Fluids in granulites of the Southern Marginal Zone of the Limpopo Belt, South Africa

The Southern Marginal Zone of the Limpopo Belt in South Africa is characterised by a granulite and retrograde hydrated granulite terrane. The Southern Marginal Zone is, therefore, perfectly suitable to study fluids during and after granulite facies metamorphism by means of fluid inclusions and equilibrium calculations. Isolated and clustered high-salinity aqueous and CO₂(-CH₄) fluid inclusions within quartz inclusions in garnet in metapelites demonstrate that these immiscible low H₂O activity fluids were present under peak metamorphic conditions (800-850 °C, 7.5-8.5 kbar). The absence of widespread high-temperature metasomatic alteration indicates that the brine fluid was probably only locally present in small quantities. Thermocalc calculations demonstrate that the peak metamorphic mineral assemblage in mafic granulites was in equilibrium with a fluid with a low H₂O activity (0.2-0.3). The absence of water in CO₂-rich fluid inclusions is due to either observation difficulties or selective water leakage. The density of CO₂ inclusions in trails suggests a retrograde P-T path dominated by decompression at T<600 °C. Re-evaluation of previously published data demonstrates that retrograde hydration of the granulites at 600 °C occurred in the presence of H₂O and CO₂-rich fluids under P-T conditions of 5-6 kbar and ~600 °C. The different compositions of the hydrating fluid suggest more than one fluid source.     

Mineralogy and Petrology of the Metamorphosed Wabush Iron Formation, Southwestern Labrador

The Wabush Iron Formation, of late Precambrian (Proterozoic)age is part of the Labrador Trough in southwestern Labrador,Canada. It is the regionally metamorphosed equivalent of lowgrade metamorphic (chlorite zone) iron-rich sediments of thecentral part of the Labrador Trough. The metamorphic grade iskyanite-staurolite zone, as concluded from conformably underlyingpelitic schist assemblages. Sedimentary textural features suchas very pronounced banding and a very rare occurrence of relicgranules are still preserved. The iron formation consists mainly of quartz, specularite, magnetite,cummingtonite-grunerite, and ferrodolomite-ankerite. Less commonare actinolite, anthophyllite, riebeckitetremolite, magnesioriebeckite,ferrosalite, orthopyroxene, aegirine-augite, aegirine, rhodonite,garnet (almandine, spessartine, calderite), siderite, rhodochrosite,calcite, and kutnahorite. Conventional wet chemical analyses or electron microprobe analyseshave been made of thirty-four phases belonging to the abovelist. Six additional electron probe analyses have been madeof phases from the underlying pelitic schists. All conventionallyanalyzed phases are characterized by complete optical, unitcell parameter, and density measurments. The analyzed assemblages from the silicate and silicate-carbonateiron formation include grunerite-ferrosalite, grunerite-eulite-siderite,grunerite-actinolite, grunerite-almandine, cummingtonite-spessartine,rhodonite-kutnahorite-calderite, aegirine-augite-riebeckite-tremolite,magnesioriebeckite-cummingtonite-rhodonite, aegirine-augite-rhodonite-rhodo-chrosite,and aegirine-rhodonite-calderite-rhodochrosite. The assemblages are concluded to be equilibrium assemblages.Of the volatile components, O₂, CO₂, and H₂O, O₂, is concludedto have behaved as an inert (buffered) component. Variationsin the activity of CO₂ are concluded to have existed betweensilicate-oxide and carbonate-oxide members of the iron formation.It is not clear, however, whether CO₂ has acted as a perfectlymobile component with strong aco₂ gradients throughout the area,or as an inert component in some parts of the area. H₂O is consideredto have been perfectly mobile. An increase in Mg/(Mg+Fe) ratioin ferromagnesian silicates is correlated with an increase inthe oxidation state of the assemblage. A similar increase in(Mg+Mn)/(Mg+Mn+Fe) is found in manganoan ferromagnesian silicateswith increasing activity of O₂. A number of ferromagnesian silicatescontain large amounts of Na⁺ and Fe³⁺ as a result of the verylow Al₂O₃ content of the iron formation. The P and T conditionsof metamorphism are deduced from experimental studies applicableto the underlying pelitic schists.     

Spessartine Garnets in a Manganiferous Carbonate Formation from Nsuta, Ghana

Abstract: Manganese carbonate ore beds and host rock manganiferous phyllites at the Nsuta mine, western Ghana, contain well developed garnet crystals. Individual crystals are idioblastic, sometimes porphyroblastic, and homogeneous, and are associated with rhodochrosite (with or without kutnahorite), quartz and muscovite. The conspicuous absence of chlorite in garnet-rich assemblages, and of garnet in chlorite-rich rocks, suggest chemical constraints may have been important in the formation of the two minerals. Gondite bands within carbonate ores are interpreted to have resulted from localised processes in which manganese carbonates, in environments rich in alumino-silicate minerals, may have been completely exhausted during metamorphic reactions.     

Synthesis of tourmaline solid solutions in the system Na2O–MgO–Al2O3–SiO2–B2O3–H2O–HCl and the distribution of Na between tourmaline and fluid at 300 to 700 °C and 200 MPa

Tourmaline has been synthesized hydrothermally at 200 MPa between 300 and 700 °C from oxide mixtures with Mg-Al ratios for the end members dravite NaMg₃Al₆(Si₆O₁₈)(BO₃)₃(OH)₃(OH) and Mg-foitite &ding6F;(Mg₂Al)Al₆ (Si₆O₁₈)(BO₃)₃(OH)₃(OH). Six different Na concentrations were investigated to determine the distribution of Na between tourmaline and fluid in the SiO₂-saturated system Na₂O-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl. Synthetic tourmaline ranges from X-site vacant (&ding6F;) tourmaline (Mg-foitite) to nearly ideal dravite with Na=0.95 apfu. There are small, but significant, amounts of proton deficiency and negligible tetrahedral Al. Chemical variation is primarily caused by the substitutions Al&ding6F;Mg_-1Na_-1 and minor AlMg_-1H_-1. Varying amounts of Na and &ding6F; determine the Mg/Al ratios. Besides tourmaline and quartz, additional Mg-Al phases are chlorite and, at 700 °C, cordierite. Albite is also present at high Na concentrations in the bulk composition. The c dimension of the tourmaline crystals increases with Na in tourmaline. The amount of Na in the X-site depends strongly on the bulk concentration of Na in the system as well as on the temperature. These factors in turn control the phase assemblage and the composition of the fluid phase. For the assemblage tourmaline + quartz + chlorite/cordierite + fluid, a linear relationship exists between Na concentration in the fluid (quenched after the run) and tourmaline with temperature: T °C [ᆭ °C]=(Na_fluid/Na_tur)앾.878-14.692 (r²=0.96). For the assemblage tourmaline + albite + quartz + fluid, it is: T °C [ᆣ °C]=(Na_fluid/Na_tur)욝.813-6.231 (r²=0.95), where Na_fluid is the concentration of Na⁺ in the final fluid (mol/l) and Na_tur is the number of Na cations in the X-site of tourmaline. The equations are valid in the temperature range of 500-715 °C. Our experiments demonstrate that the occupancy of the X-site in combination with the changing concentrations of Al and Mg can be used to monitor changes in the fluid composition in equilibrium with a growing tourmaline crystal. Currently, this relation can be applied qualitatively to natural tourmaline to explain zoning in Na- and Al/(Al+Mg).     

The Garnet+Hornblende Isograd in Calcic Schists from an Andalusite-Type Regional Metamorphic Terrain, Panamint Mountains, California

Calcic schists in the andalusite-type regional metamorphic terrainin the Panamint Mountains, California, contain the low-varianceassemblage quartz+epidote+muscovite+biotite+calcic amphibole+chlorite+plagioclase+spheneat low grade. Near the sillimanite isograd, chlorite in thisassemblage is replaced by garnet. The low variance in many calcicschists allows the determination of the nature of the reactionthat resulted in the coexistence of garnet+hornblende. A graphicalanalysis of the mineral assemblages shows that the reactioncan not be of the form biotite+epidote+chlorite+plagioclase+quartz=garnet+hornblende+muscovite+sphene+H₂Obecause garnet+chlorite never coexisted during metamorphismand the chlorite-bearing and garnet-bearing phase volumes donot overlap. The compositions of the minerals show that withincreasing grade amphibole changed from actinolite to pargasitichornblende with no apparent miscibility gap, the partitioningof Fe and Mg between chlorite and hornblende changed from K_D(Mg/Fe, chl&amp) < 1 to K_D > 1, the partitioning betweenbiotite and hornblende changed from K_D (Mg/Fe, bio/amp) <1 in chlorite-zone samples to K_D > 1 in garnet + hornblende-zonesamples, and the transition to the garnet-bearing assemblageoccurred when the composition of plagioclase was between An₅₅and An₈₀. Both the graphical analysis and an analytical analysisof the compositions of the minerals using simplified componentsderived from the natural mineral compositions indicate thatat the garnet+hornblende isograd the composition of hornblendewas colinear with that of plagioclase and biotite, as projectedfrom quartz, epidote, muscovite, and H₂O. During progressivemetamorphism, chlorite+biotite+epidote+quartz continuously brokedown to form hornblende+muscovite+sphene until the degeneracywas reached. At that point, tie lines from hornblende couldextend to garnet without allowing garnet to coexist with chlorite.Thus, the garnet+hornblende isograd was established throughcontinuous reactions within the chlorite-grade assemblage ratherthan through a discontinuous reaction. In this type of isograd,the low-grade diagnostic assemblage occurs only in Mg-rich rocks;whereas the high-grade assemblage occurs only in Fe-rich rocks.This relation accounts for the restricted occurrence of garnet+hornblendeassemblage in low-pressure terrains. In Barrovian terrains,garnet+chlorite commonly occurs, and the first appearana ofgarnet+hornblende can simply result from the continuous shiftof the garnet+chlorite tie line to Mg-rich compositions.     

Phase Equilibria of Amphibolites from the Post Pond Volcanics, Mt. Cube Quadrangle, Vermont

Amphibolites of the Post Pond Volcanics, south-west corner ofthe Mt. Cube Quadrangle, Vermont, are characterized by a greatdiversity of bulk rock types that give rise to a wide varietyof low-variance mineral assemblges. Original rock types arebelieved to have been intrusive and extrusive volcanics, hydrothermallyaltered volcanics and volcanogenic sediments with or withoutadmixtures of sedimentary detritus. Metamorphism was of staurolite-kyanitegrade. Geothermometry yields a temperature of 535 ± 20°C at pressures of 5–6 kb. Partitioning of Fe and Mg between coexisting phases is systematic,indicating a close approach to chemical equilibrium was attained.Relative enrichment of Fe/Mg is garnet > staurolite >gedrite > anthophyllite cummingtonite hornblende > biotite> chlorite > wonesite > cordierite dolomite > talc;relative enrichment in Mn/Mg is garnet > dolomite > gedrite> staurolite cummingtonite > hornblende > anthophyllite> cordierite > biotite > wonesite > chlorite >talc. between coexisting amphiboles varies as a function ofbulk Fe/Mg, which is inconsistent with an ideal molecular solutionmodel for amphiboles. Mineral assemblages are conveniently divided into carbonate+ hornblende-bearing, hornblende-bearing (carbonate-absent)and hornblende-absent. The carbonate-bearing assemblages allcontain hornblende + dolomite+ calcite + plagioclase (andesineand/or anorthite) + quartz with the additional phases garnetand epidote (in Fe-rich rocks) and chlorite ± cummingtonite(in magnesian rocks). Carbonate-bearing assemblages are restrictedto the most calcic bulk compositions. Hornblende-bearing (carbonate absent) assemblages occur in rocksof lower CaO content than the carbonate-bearing assemblages.All of these assemblages contain hornblende + andesine ±quartz + Fe-Ti oxide (rutile in magnesian rocks and ilmenitein Fe-rich rocks). In rocks of low Al content, cummingtoniteand two orthoamphiboles (gedrite and anthophyllite) are common.In addition, garnet is found in Fe-rich rocks and chlorite isfound in Mg-rich rocks. Several samples were found that containhornblende + cummingtonite + gedrite + anthophyllite ±garnet +chlorite + andesine + quartz + Fe-Ti oxide ±biotite. Aluminous assemblages contain hornblende + staurolite+ garnet ± anorthite/bytownite (coexisting with andesine)± gedrite ± biotite ± chlorite ±andesine ± quartz ± ilmenite. Hornblende-absentassemblages are restricted to Mg-rich, Ca-poor bulk compositions.These rocks contain chlorite ± cordierite ± staurolite± talc ± gedrite ± anthophyllite ±cummingtonite ± garnet ± biotite ± rutile± quartz ± andesine. The actual assemblage observeddepends strongly on Fe/Mg, Ca/Na and Al/Al + Fe + Mg. The chemistry of these rocks can be represented, to a firstapproximation, by the model system SiO₂–Al₂O₃–MgO–FeO–CaO–Na₂O–H₂O–CO₂;graphical representation is thus achieved by projection fromquartz, andesine, H₂O and CO₂ into the tetrahedron Fe–Ca–Mg–Al.The volumes defined by compositions of coexisting phases filla large portion of this tetrahedron. In general, the distributionof these phase volumes is quite regular, although in detailthere are a large number of phase volumes that overlap otherphase volumes, especially with respect to Fe/Mg ratios. Algebraicand graphical analysis of numerous different assemblages indicatethat every one of the phase volumes should shift to more magnesiancompositions with decreasing µ_H2O. It is therefore suggestedthat the overlapping phase volumes are the result of differentassemblages having crystallized in equilibrium with differentvalues of µ_H2O or µ_CO2 and that the different valuesmay have been inherited from the original H₂O and CO₂ contentof the volcanic prototype. If true, this implies that eithera fluid phase was not present during metamorphism, or that fluidflow between rocks was very restricted.     

The Dublin Gulch intrusion-hosted gold deposit, Tombstone plutonic suite, Yukon Territory, Canada

The Dublin Gulch intrusion is a member of the Tombstone plutonic suite, a linear belt of middle Cretaceous intrusions that extend across the Yukon Territory. Like many of the intrusions in this suite, the Dublin Gulch intrusion is associated with several different zones of gold and tungsten mineralization, within and immediately adjacent to the intrusion. The Eagle zone (50.3 Mt @ 0.93 g/t gold), located in the southwestern part of the Dublin Gulch intrusion, hosts the most significant concentration of gold in the area. The gold occurs in a broadly east-west-striking, steeply south-dipping series of sheeted veins. The veins consist of early quartz-scheelite-pyrrhotite-pyrite-arsenopyrite, and are associated with K-feldspar-albite alteration envelopes. These grade out to and are overprinted by sericite-carbonate-chlorite alteration. The same assemblage also occurs in veinlets that refracture sheeted quartz veins and contain the majority of the gold. The gold occurs with molybdenite, lead-bismuth-antimony sulfosalts, galena, and bismuthinite. Gold correlates strongly with bismuth (r²=0.9), a relationship common to several intrusion-related gold deposits, but has a poor correlation with all other elements. Tungsten and molybdenum have a weak inter-element correlation (r²=0.55) and paragenetically pre-date the majority of gold precipitation. Lead, zinc, copper, silver, antimony, and arsenic have moderate to strong inter-element correlations (0.58 to 0.93). The change from tungsten-bearing mineralization through to gold-bismuth-rich ores with elevated syn- to post-ore lead, zinc, copper, silver, antimony, and arsenic can be grossly correlated with a change in hydrothermal fluid composition. Early scheelite-bearing quartz contains primary CO₂-rich fluid inclusions, which are post-dated by secondary inclusions with higher salinities (up to 15 wt% NaCl equiv.) and less CO₂. These latter inclusions are interpreted to coincide with the later gold-bismuth and base metal mineralization. The favored genetic model is one in which early CO₂-rich fluids exsolved from a magma with an initially high CO₂ content, but progressively became more saline and H₂O-rich as the system evolved.     

Regression Modelling of Metamorphic Reactions in Metapelites, Snow Peak, Northern Idaho

The second of two periods of regional metamorphism that affectedpelitic rocks near Snow Peak caused complete re-equilibrationof mineral assemblages and resulted in a consistent set of metamorphicisograds. Metamorphic chlorite and biotite occur in the lowestgrade rocks. With increasing grade, garnet, staurolite, andkyanite join the assemblage, resulting in a transition zonecontaining all the above phases. At higher grade, chlorite,and finally staurolite disappear. Mass balance relations at isograds and among minerals of low-varianceassemblages have been modelled by a non-linear least-squaresregression technique. The progressive sequence can be describedin terms of schematic T-X_H2O relations among chlorite, biotite,garnet, staurolite, and kyanite at P_total above the KFMASH invariantpoint involving those phases. The first appearance of garnetwas the result of an Fe-Mg-Mn continuous reaction. As temperaturerose, the garnet zone assemblage encountered the stauroliteisograd reaction, approximated by the model reaction: 3?0 chlorite + 1?5 garnet + 3?3 muscovite + 05 ilmenite = 1?0staurolite + 3?1 biotite + 1?5 plagioclase + 3?3 quartz + 10?3H₂O. The staurolite zone corresponds to buffering along this reactionto the intersection where chlorite, biotite, garnet, staurolite,and kyanite coexist. The transition zone assemblage formed byreaction at this T–X _H2O intersection which migrates towardmore H2O-rich fluid composition with progressive reaction. Thenet reaction at the intersection is approximated by the transitionzone reaction: 1?0 chlorite +1?1 muscovite + 0?2 ilmenite = 2?7 kyanite + 1?0biotite + 0?4 albite + 4?2 H₂O. Chlorite was commonly the first phase to have been exhaustedand the remaining assemblage was buffered along a staurolite-outreaction, represented by the model reaction: 1?0 staurolite + 3?4 quartz + 0?4 anorthite + 1?4 garnet + 0?1ilmenite + 7?9 kyanite + 2?0 H₂O. Consumption of staurolite by this reaction resulted in the highestgrade assemblage, which contains kyanite, garnet, biotite, muscovite,quartz, plagioclase, ilmenite, and graphite.     

Low-Temperature, Low-Pressure Metamorphism of Mn-rich Rocks in the Lienne Syncline, Venn--Stavelot Massif (Belgian Ardennes), and the Role of Carpholite

Low-grade Mn-rich metamorphic rocks of the Lienne syncline (westernpart of the Venn–Stavelot Massif, Belgian Ardennes) havebeen re-examined to evaluate the petrological significance ofcarpholite proper, Mn^2$ Al₂[Si₂O₆](OH)₄. Metamorphic P–Tconditions of these rocks are estimated to be {small tilde}300C1–2 kbar, which is in accordance with the exclusive occurrenceof carpholite in low-P rocks such as hydrothermal environmentselsewhere. Carpholite of the Lienne syncline exclusively occursin quartz-rich segregations. Its composition is close to end-member.Thermodynamic calculations confirm that carpholite is a stablephase at low-pressure–low-temperature conditions, in contrastto ferro- and magnesiocarpholite, which are high-pressure minerals.No information is available on the high-P behaviour of carpholite.The occurrence of carpholite is partly closely associated withspessartine-bearing country rocks, or carpholite is alteredto assemblages with spessartine, sudoite, chlorite, muscoviteand paragonite. Spessartine in these rocks contains minor amountsof hydrogarnet component {(H/4)/[Si$(H/4)] = 0.03–0.06}.The presence of carpholite-spessartine assemblages in theselow-P rocks is in contrast to high-pressure metamorphic rocksfrom other areas, where parageneses such as fem/magnesiocarpholite–chloritoidor magnesiocarpholite–chlorite–kyanite occur. Theappearance of carpholite–garnet assemblages in low-P Mn-richrocks can be explained by contrasting phase relations becauseof a high Mn–Mg partition coefficient between the mineralsunder consideration. In rhodo-chrosite-bearing veins in theLienne syncline, nearly complete replacement of carpholite byspessartine and chlorite is due to the continuous reaction carpholite$ rhodochrosite $ quartz = spessartine $ chlorite $ H₂O $ CO₂,which defines a very low X_co, in the temperature range underconsideration. It is suggested that spessartine (possibly containingsome hydrogarnet component), during prograde metamorphism atlow pressure, becomes stable at a temperature of {small tilde}300C KEY WORDS: carpholite; spessartine; sudoite; Venn–Stavelot Massif; Ardemes ^*Corresponding author. Fax: x49/531/3918131. e-mail: t.theye{at}tu.bs.de     

Petrography and geochemistry of intraclastic manganese–carbonates from the ∼2.2 Ga Nsuta deposit of Ghana: Significance for manganese sedimentation in the Palaeoproterozoic of West Africa

Intraclastic Mn carbonate rocks occur in the marginal areas of the manganese–carbonate orebody (manganesestone) of the Palaeoproterozoic Nsuta deposit in the Birimian of Ghana. Macroscopically the intraclastic rocks display graded bedding and are typified by a matrix-supported fabric with subangular to subrounded particles less than a millimetre to ∼1.5 × 0.5 cm. Both clasts and matrix consist mainly of varying proportions of microcrystalline and microconcretionary carbonates, quartz, muscovite and subordinate pyrite. Within individual intraclasts, carbonate minerals (including distinctly zoned microconcretions) are essentially Mg kutnahorite and Mg–Ca rhodochrosite, similar to the carbonate minerals in the manganesestone. Whole rock chemistry of the intraclastic carbonates shows significant variability in the amounts of SiO₂, Al₂O₃, MnO, MgO, CaO, Na₂O and, to a lesser extent, K₂O. Major element contents of the manganesestone similarly vary widely, except that these have, in particular, comparably higher MnO but less SiO₂ and Al₂O₃ than the intraclastic carbonates and host rock Mn phyllite. Rare earth element (REE) concentrations in the intraclastic carbonates are approximately an order of magnitude higher than in the manganesestone. Whereas both rocks exhibit positive Eu anomalies, only the manganesestone shows a discernibly negative Ce anomaly. Petrographic and geochemical features suggest that the intraclasts are fragments of reworked Mn carbonate sediments derived from intraformational erosion and subsequent (mass flow) deposition as carbonate “turbidite” mud. Processes such as submarine slumping, sliding and other sediment gravity flows may have likely interrupted Mn sedimentation and transported partially consolidated manganiferous sediments down slopes into the early Birimian ocean.     

Very high-density carbonic fluid inclusions in sapphirine-bearing granulites from Tonagh Island in the Archean Napier Complex, East Antarctica: implications for CO2 infiltration during ultrahigh-temperature (T>1,100 °C) metamorphism

The ultrahigh-temperature (UHT) metamorphism of the Napier Complex is characterized by the presence of dry mineral assemblages, the stability of which requires anhydrous conditions. Typically, the presence of the index mineral orthopyroxene in more than one lithology indicates that H₂O activities were substantially low. In this study, we investigate a suite of UHT rocks comprising quartzo-feldspathic garnet gneiss, sapphirine granulite, garnet-orthopyroxene gneiss, and magnetite-quartz gneiss from Tonagh Island. High Al contents in orthopyroxene from sapphirine granulite, the presence of an equilibrium sapphirine-quartz assemblage, mesoperthite in quartzo-feldspathic garnet gneiss, and an inverted pigeonite-augite assemblage in magnetite-quartz gneiss indicate that the peak temperature conditions were higher than 1,000 °C. Petrology, mineral phase equilibria, and pressure-temperature computations presented in this study indicate that the Tonagh Island granulites experienced maximum P-T conditions of up to 9 kbar and 1,100 °C, which are comparable with previous P-T estimates for Tonagh and East Tonagh Islands. The textures and mineral reactions preserved by these UHT rocks are consistent with an isobaric cooling (IBC) history probably following an counterclockwise P-T path. We document the occurrence of very high-density CO₂-rich fluid inclusions in the UHT rocks from Tonagh Island and characterize their nature, composition, and density from systematic petrographic and microthermometric studies. Our study shows the common presence of carbonic fluid inclusions entrapped within sapphirine, quartz, garnet and orthopyroxene. Analysed fluid inclusions in sapphirine, and some in garnet and quartz, were trapped during mineral growth at UHT conditions as 'primary' inclusions. The melting temperatures of fluids in most cases lie in the range of -56.3 to -57.2 °C, close to the triple point for pure CO₂ (-56.6 °C). The only exceptions are fluid inclusions in magnetite-quartz gneiss, which show slight depression in their melting temperatures (-56.7 to -57.8 °C) suggesting traces of additional fluid species such as N₂ in the dominantly CO₂-rich fluid. Homogenization of pure CO₂ inclusions in the quartzo-feldspathic garnet gneiss, sapphirine granulite, and garnet-orthopyroxene gneiss occurs into the liquid phase at temperatures in the range of -34.9 to +4.2 °C. This translates into very high CO₂ densities in the range of 0.95-1.07 g/cm³. In the garnet-orthopyroxene gneiss, the composition and density of inclusions in the different minerals show systematic variation, with highest homogenization temperatures (lowest density) yielded by inclusions in garnet, as against inclusions with lowest homogenization (high density) in quartz. This could be a reflection of continued recrystallization of quartz with entrapment of late fluids along the IBC path. Very high-density CO₂ inclusions in sapphirine associated with quartz in the Tonagh Island rocks provide potential evidence for the involvement of CO₂-rich fluids during extreme crustal temperatures associated with UHT metamorphism. The estimated CO₂ isochores for sapphirine granulite intersect the counterclockwise P-T trajectory of Tonagh Island rocks at around 6-9 kbar at 1,100 °C, which corresponds to the peak metamorphic conditions of this terrane derived from mineral phase equilibria, and the stability field of sapphirine + quartz. Therefore, we infer that CO₂ was the dominant fluid species present during the peak metamorphism in Tonagh Island, and interpret that the fluid inclusions preserve traces of the synmetamorphic fluid from the UHT event. The stability of anhydrous minerals, such as orthopyroxene, in the study area might have been achieved by the lowering of H₂O activity through the influx of CO₂ at peak metamorphic conditions (>1,100 °C). Our microthermometric data support a counterclockwise P-T path for the Napier Complex.     

Petrogenesis and implications of jadeite‐bearing kyanite eclogite from the Sanbagawa belt (SW Japan)

Jadeite‐bearing kyanite eclogite has been discovered in the Iratsu body of the Sanbagawa belt, SW Japan. The jadeite + kyanite assemblage is stable at higher pressure–temperature (P–T) conditions or lower H₂O activity [a(H₂O)] than paragonite, although paragonite‐bearing eclogite is common in the Sanbagawa belt. The newly discovered eclogite is a massive metagabbro with the peak‐P assemblage garnet + omphacite + jadeite + kyanite + phengite + quartz + rutile. Impure jadeite is exclusively present as inclusions in garnet. The compositional gap between the coexisting omphacite (P2/n) and impure jadeite (C2/c) suggests relatively low metamorphic temperatures of 510–620 °C. Multi‐equilibrium thermobarometry for the assemblage garnet + omphacite + kyanite + phengite + quartz gives peak‐P conditions of ~2.5 GPa, 570 °C. Crystallization of jadeite in the metagabbro is attributed to Na‐ and Al‐rich effective bulk composition due to the persistence of relict Ca‐rich clinopyroxene at the peak‐P stage. By subtracting relict clinopyroxene from the whole‐rock composition, pseudosection modelling satisfactorily reproduces the observed jadeite‐bearing assemblage and mineral compositions at ~2.4–2.5 GPa, 570–610 °C and a(H₂O) >0.6. The relatively high pressure conditions derived from the jadeite‐bearing kyanite eclogite are further supported by high residual pressures of quartz inclusions in garnet. The maximum depth of exhumation in the Sanbagawa belt (~80 km) suggests decoupling of the slab–mantle wedge interface at this depth.     

Proterozoic low-sulfidation epithermal Au-Ag mineralization in the Mallery Lake area, Nunavut, Canada

The Mallery Lake area contains pristine examples of ancient precious metal-bearing low-sulfidation epithermal deposits. The deposits are hosted by rhyolitic flows of the Early Proterozoic Pitz Formation, but are themselves apparently of Middle Proterozoic age. Gold mineralization occurs in stockwork quartz veins that cut the rhyolites, and highest gold grades (up to 24 g/t over 30 cm) occur in the Chalcedonic Stockwork Zone. Quartz veining occurs in two main types: barren A veins, characterized by fine- to coarse-grained comb quartz, with fluorite, calcite, and/or adularia; and mineralized B veins, characterized by banded chalcedonic silica and fine-grained quartz, locally intergrown with fine-grained gold or electrum. A third type of quartz vein (C), which crosscuts B veins at one locality, is characterized by microcrystalline quartz intergrown with fine-grained hematite and rare electrum. Fluid inclusions in the veins occur in two distinct assemblages. Assemblage 1 inclusions represent a moderate temperature (Th=150 to 220 °C), low salinity (~1 eq. wt% NaCl, with trace CO₂), locally boiling fluid; this fluid type is found in both A and B veins and is thought to have been responsible for Au-Ag transport and deposition. Assemblage 2 inclusions represent a lower temperature (Th=90 to 150 °C), high salinity calcic brine (23 to 31 wt% CaCl₂-NaCl), which occurs as primary inclusions only in the barren A veins. Assemblage 1 and 2 inclusions occur in alternating quartz growth bands in the A-type veins, where they appear to represent alternating fluxes of dilute fluid and local saline groundwater. No workable primary fluid inclusions were observed in the C veins. The A-vein quartz yields '¹⁸O values from 8.3 to 14.5‰ (average=10.9ǃ.7‰ [1C], n=30), whereas '¹⁸O values for B-vein quartz range from 11.2 to 14.0‰ (average=13.0ǂ.9‰, n=12). Calculated '¹⁸O_H2O values for the dilute mineralizing fluid from B veins range from -2.6 to 0.2‰ (average=-0.8ǂ.9‰, n=12) and are consistent with a dominantly meteoric origin. No values could be calculated for the brine, however, because all A-vein quartz samples contain mixed fluid inclusion populations. However, the fact that A-vein quartz samples extend to lower '¹⁸O values than the B veins suggests that the brine had a lighter isotopic signature relative to the dilute fluid. Hydrogen isotopic ratios of fluid inclusion waters extracted from eleven quartz samples of both vein types range from 'D_FI=-56 to -134‰, but show no particular correlation with vein type. In most respects, the mineralogical and fluid characteristics of the Mallery Lake system are comparable to those of Phanerozoic low-sulfidation deposits, and although the presence of high salinity brines is unusual in such deposits, it is not unknown (e.g., Creede, Colorado). In addition, one of the few other examples of well-preserved, Precambrian, low-sulfidation epithermal deposits, from the Central Pilbara tectonic zone, Australia, contains a similarly bimodal fluid assemblage. The significance of these saline brines is not clear, but from this study we infer that they were not directly involved with Au-Ag transport or deposition.     

Ferromanganese carbonate metasediments of the Sob area,Polar Urals: Bedding conditions,composition, and genesis

The paper presents the results of study of ferromanganese carbonate rocks in the Sob area (Polar Urals), which is located between the Rai-Iz massif and the Seida–Labytnangi Railway branch. These rocks represent low-metamorphosed sedimentary rocks confined to the Devonian carbonaceous siliceous and clayey–siliceous shales. In terms of ratio of the major minerals, ferromanganese rocks can be divided into three varieties composed of the following minerals: (1) siderite, rhodochrosite, chamosite, quartz, ± kutnahorite, ± calcite, ± magnetite, ± pyrite, ± clinochlore, ± stilpnomelane; (2) spessartite, rhodochrosite, and quartz, ± hematite, ± chamosite; (3) rhodochrosite, spessartite, pyroxmanite, quartz ± tephroite, ± fridelite, ± clinochlore, ± pyrophanite, ± pyrite. In all varieties, the major concentrators of Mn and Fe are carbonates (rhodochrosite, siderite, kutnahorite, Mn-calcite) and chlorite group minerals (clinochlore, chamosite). The chemical composition of rocks is dominated by Si, Fe, Mn, carbon dioxide, and water (L.O.I.): total SiO₂ + Fe₂O ₃ ^tot + MnO + L.O.I. = 85.6?98.4 wt %. The content of Fe and Mn varies from 9.3 to 55.6 wt % (Fe₂O ₃ ^tot + MnO). The Mn/Fe ratio varies from 0.2 to 55.3. In terms of the aluminum module Al_M = Al/(Al + Mn + Fe), the major portion of studied samples corresponds to metalliferous sediments. The δ¹³C_carb range (–30.4 to–11.9‰ PDB) corresponds to authigenic carbonates formed with carbon dioxide released during the microbial oxidation of organic matter in sediments at the dia- and/or catagenetic stage. Ferromanganese sediments were likely deposited in relatively closed seafloor zones (basin-traps) characterized by periodic stagnation. Fe and Mn could be delivered from various sources: input by diverse hydrothermal solutions, silt waters in the course of diagenesis, river discharges, and others. The diagenetic delivery of metals seems to be most plausible. Mn was concentrated during the stagnation of bottom water in basin-traps. Interruption of stagnation promoted the precipitation of Mn. The presence of organic matter fostered a reductive pattern of postsedimentary transformations of metalliferous sediments. Fe and Mn were accumulated initially in the oxide form. During the diagenesis, manganese and iron oxides reacted with organic matter to make up carbonates. Relative to manganese carbonates, iron carbonates were formed under more reductive settings and higher concentrations of carbon dioxide in the interstitial solution. Crystallization of manganese and iron silicates began already at early stages of lithogenesis and ended during the regional metamorphism of metalliferous sediments.     

Phase equilibria and the pressure-temperature path of the highest-grade Ryoke metamorphic rocks in the Yanai district, SW Japan

The garnet-cordierite zone, the highest-grade zone of the Ryoke metamorphic rocks in the Yanai district, SW Japan, is defined by the coexistence of garnet and cordierite in pelitic rocks. Three assemblages in this zone are studied in detail, i.e. spinel + cordierite + biotite, garnet + cordierite + biotite and garnet + biotite, all of which contain quartz, K-feldspar and plagioclase. The Mg/(Fe + Mg) in the coexisting minerals decreases in the following order: cordierite, biotite, garnet and spinel. Two facts described below are inconsistent with the paragenetic relation in the K₂OFeOMgOAl₂O₃SiO₂H₂O (KFMASH) system in terms of an isophysical variation. First, garnet and biotite in the last assemblage have Mg/(Fe + Mg) higher than those in the second. Second, the first two assemblages are described by the reaction,

Minerals of the viridine hornfels from Darmstadt,Germany

Viridine containing the highest amounts of Mn₂O₃ detected thus far (up to 20.5 mol % “Mn₂SiO₅”) coexists in a metasedimentary hornfels with spessartine, Mn-phlogopite (mangan-ophyllite), Mn-phengite (alurgite), hematite, quartz and probably some primary braunite. In layers poorer in viridine spessartine is absent but piemontite appears as an additional phase. Microprobe analyses of all these phases are presented which indicate very strong fractionation of Mg and Mn in coexisting phlogopite and garnet, and of Fe and Mn in coexisting hematite and braunite. Sericitic aggregates consisting of phengitic muscovite and braunite are interpreted as retrograde alteration products of viridine, but might partly be pinitic alterations of a former Mg-rich cordierite. Due to the occurrence of the assemblage spessartine-viridine-quartz Mn-cordierite cannot have been a stable phase prior to retrograde alterations. In general the stability field of viridine is extended towards higher temperatures as compared to that of pure andalusite, Al₂SiO₅. Due to the coexistence of phlogopite and muscovite (phengite) the temperature of contact metamorphism cannot have exceeded some 550°–650° C depending on the prevailing water pressure.     

Mineral Compositions and Equilibria in the Metamorphosed Iron Formation of the Gagnon Region, Quebec, Canada

Forty-seven specimens of the Wabush Iron Formation were collectedfrom ten outcrop areas. Twenty-five specimens contain the assemblage(1), quartz+clinopyroxene+calcite with or without orthopyroxene,grunerite, magnetite, ankerite, and siderite. Five specimenscontain assemblage (2), quartz+clinopyroxene+actinolite+calcite+magnetite+hematite,and two contain assemblage (3), quartz+orthopyroxene+actinolite+magnetite+hematite.In three specimens of assemblage (1), graphite occurs in theabsence of magnetite; pyrrhotite and pyrite occur separatelyor together in specimens with assemblage (1). Thirty-nine clinopyroxenes, 38 orthopyroxenes, 18 grunerites,7 actinolites, 16 calcites, 1 ankerite, and 1 siderite wereanalyzed for iron, manganese, and calcium by X-ray emissionspectrography. Magnesium contents were estimated by assumingstoichiometric proportions. Minerals occurring with hematite show low Fe/(Fe+Mg) ratios,and those in the other assemblages show higher values with awide range of variation. In orthopyroxene, Fe/(Fe+ Mg) rangesfrom 0·17 (with hematite) to 0·77. Regularity in the distributions of Fe, Mn, and Ca between pairsof coexisting minerals shows that equilibrium was attained inmost of the rocks studied. This regularity is also accomplishedin the distribution of Mn between calcite and coexisting silicatesas well as between the silicates themselves. Small differencesin the distributions of Ca and Fe depend on both outcrop areaand mineral assemblage. Phase rule considerations suggest that the specimens with dolomite-ankeriteor magnesitesiderite do not represent equilibrium assemblages.Variations in orthopyroxene compositions in assemblages withpyrite or pyrrhotite, or both, and magnetite indicate non-equilibrationof sulfides with silicates. The presence of the oxygen buffer,magnetite+hematite, attests to the immobility of oxygen duringmetamorphism. Within each outcrop area, over which the temperature and pressureare assumed to have been uniform, variations in the compositionsof the silicates in the sub-assemblages quartz+ orthopyroxene+gruneriteand quartz+orthopyroxene+clinopyroxene+calcite indicate gradientsof µ_H2O µ_CO2 and respectively. As characterizedby the composition of orthopyroxene, both gradients are relativelylow along strike, and high across strike. The direction of gradientsacross strike is almost without reversals, which is consistentwith intergranular diffusion of H₂O and CO₂. Phase rule restrictionsfor a majority of assemblages are not in accord with the simultaneousimposition of µ_H2O and µ_CO2 gradients on the rocks,nor the formation of an H₂O-CO₂ fluid phase during metamorphism.     

Composite carbonate and silicate multiphase solid inclusions in metamorphic garnet from ultrahigh‐P eclogite in the Dabie orogen

Composite multiphase solid (MS) inclusions composed of carbonate and silicate minerals have been found for the first time in metamorphic garnet from ultrahigh‐P eclogite from the Dabie orogen. These inclusions are morphologically euhedral to subhedral, and some show relatively regular shapes approaching the negative crystal shape of the host garnet. Radial fractures often occur in garnet hosting the inclusions. The inclusions are primarily composed of variable proportions of carbonate and silicate minerals such as calcite, quartz, K‐feldspar and plagioclase, with occasional occurrences of magnetite, zircon and barite. They are categorized into two groups based on the proportions of carbonate and silicate phases. Group I is carbonate‐dominated with variable proportions of silicate minerals, whereas Group II is silicate‐dominated with small proportions of carbonates. Trace element analysis by LA‐ICPMS for the two groups of MS inclusions yields remarkable differences. Group I inclusions exhibit remarkably lower REE contents than Group II inclusions, with significant LREE enrichment and large fractionation between LREE and HREE in the chondrite‐normalized REE diagram. In contrast, Group II inclusions show rather flat REE patterns with insignificant fractionation between LREE and HREE. In the primitive mantle‐normalized spidergram, Group I inclusions exhibit positive anomalies of Zr and Hf, whereas Group II inclusions show negative anomalies of Zr and Hf. Nevertheless, both groups exhibit positive anomalies of Ba, U, Pb and Sr, but negative anomalies of Nb and Ta, resembling the composition of common continental crust. Group I inclusions have higher Ba and U contents than Group II inclusions. Combined with petrological observations, the two groups of MS inclusions are interpreted as having crystallized from composite silicate and carbonate melts during continental subduction‐zone metamorphism. The differences in trace element composition between the two groups are primarily attributed to the proportions of carbonate and silicate phases in the MS inclusions. The silicate melts were derived from the breakdown of hydrous minerals such as paragonite and phengite, whereas the occurrence of carbonate melts indicates involvement of carbonate minerals in the partial melting and thus has great bearing on recycling of supracrustal carbon into the mantle. The coexistence of silicate and carbonate melts in the eclogitic garnet provides insights into the nature of hydrous melts in the subduction factory.     

Prograde and retrograde history of eclogites from the Eastern Blue Ridge, North Carolina, USA

Abstract The prograde metamorphism of eclogites is typically obscured by chemical equilibration at peak conditions and by partial requilibration during retrograde metamorphism. Eclogites from the Eastern Blue Ridge of North Carolina retain evidence of their prograde path in the form of inclusions preserved in garnet. These eclogites, from the vicinity of Bakersville, North Carolina, USA are primarily comprised of garnet–clinopyroxene–rutile–hornblende–plagioclase–quartz. Quartz, clinopyroxene, hornblende, rutile, epidote, titanite and biotite are found as inclusions in garnet cores. Included hornblende and clinopyroxene are chemically distinct from their matrix counterparts. Thermobarometry of inclusion sets from different garnets record different conditions. Inclusions of clinozoisite, titanite, rutile and quartz (clinozoisite + titanite = grossular + rutile + quartz + H₂O) yield pressures (6–10 kbar, 400–600 °C and 8–12 kbar 450–680 °C) at or below the minimum peak conditions from matrix phases (10–13 kbar at 600–800 °C). Inclusions of hornblende, biotite and quartz give higher pressures (13–16 kbar and 630–660 °C). Early matrix pyroxene is partially or fully broken down to a diopside–plagioclase symplectite, and both garnet and pyroxene are rimmed with plagioclase and hornblende. Hypersthene is found as a minor phase in some diopside + plagioclase symplectites, which suggests retrogression through the granulite facies. Two‐pyroxene thermometry of this assemblage gives a temperature of c. 750 °C. Pairing the most Mg‐rich garnet composition with the assemblage plagioclase–diopside–hypersthene–quartz gives pressures of 14–16 kbar at this temperature. The hornblende–plagioclase–garnet rim–quartz assemblage yields 9–12 kbar and 500–550 °C. The combined P–T data show a clockwise loop from the amphibolite to eclogite to granulite facies, all of which are overprinted by a texturally late amphibolite facies assemblage. This loop provides an unusually complete P–T history of an eclogite, recording events during and following subduction and continental collision in the early Palaeozoic.