shows no obvious relationship with Mg. Copper was progressively enriched in the magma during the main stages of fractionation until precipitation of sulphide occurred, which caused impoverishment of Cu in the final liquid. Copper also is present in the silicates, it substitutes for Na in the feldspars and Fe²+ in pyroxenes and iron oxides.     

Zoned clinopyroxenes from the volcanic rocks of almopia (Voras Mts), Central Macedonia,Greece

Summary In the zoned clinopyroxene phenocrysts from the volcanic rocks of Almopia the Mg/Fe ratio and the contents of Mn, and mostly of Na, increase from the core towards the rim of the crystals, whereas the Fe³⁺/Fe²⁺ ratio, and in many cases the contents of Ca, decrease. On the contrary, the content of Si decreases from inside outwards or remains almost constant whereas Al and Ti increase.The high Ca-content of the clinopyroxenes, low Ti, and limited Fe-enrichment, with a trend from Ca_43.3: Mg_47.0: (Fe + Mn)_9.7 to Ca_46.6: Mg_42.2: (Fe + Mn)_11.2, illustrate the shoshonitic to cale-alkaline nature of the parental magma.The composition of the clinopyroxenes indicates that, of all possible controlling factors, the high water-vapour pressure is considered to play an important role for the Al^IV fluctuations during the crystallization.

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Zonierte klinopyroxene der vulkanite von almopia (Voras-Gebirge), Zentral-Mazedonien, Griechenland

Zusammenfassung Bei den zonierten Klinopyroxeneinsprenglingen der Vulkanite von Almopia nehmen das Mg/Fe-Verhältnis und die Gehalte an Mn und meistens an Na in den einzelnen Zonen vom Kern zum Rand zu, während das Fe³⁺/Fe²⁺-Verhältnis, und in vielen Fällen die Gehalte an Ca, abnehmen. Im Gegensatz dazu nimmt der Gehalt an Si von innen nach außen ab oder bleibt fast konstant, während Al und Ti zunehmen.Der hohe Ca-Gehalt und gleichzeitig niedrige Ti-Gehalt der Klinopyroxene, zusammen mit ihrer begrenzten Fe-Anreicherung und einem Trend von Ca_43.3: Mg_47.0: (Fe + Mn)_9.7 bis Ca_46.6: Mg_42.2: (Fe + Mn)_11.2 weisen auf die shoshonitische bis kalk-alkalische Natur des Stammagmas hin. Die Zusammensetzung der Klinopyroxene weist darauf hin, daß der hohe Wasserdampfdruck im Magma auch eine wichtige Rolle für Schwankungen im Al^IV-Gehalt während der Kristallisation darstellt.

     

Crystallization trends of pyroxenes from alkaline subvolcanites of Punta delle Pietre Nere (Gargano,Southern Italy)

Summary The results of microprobe analyses of clinopyroxenes from alkaline melasyenites and layered melagabbros, produced by intra-plate magmatism of Paleocene age at Punta delle Pietre Nere, are here given and discussed.The analysed pyroxenes range from diopsidic to acmite-rich compositions.The first crystallized pyroxenes (diopside) show Al^VI contents suggesting shallow depths of crystallization. In addition pyroxenes from melasyenite and those from melagabbro display different Cr contents, Al/Ti and Mg/(Mg+Fe²⁺+Fe³⁺) ratios confirming their crystallization from melts produced by different parental liquids.Diopsides and salites show an overall trend towards high Al, Ti and Fe³⁺, suggesting that the crystallization occurred under decreasing SiO₂/Al₂O₃ ratios and under relatively highpH₂O–pO₂ conditions.Pyroxenes from the Pietre Nere melasyenite show a progressive variation towards acmite rich compositions at Mg/(Mg+Fe²⁺+Fe³⁺) lower than 0.5; those from the layered melagabbro, instead, show a continuous enrichment in Ca Fe³⁺ AlSiO₆. This different behaviour is due to the co-crystallization, with the latest pyroxenes, of phases with different K/Na and Si/Al ratios.

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Kristallisations-Tendenzen der Pyroxene aus Alkali-Subvulkaniten auf Punta delle Pietre Nere (Gargano, Süditalien)

Zusammenfassung Es werden die Ergebnisse der Mikrosonden-Untersuchungen von Klinopyroxenen aus Alkali-Melasyeniten und schichtigen Alkali-Melagabbros, die durch Intra-plate-Magmatismus paläozenen Alters auf Punta delle Pietre Nere entstanden sind, beschrieben und erörtert.Die untersuchten Pyroxene reichen von diopsidischen bis zu Akmit-reichen Zusammensetzungen.Die zuerst kristallisierten Pyroxene (Diopsid) zeigen Al^VI-Gehalte, die auf geringe Tiefe des Kristallisationsvorganges hinweisen. Dazu zeigen die Pyroxene aus dem Melasyenit und aus dem Melagabbro unterschiedliche Cr-Gehalte; die Al/Ti- und Mg/(Mg+Fe²⁺+Fe³⁺)-Verhältnisse bestätigen deren Kristallisation aus Schmelzen, die aus unterschiedlichen Ursprungsmagmen stammen.Die Diopside und Salite zeigen eine einheitliche Tendenz zu hohem Al-, Ti- und Fe³⁺-Gehalt; dies deutet darauf hin, daß die Kristallisation unter abnehmenden SiO₂/Al₂O₃-Verhältnissen und unter relativ hohenpH₂O–pO₂-Bedingungen stattfand.Die Pyroxene aus dem Punta delle Pietre Nere-Melasyenit zeigen eine zunehmende Änderung zu Akmit-reichen Zusammensetzungen bei weniger als 0,5 Mg/(Mg+Fe²⁺+Fe³⁺); die Pyroxene aus dem schichtig differenzierten Melagabbro zeigen dagegen eine allmähliche Zunahme von CaFe³⁺AlSiO₆. Dieses unterschiedliche Verhalten rührt daher, daß Mineralphasen mit unterschiedlichen K/Na- und Si/Al-Verhältnissen zugleich mit den zuletzt gebildeten Pyroxenen kristallisierten.

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With 6 Figures     

Coexisting pyroxenes from the basic granulites of Visakhapatnam area in the Eastern Ghats terrain

Fifteen pairs of coexisting pyroxenes from basic granulites associated with leptynites in the khondalite suite of rocks are analysed and the distribution of Mg and Fe²⁺ ratios is presented. Temperature estimates for the coexisting pyroxenes from the basic granulites of Visakhapatnam may be expressed as 750±100†C corresponding to intermediate pressure granulites.     

The solid solution chemistry of vesuvianite

Solid solution in vesuvianite is elucidated by examining chemical trends and cation abundances in 22 microprobe analyses of samples from the Big Maria Mountains, southeastern California. Two recent structure refinements indicate 50 filled cation sites per formula, providing the basis for data normalization. Previous optical absorption and Mössbauer studies help clarify site occupancies. Stoichiometric abundances of Si and Ca + Na indicate 18 and 19 per formula, filling all 4- and 8-fold sites respectively. The four 6-fold A-sites are filled with Al. The solid solution occurs mainly within the eight 6-fold AlFe-sites (Al, Mg, Fe²⁺, Fe³⁺, Ti) and one 5-fold B-site (Mg, Fe²⁺, Fe³⁺). Chemical trends and crystal chemical constraints delineate eight independent substitutions.An extensive solid solution in the elements Mg, Fe, Al, and Ti suggests considerable potential as a petrogenetic indicator. In order to treat equilibria involving vesuvianite thermodynamically, a reference composition must be chosen and activity-composition relations modeled. For a reference composition, Mg-vesuvianite (Fe, Ti, Na-free) was chosen because of its chemical simplicity, but problems in ascertaining its stoichiometry have led previous workers to propose at least six different formulas. In this study, its formula is determined from the microprobe analyses by applying exchange vectors to substitute components of pure Mg-vesuvianite for Fe and Ti. This yields Ca₁₉Mg₂Al₁₁-Si₁₈ O₆₉(OH)₉, with AlFe-sites=MgAl₇, and B-sites=Mg. Subdivision of the AlFe-sites into at least two distinct sites is suggested by observed chemical trends which are explanable only when different substitutions are considered to operate within different AlFe-sites.A thermodynamic mole fraction is formulated for Mg-vesuvianite based on an ideal mixing-on-sites solution model. A method is provided for estimating the distribution of Fe between the AlFe- and B-sites. Thermodynamic mole fractions calculated using Fe site distributions estimated from microprobe data yield results similar to those calulated using Fe site distributions determined from Mössbauer analysis.     

一种新的闪石共存对—铁闪石与铁韭闪石对

新近在我国山西省娄烦县尖山铁矿的角闪片岩中发现一种取向连生的镁铁质闪石与钙质闪石共存对。电子探针分析确定它们分别为铁闪石Ｋ０．００１（Ｎａ０．０２７Ｃａ０．０７３Ｍｎ０．０３１Ｆｅ＾２＋１．８０１）１．９３２（Ｆｅ＾２＋２．９４８Ｍｇ１．９６４Ｔｉ０．００２Ａｌ０．０８７）５Ｓｉ８．０６９Ｏ２２．１０（ＯＨ）２与铁韭闪石（Ｋ０．１３５Ｎａ０．４６１）０．５９６（Ｎａ０．０８８Ｃａ１．８５３Ｍｎ０．     

Aluminium in coexisting pyroxenes as a sensitive indicator of changes in metamorphic grade within the Mafic Granulite Terrane of the Fraser Range,Western Australia

Three pairs of coexisting pyroxenes of mafic granulites from each of two locations 100 km apart show large chemical differences, especially in Al, Fe, Mn, Ti and Na. Al content of the pyroxenes at the higher pressure locality is more nearly independent of Al of the host rock than are the pyroxenes from the lower pressure locality. All the data confirm that although no significant difference in temperature has emerged, there was a large difference in pressure between the two localities. Al is found to be a more effective discriminant of metamorphic conditions than . As the three pairs of pyroxenes cover a wide range of Fe at each locality, the close relationship of Al and Na (and of Ca-tschermak and jadeite) to Fe becomes evident. This shows that a normalizing procedure should be adopted before comparing localities with different Al, Mn, Ti, Na and other elements or derived components such as jadeite and Ca-tschermak.     

Geochemical Indication of Sinian Bedded Siliceous Rocks in the Hunan-Guizhou-Guangxi Area and Their Environmental Significance

In the Hunan-Guizhou-Guangxi area there have developed very thick bedded siliceous rocks of the late Sinian. The rocks have a fairly pure composition, with an average content of siliceous minerals exceeding 95%. They are relatively rich in Fe and Mn, and poor in Al, Ti and Mg. The Fe/Ti, (Fe+Mn)/Ti, Al/(Al+Fe+Mn) and U/Th ratios and the Al-Fe-Mn and Fe-Mn-(Ni+Co+Cu)×10 triangle diagrams all show that they are hydrothermal sedimentary siliceous rocks. In the rocks the total amount of REEs is low, the δCe shows an obvious negative anomaly and the 8Eu a weak anomaly, and LREE>HREE, all indicating that they are products of hydrothermal processes. The δ30Si and δ18O values, as well as the formation temperature of the rocks all clearly show that the silica forming the rocks comes from hot water. Besides, analyses of the depositional environment of the rocks using the MnO/TiO2 ratio and the δCe and δ30Si values yield the same conclusion that they are formed in environments from continental marginal slope     

Amphiboles of a Metagabbro--Amphibolite Sequence, Hidaka Metamorphic Belt, Hokkaido

The western part of the Hidaka Metamorphic Belt, Hokkaido, consistsof primary pyroxene gabbro and lesser amounts of olivine gabbrothat have been dynamically metamorphosed to metagabbro—gabbroicamphibolite-amphibolite-epidote amphibolite during uplift andshearing about 23 m.y. ago. Textures and the presence of relic and recrystallized amphiboleand plagioclase in the same rock indicate incomplete reactionand non attainment of equilibrium during recrystallization. EPMA and bulk analyses of 165 amphiboles indicate a continuousoverall compositional range from actinolite to dark green hornblende(with 100 mg/(Mg+Fe²⁺+Fe³⁺Mn) ratios varying from 89.5 to 32.0)marked by increasing Al, Fe, Ti, and Na. A compositional gapis usually present between relic and recrystallized amphibolesin any one rock which becomes more prominent with increasingshearing. In addition to host rock chemical control, amphibole compositionis largely dependent on the An content of coexisting plagioclase.Locally epidote and sphene exert a strong influence on bothamphibole and plagioclase compositions. Amphibole Ti and Mncontents decrease with shearing and Fe enrichment of the hostrocks largely as a result of the incoming of rutile, sphene,and Fe-Ti oxides. Analysis of host rock oxidation ratio andamphibole compositions indicates that the rocks essentiallybehaved as closed systems to oxygen during metamorphism. Al^1V-Al^IV, Al^IV-Fe³⁺, and Al^IV-(Na, K)^A are the main substitutionsin the amphiboles. Within any one rock the recrystallized amphibolesare enriched in Al, Fe, Ti, and Na relative to the relice amphiboles.Increasing metamorphism results in a progressive change of amphiboles(recrystallized) to more Fe and Si (rather than Al) rich compositionsreflecting the trend towards greenschist where Fe-actinolite(+Mg chlorite) would be stable. Differentiation of the amphiboles is within the limits of SiAlreplacement and the compositional limits of the early stagereaction rim and replacement amphiboles in the host olivineand pyroxene metagabbros.     

Chemistry,subsolidus relations and electron petrography of pyroxenes from the late ferrodiorites of the Skaergaard intrusion,East Greenland

The ferroaugites, inverted ferrowollastonites and the brown and green ferrohedenbergites from the Upper Zone (UZb and UZc) of the Skaergaard intrusion (Brown and Vincent, 1963) have been studied with the electron microprobe, and where necessary, with the electron microscope. The cloudy “inclusions” in the inverted ferrowollastonite (Wo_ss) of 4471 are established to be strain fields associated with stacking faults, dislocations and sub-grain boundaries. The green pyroxenes of 1881 have undoubtedly inverted from Wo_ss, as both major and minor element chemistry show. The orientation of the tie-line joining coexisting Ca-rich and Ca-poor pyroxenes has also been established for this part of the quadrilateral, together with the Fe-Mg values at which the 4471 inverted Wo_ss would project on to Brown and Vincent's (1963) trend line for Ca-rich pyroxenes. These Fe-Mg values are the same as those of the 1881 brown ferrohedenbergites (Hed_ss). The subsolidus cooling history of the inverted Wo_ss has been examined in the light of the present data. It is proposed that a Wo_ss of solidus composition Wo₃₉ may either (a) react to a two-phase assemblage of Hed_ss (composition Wo_42.5) + metastable clinoferrosilite, or (b) invert metastably to a Hed_ss of the same composition. For specimen 4471, these two types of subsolidus behaviour may occur in different crystals within the same large mosaic-patterned grain. The proposed model is consistent with difficulty in nucleation of clinoferrosilitic lamellae, combined with the sluggishness of reactions at low temperatures for these Fe-rich compositions. In both case (a) and (b), inversion to Hed_ss (with or without the formation of mosaic texture) precedes exsolution of clinoferrosilite. The two final subsolidus compositions for the host are ～Wo₄₆ and ～Wo₄₂, for types (a) and (b) respectively, and the final subsolidus composition of the lamellae is Wo₀-Wo₂. The brown and green pyroxenes of 4330 show distinct differences in chemistry, the green being richer in Si, and depleted in Al and Ti relative to the brown. The 4330 green pyroxenes are poorer in Mn, and richer in Na, compared to the green inverted Wo_ss. The green colour in these UZc pyroxenes may be due to the drop in Ti content relative to brown pyroxenes.     

The Zoned Clinopyroxenes of the Shiant Isles Sill, Scotland

The zoned clinopyroxenes in samples from a near-vertical sectionthrough the main Shiant Isles sill have been studied using theelectron microprobe. In terms of Ca: Mg: Fe the over-all fractionationtrend is much greater than had been believed from bulk pyroxeneanalyses and is of a distinctive calcic augite-hedenbergitetype. In this respect it differs from both the augite-ferroaugiteand salite-aegirine trends generally regarded as typical oftholeiitic and alkaline basic magmas respectively, and it isproposed that this trend represents a third major type typicalof mildly alkaline basic magmas. The Al, Ti, and Na contentsof the pyroxenes are dependent on the degree of fractionationas represented by Mg/(Mg+Fe) and it is suggested that the Aland Ti contents are controlled by the Ti content of the liquidand the crystallization of titaniferous magnetite whereas theentry of Na into the pyroxene as aegirine is dependent on theactivity of Fe³⁺ in the liquid. To provide a basis for discussion of the crystallization ofthe zoned clinopyroxenes the existing petrogenetic hypothesesfor the Shiant Isles sill are reviewed and a new model proposedfor its emplacement and differentiation. It is concluded thatthe differences between the pyroxenes of the mildly alkalineShiant Isles sill and those of more strongly alkaline basicmagmas result from fundamental chemical differences in the magma.The lower Ca contents of the early pyroxenes are due to theslightly higher Si activity of the magma and the subsequenttrend towards hedenbergite rather than aegirine is due to crystallizationunder conditions of relatively lower oxygen fugacity, probablyas a result of lower initial H₂O content of the magma.     

河北矾山杂岩体中单斜辉石的研究

河北矾山杂岩体属于二氧化硅不饱和的超钾质碱性-过碱性岩浆系列,由单斜辉石岩、辉石正长岩和碱长正长岩等不同类型岩石组成。各类型岩石主要组成矿物为单斜辉石、黑云母、石榴石和正长石。本文利用电子探针对单斜辉石进行了详细研究,发现所有单斜辉石属于高钙透辉石,随着岩浆的演化,主要表现为Fe²⁺对Mg²⁺的替代关系,结晶趋势为透辉石→钙铁辉石,这揭示矾山杂岩体岩浆体系的特点是高温、中等大小的氧逸度、贫硅、富碱（尤其是钾）。辉石中的Al^IV含量取决于岩浆的硅饱和度,硅越不饱和,Al^IV含量越高;Al^VI含量则与体系中的Al含量呈正相关关系。由Al对Si的替代引起的电荷不平衡主要由八面体位置的Fe³⁺来补偿,其次为少量的Ti⁴⁺和更少量的Al³⁺。体系中的Ti含量与体系的温度呈正相关关系,而Na含量则与辉石中的Ti和Fe³⁺含量成正相关关系。不同类型岩石中单斜辉石从核部到边部随着Mg^#的降低,Al、Ti含量呈现不同的演化趋势,这是因为它们于岩浆演化的不同阶段开始结晶,经历了不同的岩浆演化史。碱性岩中高钙辉石的出现和成分环带的普遍发育是由岩浆的贫硅富钾特征决定的。单斜辉石的成分不仅受控于结晶时的温度、压力条件,也受控于岩浆的总成分及其变异。     

Rhönite in undersaturated alkaline gabbroic rocks,Central Alborz,North Iran: petrography and mineral chemistry

The Kamarbon alkaline gabbroic intrusion crops out in Central Alborz, north Iran, along the northern margin of the Alpine-Himalayan belt. The gabbroic intrusion includes theralites at margins which replace with teschenites toward the center. In teschenitic rocks, the main minerals are diopside, clinopyroxene, and rhönite. In this research, the occurrence of rhönite is reported in Kamarbon teschenitic gabbros, and also its mineralogical properties, paragenesis, and source magma are investigated. Based on whole rock and microprobe analysis data, we try to clarify the formation of Kamarbon gabbro and the crystallization condition of rhönite. In teschenitic gabbros, rhönite reveals the composition (Na, Ca)_1.97(Ti, ^VIAl, Fe⁺³, Fe⁺², Mn, Mg)_5.99(Si, ^IVAl)_6.02O₂₀. On the basis of petrographical observations and mineral chemistry, we suggest that the teschenites were formed in distinctive lower pressures and temperatures than theralites, below 1.9 kbar and 1075 °C. Rhönite was crystallized (at the mentioned P-T condition) as a primary phase, in the late stage of crystallization at shallow depth corresponding with 6–10 km, in teschenites. Important factors of the rhönite crystallization in undersaturated magmas can be regardarded as Al and Ti enrichment and Si depletion; the same enrichment and depletion are also observed in the associated clinopyroxenes.