Processes of regional metamorphism and ultrametamorphism and some problems of the geology of the deep-lying sections of folded zones

On the basis of 135 pairs of chemical analyses of coexisting hornblendes and biotites, we have established a relationship between the contents of Al^IV, Al^VI, Fe³⁺, Mg, Ti, Na, and K and the overall iron index in the hornblendes and the depth of granitoid formation. This relationship has been emphasized by the R-method of factor analysis. We have examined the strength and nature of the correlations between the elements in the hornblendes and have considered the types of Isomorphism in the amphiboles according to depth, from the viewpoint of crystal chemistry. A regular increase in the amounts of A^IV in hornblende from <0.8 to > 1.6 formula units; of (Al^VI + Fe³⁺ + Ti) from <0.5 to >1. 0 formula units; of (K + Na) from <0.35 to >0. 64 formula units; and of Group A from <0.24 to >0.51 formula units has been recorded from the near-surface granitoids to the ultra-abyssal types. Biotites In this respect display no adequately clear and reliable information.—Authors.     

A Comparison of amphiboles from medium- and low-pressure metabasites

A comparison of published metabasite amphibole analyses from medium and low-pressure metamorphic terrains reveals that there is no systematic variation in Na, Na^M4, Al or Al^VI as a function of pressure. This may be due to blurring of the differences by variation in oxidation state, or by analytical differences between laboratories. It is not due to variable Mg/Fe in whole rocks. Differences that can be recognised are generally higher Ti/Al ratios in the low-pressure amphiboles, and a very poorly developed compositional gap between actinolite and hornblende compared with a well-developed gap at medium pressures. These features, together with the relatively low-grade appearance of calcic plagioclase at low pressures, provide the best means of distinguishing metabasites from the two facies series.All three features can be explained by the configuration of cation-exchange equilibria at the greenschist/amphibolite facies boundary. Enrichment in Ti at low-pressures is due to the positive slope of reactions partitioning Ti into the amphibole. The composition gap in amphiboles at medium-pressure is due to overstepping of the tschermakite-enriching equilibrium. At low pressures this overstepping still occurs, but the equilibrium tschermakite-content in the amphibole is much lower for a given amount of overstepping. The relatively low-grade appearance of oligoclase at low pressures is due to convergence of the tschermakite and anorthite-enriching equilibria with decreasing pressure.     

The compositional variation of synthetic sodic amphiboles at high and ultra-high pressures

Sodic amphiboles in high pressure and ultra-high pressure (UHP) metamorphic rocks are complex solid solutions in the system Na₂O–MgO–Al₂O₃–SiO₂–H₂O (NMASH) whose compositions vary with pressure and temperature. We conducted piston-cylinder experiments at 20–30?kbar and 700–800?°C to investigate the stability and compositional variations of sodic amphiboles, based on the reaction glaucophane=2jadeite+talc, by using the starting assemblage of natural glaucophane, talc and quartz, with synthetic jadeite. A close approach to equilibrium was achieved by performing compositional reversals, by evaluating compositional changes with time, and by suppressing the formation of Na-phyllosilicates. STEM observations show that the abundance of wide-chain structures in the synthetic amphiboles is low. An important feature of sodic amphibole in the NMASH system is that the assemblage jadeite–talc?±?quartz does not fix its composition at glaucophane. This is because other amphibole species such as cummingtonite (Cm), nyböite (Nyb), Al–Na-cummingtonite (Al–Na-Cm) and sodium anthophyllite (Na-Anth) are also buffered via the model reactions: 3cummingtonite?+?4quartz?+?4H₂O=7talc, nyböite?+?3quartz=3jadeite?+?talc, 3Al–Na-cummingtonite + 11quartz + 2H₂O=6jadeite + 5talc, and 3 sodium anthophyllite?+?13quartz?+?4H₂O=3 jadeite + 7talc. We observed that at all pressures and temperatures investigated, the compositions of newly grown amphiboles deviate significantly from stoichiometric glaucophane due to varying substitutions of Al^IV for Si, Mg on the M(4) site, and Na on the A-site. The deviation can be described chiefly by two compositional vectors: [Na^AAl^IV]<=>[□^ASi] (edenite) toward nyböite, and [Na^(M4)Al^VI]<=>[Mg^(M4)Mg^VI] toward cummingtonite. The extent of nyböite and cummingtonite substitution increases with temperature and decreases with pressure in the experiments. Similar compositional variations occur in sodic amphiboles from UHP rocks. The experimentally calibrated compositional changes therefore may prove useful for thermobarometric applications.     

Statistical chemistry of calcic amphiboles

Principal components analysis is used to study the chemistry of 639 calcic amphiboles. Eigenvectors representing multiple partial correlation coefficients give various sets of substitutional relationships. The relative significance of each set can be noted by the percent variation of the data it represents. The highest percent variation (36%) is associated with the substitutions $$Si + Mg \rightleftharpoons Al^{IV} + Al^{VI} + Ti + Fe^{3 + } + Fe^{2 + } + Na + K$$ . Other expected substitutions among the ions such as Al^IV + Na ? Si, the positive correlation between Al^IV and Al^VI etc. are shown statistically. The substitution of Al in T ₁ and T ₂ positions imposes an ordering in the M ₁, M ₂ and M ₃ sites. Variability of OH in the amphiboles is found to be significant. There is no definite correlation between OH and Fe³⁺ but OH and Ti are positively correlated. Under certain conditions and provided the concentration of Al^IV does not change significantly, Fe and Mg may be assumed to mix ideally in the amphibole solid solution.     

Coexisting Amphiboles from Blueschist Facies Metamorphic Rocks

Four pairs of associated calcic and sodic amphiboles from blueschistfacies metamorphic rocks were analyzed with the electron microprobeand studied by single-crystal X-ray diffraction techniques.Except for ranges in the ratios Mg/(Mg+Fe) and Fe³⁺/(Fe³⁺+Al+Ti),the sodic amphiboles are similar in chemical composition. Theamount of calcium in the M(4)-site ranges only from 0·18to 0·21 ion per formula unit. The calcic amphiboles,in addition to a range in Mg/(Mg+Fe), vary in Na/(Na+Ca) ratio(0·29–0·48). Three of the calcic amphibolescontain less than 1·5 calcium ions per formula unit,indicating a significant solid solution of sodic amphibole componentsin the calcic amphibole phase. The a and b unit-cell parametersof the calcic amphiboles decrease with increased content ofthe sodic component.     

Optical spectroscopy study of natural Fe, Ti-bearing calcic amphiboles

Over thirty samples of natural Ti-bearing amphiboles with Ti- and Fe-contents ranging from 0.111 to 0.729 atom per formula unit (a.p.f.u.) and from 0.479 to 2.045 a.p.f.u., respectively, were studied by means of optical absorption spectroscopy and microprobe analysis. Thirteen samples were also studied by Mössbauer spectroscopy. A strong pleochroic absorption edge, causing the dark brown colours of Ti-bearing amphiboles, is attributed to ligand-metal and metal-metal charge transfer transitions involving both iron and titanium ions (O^2?→ Fe³⁺, Fe²⁺, O^2?→ Ti⁴⁺ and Fe²⁺ + Ti⁴⁺→ Fe³⁺ + Ti³⁺). A broad intense Y-polarized band ～22?000?cm^?1 (ν_1/2?≈?3700?cm^?1) in spectra of two low iron amphiboles with a relatively low Fe³⁺/Fe_total ratio, both from eclogite-like rocks in kimberlite xenoliths, was attributed to electronic Fe²⁺(M3) + Ti⁴⁺(M2)→Fe³⁺(M3)+Ti³⁺(M2) IVCT transitions. The IVCT bands of other possible ion pairs, involving Ti⁴⁺ and Fe²⁺ in M2 and M1, M4 sites, respectively, are presumed to be at higher energies, being obscured by the absorption edge.     

The Crossite Content of Ca-Amphibole as a Guide to Pressure of Metamorphism

A correlation between the crossite component (NaM₄) in Ca-amphiboleand pressure of metamorphism has long been recognized (Shido& Miyashiro, 1959), but only recently has the reaction beenidentified which buffers this aspect of amphibole composition(Brown, 1974): Ca-amphibole+iron oxide+albite+chloriteI+H₂O (±stilp,qtz) = crossite+epidote (±muscovite, qtz). The exact stoichiometry of the reaction depends on compositionalvariables in the minerals, especially Fe²⁺/Mg and Fe³⁺/Al. Ca-amphiboleshould have fixed NaM₄, at any given T and P, where it coexistswith iron oxide, albite, and chlorite. Comparison of Ca-amphibole composition with mineral assemblage,in rocks from Otago, N.Z., and elsewhere, supports this hypothesis.In any terrane NaM₄ is nearly constant at a particular metamorphicgrade where amphibole exists in the buffering assemblage, butvaries widely outside of this assemblage. Variations in Fe²⁺/Mgand Fe³⁺/Al in the amphibole have relatively little effect onNaM₄, but in high pressure amphiboles NaM₄ varies inverselywith Al^iv. Ca-amphiboles from high pressure areas have substantially moreNaM₄ (Otago, 0.6 of 2.0) than those from lower pressure areas(Sierra contact aureoles, 0.1). These relations suggest thatin the buffering assemblage, the NaM₄ content of Ca-amphiboleshould be a useful relative barometer for low to medium grademetamorphic rocks.     

Actinolite-hornblende pairs in metamorphosed gabbros,Hidaka mountains,Hokkaido

Actinolite-actinolitic hornblende and actinolitic hornblende-hornblende pairs are described from gabbroic amphibolites and epidote amphibolites formed by dynamic metamorphism during uplift of gabbroic rooks in the Hidaka Metamorphic Belt, Hokkaido. Electron microprobe analyses indicate that coupled substitutions involved in the transition from actinolite to hornblende are essentially those of edenite and tschermakite-ferritschermakite together with smaller amounts of glaucophane-riebeckite, i.e. Al^IV, Al^VI, Fe³⁺, A-site occupancy and Na^M4 increase with replacement of Mg by Fe²⁺+ Mn and Si by Al^IV. During metamorphism the amount of deformation due to shearing has affected the degree of compositional discontinuity in the actinolite-hornblende series and the compositional gap is most pronounced in the epidote amphibolite. The coexisting actinolite-hornblende do not represent an equilibrium pair as textural relations indicate that the actinolitic amphiboles are relics. It is suggested that shearing deformation during uplift has caused an overstepping of the changing physico-chemical conditions of metamorphism so that compositional readjustment of amphiboles was not achieved. Equilibrium-disequilibrium actinolite-hornblende pairs are discussed from other localities where rocks of basaltic composition have been metamorphosed.     

Phase equilibria in rocks of the paleoproterozoic banded iron formation (BIF) of the Lebedinskoe deposit, Kursk Magnetic Anomaly, and the petrogenesis of BIF with alkali amphiboles

BIF with alkali amphibole at the Lebedinskoe iron deposits, the largest in Russia, were metamorphosed at 550°C and 2–3 kbar and contain ferriwinchite, riebeckite, actinolite, grunerite, and aegirine-augite. All reaction textures observed in the rocks were produced during the prograde metamorphic stage and represent the following succession of mineral replacements: Gru → Rbk, Act → Win → Rbk. Data obtained on the textural relations and compositional variations of Ca, Ca-Na, and Na Al-free amphiboles point to the complete miscibility in the actinolite-ferriwinchite and ferriwinchite-riebeckite isomorphic series. Riebeckite is formed in BIF during the prograde metamorphic stage, with the participation of a fluid insignificantly enriched in Na⁺ and at increasing oxygen fugacity. The critical factors controlling the development of alkali amphiboles and Ca-Na pyroxenes in carbonate-bearing BIF is the oxygen activity and the presence of at least low concentrations of Na⁺ ions in the fluid. The minerals contain Fe³⁺, and all reactions producing them are oxidation reactions. The origin of riebeckite late in the course of the mineral-forming process is caused by the Ca²⁺Mg²⁺ → Na⁺Fe³⁺ heterovalent isomorphic replacement in calcic and calcic-sodic amphiboles and by the oxidation of grunerite in the presence of a fluid enriched in Na ions.     

Mineral reactions participating in intragranular fracture propagation: implications for stress corrosion cracking

Two examples of mineral reactions accompanying intragranular fracturing of silicates are described from amphibolites at the Grenville front, Coniston, Ontario, and a granodiorite within the Miéville shear zone, Switzerland. At these localities coarse grained (> 1 mm) hornblende and biotite respectively have undergone initial deformation by intense transgranular fracturing. The ambient temperature of deformation is estimated at 400–500°C for the amphibolites, and 250–300°C for the granodiorite.Fracture intensity within hornblende increases with progressive deformation until fractures coalesce and grains lose cohesion. Fractures are occupied by hornblende in close optical continuity with the parent grain, and typically contain median sutures decorated by arrays of solid inclusions. Relative to the parent grain, hornblende in fractures is depleted in Ti, Al, plus K, and enriched in Mg. Given the preferential partitioning of Mg, Al^VI and Ti into the M2 site of calcic amphiboles, the decrease of Ti and Al^VI in the host-to-crack transition is consistent with the corresponding increase of the Mg/(Mg + Fe²⁺) ratio.Fractures within biotite are bounded by an envelope of paler brown biotite which corresponds to a decrease of Ti and increase of Fe + Mg relative to regions unaffected by cracking. Fractures are occupied by secondary ilmenite, low-Ti biotite and high-Ti muscovite. Ti and Al do not vary significantly as a function of Mg/(Fe + Mg) in the host-to-crack transition, as anticipated from the approximately equal partitioning of these two cations into the M1 and M2 octahedral cation sites. The direct relationship of the mineral reactions to the fractures is taken as evidence for the participation of the reactions in crack propagation. These features may thus represent examples of natural stress corrosion cracking.     

Detrital glaucophane in graywackes of the Rhenohercynian Harz mountains and the geodynamic implications

Detrital blue amphibole was found for the first time in two samples of the Famennian section of the South Harz-Selke Graywacke and the Tanne Graywacke (Middle Visean) of the Harz Mountains. Microprobe analyses reveal that the blue amphiboles represent glaucophane with Fe³⁺/(Fe³⁺+Al^VI)=0.22 molar ratio. The minimum pressure required for the formation of glaucophane of this composition is estimated to be approximately 8 kbar. The source area of the detrital glaucophane is assumed to be located between the Northern Phyllite Zone and the Mid-German Crystalline Rise, in areas which have been downfaulted (?subducted) during the Variscan orogeny. The age of blueschist-facies metamorphism in the source area must be of pre-Upper Devonian age. This metamorphic event is significantly older than the Lower Carboniferous high-pressure/low-temperature metamorphism documented in parts of the northern Phyllite zone. Hence, the convergent tectonics connected with blueschist-facies metamorphism is not restricted to the Lower Carboniferous, but can be traced back at least to the early Upper Devonian. These data are in accordance with a southerly directed underplating (?subduction) at the northern margin of the Saxothuringian zone active during at least from early Upper Devonian to Lower Carboniferous.     

Mineral chemistry of Plio-Quaternary subvolcanic rocks,southwest Yazd Province,Iran

The NW–SE-trendingLate Cretaceous–Cenozoic Urumieh-Dokhtar Magmatic Arc (UDMA) in southwest Iran hosts numerous Plio-Quaternary subvolcanic porphyritic andesitic to rhyodacitic domes intruded into a variety of rock sequences. Bulk-rock geochemical data show that the calc-alkaline dacitic to rhyodacitic subvolcanic rocks share compositional affinities with high-silica adakites, including high ratios of Na₂O/K₂O >1, Sr/Y (most >70), and La/Yb (>35), high Al₂O₃ (>15 wt.%), low Yb (<1.8 ppm) and Y (<18 ppm) contents, no significant Eu anomalies, and flat to gently upward-sloping chondrite-normalized heavy rare-earth element (HREE) patterns. All analysed rocks are characterized by enrichment in large-ion lithophile elements (LILEs) and depletion in high field strength elements (HFSEs). They also display typical features of subduction-related calc-alkaline magmas. In chondrite-normalized rare-earth element patterns, the light rare-earth elements (LREEs) are enriched ((La/Sm) _N = 3.49–7.89) in comparison to those of the HREE ((Gd/Yb) _N = 1.52–2.38). Except for the G-Aliabad Dome, plagioclase crystals in the Shamsabad, Ostaj, Abdollah, and Bouragh Domes are mostly oligoclase to andesine (An_19–49). Amphibole and biotite are abundant ferromagnesian minerals in the subvolcanic rocks. Calcic amphiboles are dominantly magnesiohornblende, magnesiohastingsite, and tschermakite with Mg/(Mg + Fe_tot) ratios ranging from 0.58 to 0.78. In all the studied domes, amphiboles are typically ferric iron-rich, but that those the Shamsabad Dome have the highest Fe³⁺/(Fe³⁺ + Fe²⁺) ratios, between 0.69 and 0.98. Amphiboles from the Ostaj and Shamsabad Domes are relatively rich in F (0.39–1.01 wt.%) in comparison to the other studied domes. This phase commonly shows pargasitic and hastingsitic substitutions with a combination of tschermakitic and edenitic types.

Temperature-corrected Al-in-hornblende data show that amphibole phenocrysts from the Ostaj, Abdollah, and G-Aliabad Domes crystallized at pressures ranging from 2.14 to 3.42 kbar, 3.49 to 3.96 kbar, and 2.02 to 3.47 kbar, respectively. Temperatures of crystallization calculated with the amphibole–plagioclase thermometer for the Ostaj, Abdollah, and G-Aliabad subvolcanic domes range from 735°C to 826°C (mean = 786 ± 29), 778°C to 808°C (mean = 791 ± 13), and 866°C to 908°C (mean = 885 ± 12), respectively. In the annite–siderophyllite–phlogopite–eastonite quadrilateral, biotite from the G-Aliabad, Bouragh, and Ostaj Domes are characterized by relatively low total Al contents with variable Fe_tot/(Fe_tot + Mg) values from 0.26 to 0.43. All biotite analyses define a nearly straight line in the X _Mg versus Fe_tot plot, with r = –0.96 correlation coefficient. In comparison to other domes, the F content of biotite from the G-Aliabad Dome shows high concentrations in the range of 1.80–2.57 wt.% (mean = 2.20). Inferred pre-eruptive conditions based on the calcic amphibole thermobarometric calculations for the Shamsabad, Abdollah, and Ostaj Domes show that the calc-alkaline subvolcanic magma chamber, on average, was characterized by a water content of 6.10 wt.%, a relatively high oxygen fugacity of 10^–10.66 (ΔNNO + 1.28), a temperature of 896°C, and a pressure of 2.75 kbar.     

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.     

Composition of hornblendes formed during the hercynian progressive metamorphism of the Aracena metamorphic belt (SW Spain)

This paper attempts to illustrate the chemical variations of metamorphic hornblendes regarding host rocks and prograde variations. Changes related to bulk chemistry (orthoamphibolites) mainly concern Si, Al, Mg, Fe_tot and Ca. The Mg, Fe²⁺ and Fe³⁺ contents of hornblendes are, however, not strictly related to host rook compositions and Mg enrichments are correlated with increasing Fe³⁺ contents in the amphiboles. Thus, variations of oxygen fugacity may control the Mg contents of the Ca amphiboles studied but this does not show clear relations with the prograde metamorphism. The most sensitive but irregular variation related to the metamorphic conditions is the prograde enrichment of the alkalis into the A vacant position and an increase of the (Na+K)_tot/Na+K+Ca ratios of the amphiboles. Increasing Ti and Al^IV contents as well as decreasing Al^VI concentrations are also, but much less evidently, related to increasing T and P. A variation trend from tschermakitic to edenitic hornblendes may be drawn using Shido's end members calculation; this tendency and the relative deficiency of Al^VI contents in the low-grade members suggests that the amphiboles studied were subjected to conditions of a low-pressure metamorphism type. Such a conclusion is in agreement with the occurrence of andalusite-cordierite/sillimanite-cordierite associations in the metapelitic rocks, and the absence of Fe-rich garnet and epidote from the orthoamphibolites of the amphibolite facies at Aracena. Comparisons with Ca amphiboles from other metamorphic areas show, in agreement with various authors, that Abukuma hornblendes are similar to those encountered in high-grade thermal aureoles and tonalitic intrusives but different from the hornblendes of Barrovian metamorphism types.     

Calcic amphiboles in calc-alkaline and alkaline magmas: thermobarometric and chemometric empirical equations valid up to 1,130°C and 2.2 GPa

The following article presents constraints of the stability of Mg-rich (Mg/(Mg + Fe²⁺) > 0.5) calcic amphibole in both calc-alkaline and alkaline magmas, testing of previous thermobarometers, and formulation of new empirical equations that take into consideration a large amount of literature data (e.g. more than one thousand amphibole compositions among experimental and natural crystals). Particular care has been taken in choosing a large number of natural amphiboles and selecting quality experimental data from literature. The final database of experimental data, composed of 61 amphiboles synthesized in the ranges of 800–1,130°C and 130–2,200 MPa, indicates that amphibole crystallization occurs in a horn-like P–T stability field limited by two increasing curves (i.e. the thermal stability and an upper limit), which should start to bend back to higher pressures. Among calcic amphiboles, magnesiohornblendes and tschermakitic pargasites are only found in equilibrium with calc-alkaline melts and crystallize at relatively shallow conditions (P up to ~1 GPa). Kaersutite and pargasite are species almost exclusively found in alkaline igneous products, while magnesiohastingsite is equally distributed in calc-alkaline and alkaline rocks. The reliability of previous amphibole applications was checked using the selected experimental database. The results of this testing indicate that none of the previous thermobarometers can be successfully used to estimate the P, T and fO₂ in a wide range of amphibole crystallization conditions. Multivariate least-square analyses of experimental amphibole compositions and physico-chemical parameters allowed us to achieve a new thermobarometric model that gives reasonably low uncertainties (T ± 23.5°C, P ± 11.5%, H₂O_melt ± 0.78wt%) for calc-alkaline and alkaline magmas in a wide range of P–T conditions (up to 1,130°C and 2,200 MPa) and ∆NNO values (±0.37 log units) up to 500 MPa. The ^AK-^[4]Al relation in amphibole can be readily used to distinguish crystals of calc-alkaline liquids from those of alkaline magmas. In addition, several chemometric equations allowing to estimate the anhydrous composition of the melts in equilibrium with amphiboles of calc-alkaline magmas were derived.     

The petrology of a complex sodic and sodic–calcic amphibole association and its implications for the metasomatic processes in the jadeitite area in northwestern Myanmar,formerly Burma

In the Myanmar jadeitite area of Pharkan, amphibole felses occur between jadeitites and serpentinized dunites. These so-called amphibole fels boundary zones were studied optically and by electron microprobe, and found to include the six amphibole species magnesiokatophorite (Mg-kat), nyböite (Nyb), eckermannite (Eck), glaucophane (Gln), richterite (Rich) and winchite (Win). In most samples, the two main amphibole species Mg-kat and Eck coexist with amphiboles containing variable amounts of components of the remaining four species, as well as with the clinopyroxenes jadeite (Jd), omphacite (Omp) and kosmochlor (Ko). However, Mg-kat, Nyb and Eck are also present as separate phases as well as in zoned porphyroblasts with Mg-kat in the core, Nyb in the inner rims, and Eck in the outer rims. The analytical data on such zoned amphiboles reveal that the chemistry changes from core to inner rim by virtue of the substitution NaAlCa _-1Mg _-1 (glaucophane vector), and from the inner to the outer rim along MgSiAl _-1Al _-1 (tschermak vector). The overall substitution from core to outer rim is, therefore, along NaSiCa _-1Al _-1 (plagioclase vector). Based on the Si content, three groups can be distinguished within Eck: Eck coexisting with Nyb has low Si contents of <7.6 a.p.f.u., Eck rimming Nyb has higher Si contents of 7.6–8.0 a.p.f.u., and fine-grained Eck in the matrix has Si contents of 7.9–8.0 a.p.f.u. Plotting the amphibole analyses in a compositional volume with the axes (Na+K) in A, Na in M(4), and tetrahedral Si shows that three groups of amphibole compositions can be distinguished, one being subdivided into three subsets. Group A contains Rich and Mg-kat, B comprises of Win and Gln, whereas the subsets C can be defined as follows: C1: high-Na amphiboles with low tetrahedral Si; these are mainly amphiboles from the Eck field but overlap with the two fields of Gln and Win; C2: high-Na and low-Si Ecks overlapping to high-Si Nybs; this group is midway between Eck and Nyb end members; C3: high-Na Mg-kats. Textural observations indicate three stages of sodic and sodic–calcic amphibole growth: stage 1 are amphiboles of group A (Mg-kat+Rich), stage 2 are amphiboles of group C2 (Nyb+Eck with Si<7.6 a.p.f.u.), and stage 3 are amphiboles of groups C1 and B (Eck with Si>7.6 a.p.f.u., +Gln+Win). Based on the subdivision into the compositional groups A–C, the only hint to a miscibility gap is provided by the large gap in the (Na+K) content on the A site which may point to a possible solvus in the system Eck–Win. Overall, the amphiboles investigated here show discontinuities in their growth compositions, rather than miscibility gaps. Textural observations suggest amphibole formation during fluid infiltration in the contact zone between the jadeitite bodies and the surrounding peridotite under high-pressure conditions (>1.0 GPa) and rather low temperatures of about 250–370 °C. Based on compositional trends within the amphiboles as well as phase-equilibrium constraints between amphibole and coexisting pyroxene solid solutions, the chemical composition of zoned amphibole porphyroblasts indicates two growth episodes—increasing pressures from stage 1 to stage 2 lead to the formation of Nyb from Mg-kat, and subsequently decreasing pressures lead to the formation of stage 3 Eck from Rich.     

Fe isotope systematics of coexisting amphibole and pyroxene in the alkaline igneous rock suite of the Ilímaussaq Complex,South Greenland

The Ilímaussaq intrusion, South Greenland, provides an exceptional test case for investigating the changes of stable Fe isotope fractionation of solidus phases with changes in the Fe³⁺/∑Fe ratio of an evolving melt. The intrusion comprises a sequence of four melt batches that were fed from the same parental alkali basaltic magma. Differentiation produced cumulate rocks that range from augite syenite (phase I) over peralkaline granite (phase II) to agpaitic syenites (phases IIIa and IIIb). Fe³⁺/∑Fe ratios in amphiboles increase substantially from phase I to phase II and III rocks and mark a major change in the parental magma composition from augite syenites to peralkaline granites and agpaitic syenites. Before this transition, olivine, clinopyroxene, and amphibole in augite syenite, the most primitive rock type in the Ilímaussaq Complex, have a uniform Fe isotope composition that is identical to that of the bulk of igneous crustal rocks and approximated by the average isotopic composition of basalts (δ^56/54Fe_IRMM-014 = 0.072 ± 0.046‰). After the transition, amphiboles in the peralkaline granites and agpaitic syenites yield significantly heavier Fe isotope compositions with δ^56/54Fe_IRMM-014 values ranging from 0.123 to 0.237‰. Contamination of the Ilímaussaq magma by ongoing crustal assimilation as cause for this increase can be excluded on the grounds of Nd isotope data. Large-scale metasomatic overprint with an external fluid can also be dismissed based on amphibole O and Li isotope systematics. Rather, the increase towards heavy Fe isotope compositions most likely reflects the change in chemical compositions of amphiboles (calcic in augite syenite to sodic in the agpaitic syenites) and their Fe³⁺/ΣFe ratios that mirror changes in the chemical composition of the melt and its oxygen fugacity. A sensitive adjustment of equilibrium Fe isotope fractionation factors to amphibole ferric/ferrous ratios is also supported by beta-factors calculated from Mössbauer spetroscopy data. Comparison of the measured isotope fractionation between clinopyroxene and amphibole with that predicted from Mössbauer data reveal Fe isotope systematics close to equilibrium in augite syenites but Fe isotopic disequilibrium between these two phases in phase IIIa agpaitic syenites. These results are in agreement with O and Li isotope systematics. While amphiboles in all Ilímaussaq lithologies crystallized at temperatures between 650 and 850 °C, textural evidence reveals later clinopyroxene crystallization at temperatures as low as 300–400 °C. Therefore, isotopic equilibrium at crystallization conditions between these two phases can not be expected, but importantly, subsolidus reequilibration can also be dismissed.     

The crystal chemistry and mössbauer study of schorlomite

Six schorlomite samples with TiO₂ contents varying between 9.70 and 15.34 weight percent were studied by means of Mössbauer spectroscopy and chemical analysis. The measured Mössbauer spectra have complex shapes. The spectra of these samples were fitted with six doublets, which can be assigned to ^VIIIFe²⁺, ^VIFe²⁺, ^VIFe³⁺, ^IVFe³⁺ and two electron delocalizations, ^IVFe³⁺ ? ^VIIIFe²⁺ and ^IVFe³⁺ ? ^VIFe²⁺, respectively. The assignment of iron absorption doublets and their Mössbauer parameters are discussed in terms of the single crystal structure data of one of the samples studied in this work. Cation distributions are also given. The occupancies of cations at the tetrahedral (Z) site are Fe³⁺>Al³⁺, Ti⁴⁺, and the relative enrichments at Z site are always Fe³⁺>Ti⁴⁺. Most of the six samples contain Ti³⁺. Ti³⁺/ΣTi ratios range from 1.43 percent to 6.40 percent. Fe²⁺/ΣFe ratios vary from 8.84 percent to 11.31 percent. Four types of substitution must be considered for Ti entering the garnet structure.     

Metasomatic oxidation of upper mantle periodotite

Examination of Fe³⁺ in metasomatized spinel peridotite xenoliths reveals new information about metasomatic redox processes. Composite xenoliths from Dish Hill, California possess remnants of magmatic dikes which were the sources of the silicate fluids responsible for metasomatism of the peridotite part of the same xenoliths. Mössbauer spectra of mineral separates taken at several distances from the dike remnants provide data on Fe³⁺ contents of minerals in the metasomatized peridotite. Clinopyroxenes contain 33% of total iron (Fe_T) as Fe³⁺ (Fe³⁺/Fe_T=0.33); orthopyroxenes contain 0.06–0.09 Fe³⁺/Fe_T; spinels contain 0.30–0.40 Fe³⁺/Fe_T; olivines contain 0.01–0.06 Fe³⁺/Fe_T; and metasomatic amphibole in the peridotite contains 0.85–0.90 Fe³⁺/Fe_T. In each mineral, Fe³⁺ and Fe²⁺ cations per formula unit (p.f.u.) decrease with distance from the dike, but the Fe³⁺/Fe_T ratios of each mineral do not vary. Clinopyroxene, spinel, and olivine Fe³⁺/Fe_T ratios are significantly higher than in unmetasomatized spinel peridotites. Metasomatic changes in Fe³⁺/Fe_T ratios in each mineral are controlled by the oxygen fugacity of the system, but the mechanism by which each phase accommodates this ratio is affected by crystal chemistry, kinetics, rock mode, fluid composition, fluid/rock ratio, and fluid-mineral partition coefficients. Ratio increases in pyroxene and spinel occur by exchange reactions involving diffusion of Fe³⁺ into existing mineral grains rather than by oxidation of existing Fe²⁺ in peridotite mineral grains. The very high Fe³⁺/Fe_T ratio in the metasomatic amphibole may be a function of the high Fe³⁺/Fe_T of the metasomatic fluid, crystal chemical limitations on the amount of Fe³⁺ that could be accommodated by the pyroxene, spinel, and olivine of the peridotite, and the ability of the amphibole structure to accommodate large amounts of 3 + valence cations. In the samples studied, metasomatic amphibole accounts for half of the bulk-rock Fe₂O₃. This suggests that patent metasomatism may produce a greater change in the redox state of mantle peridotite than cryptic metasomatism. Comparison of the metasomatized samples with unmetasomatized peridotites reveals that both Fe²⁺ and Fe³⁺ cations p.f.u. were increased during metasomatism and 50% or more of iron added was Fe³⁺. With increasing distance from the dike, the ratio of added Fe³⁺ to added Fe²⁺ increases. The high Fe³⁺/Fe_T of amphibole and phlogopite in the dikes and in the peridotite, and the high ratios of added Fe³⁺/added Fe²⁺ in pyroxenes and spinel suggest that the Fe³⁺/Fe_T ratio of the metasomatic silicate fluid was high. As the fluid perolated through and reacted with the peridotite, Fe³⁺ and C–O–H volatile species were concentrated in the fluid, increasing the fluid Fe³⁺/Fe_T.