Chemographic analysis of assemblages involving pyrophyllite, chloritoid, chlorite, kaolinite, kyanite, quartz: application to metapelites in the Witwatersrand goldfields, South Africa

The Witwatersrand goldfields contain abundant assemblages that include pyrophyllite, chloritoid, chlorite, kaolinite and/or kyanite, with quartz. A chemographic analysis of the system Fe(Mg)-Al-Si-O-H involving these minerals yields 22 potential phase diagrams. Using orientation criteria and thermodynamic calculations as further constraints, this list has been reduced to three possible diagrams. New thermodynamic data favour one of these in particular.
This chemographic analysis demonstrates that formation of chloritoid is not restricted to the breakdown reaction of kaolinite plus chlorite in the F(M)ASH system, as stated by previous studies, but could be from pyrophyllite + chlorite → chloritoid + quartz + H₂O.
The metamorphic temperature variation between Witwatersrand goldfields exceeded 65 C, based on chlorite and chloritoid compositions. The lower and upper pressure limits are constrained by the andalusite to kyanite, and the sudoite/chlorite to carpholite boundaries, i.e. 1.5–2.8, and 7 kbar, respectively. The widespread pyrophyllite, chlorite and Fe-chloritoid in all the Witwatersrand goldfields, and the local occurrence of sudoite indicate a consistent low-pressure environment in which Mg-chloritoid would not be stable.     

Metamorphic veining and mass transfer in a chemically closed system: a case study in Alpine metabauxites (western Vanoise)

In western Vanoise (French Alps), karstic pockets of Triassic‐to‐Jurassic metabauxites embedded in carbonate rocks and containing several generations of metamorphic veins were studied. During blueschist facies metamorphism, a cumulative amount of ～13 vol% of water is inferred to have been produced locally by successive dehydration reactions, and part of this fluid remained in the bauxitic lenses during most of the metamorphic cycle. Field and geochemical evidence show that these rocks have been isolated from large‐scale fluid flow (closed‐system behaviour). It is proposed that the internally derived fluid has promoted the opening of fluid‐filled open spaces (as attested by the euhedral habits of vein minerals) and served as medium for mass transfer from rock to vein. Indeed, the vein infill is obviously the result of chemical interactions, at the millimetre‐to‐centimetre scale, between the rock minerals and the locally produced aqueous fluid. Two vein types can be distinguished based on mineralogical and textural features: (i) some veins are filled with newly formed products of either prograde (chloritoid) or retrograde (chlorite) metamorphic reactions; in this case, fluid‐filled open spaces seem to offer energetically favourable nucleation/growth sites; (ii) the second vein type is infilled with cookeite or pyrophyllite, that were present in the host rock prior to the vein formation. In this closed chemical system, the components for the vein infill minerals have been transferred from rock to vein through the fluid, in a dissolution–transport–precipitation process, possibly stress‐assisted. These different vein generations all contain Al‐rich mineral infills, suggesting that Al was a mobile element (cm scale) during metamorphism. In these HP rocks, fluid flow may have been restricted, and if so mass transfer occurred by diffusion in an almost stagnant fluid. Metamorphic veins can be seen as witnesses of fluid and mass redistribution that partly accommodate the rock deformation (lateral segregation).     

Metamorphism of the Witwatersrand gold fields: conditions during peak metamorphism

Abstract Pelitic assemblages from all major Witwatersrand gold fields record metamorphic conditions of the greenschist facies, with minimal regional grade changes over at least 200 km strike length. Diagnostic metamorphic assemblages are less common in the volumetrically dominant quartzites, the actively-exploited auriferous conglomerates and some of the regionally persistent metapelitic horizons. Bulk rock composition has been a major control on assemblage development.
Key metapelitic assemblages include pyrophyllite, chloritoid, chlorite and muscovite in each gold field, with less common metamorphic biotite. Accessory minerals are pyrite, tourmaline, rutile and zircon. The abundance of chloritoid and pyrophyllite in thin shaly units, together with their minor, but widespread, distribution in quartzites and conglomerates, indicate that metamorphic temperatures reached 350°C ± 50°C in all the gold fields. Pressures are less-well constrained, 1–2 kbar being inferred. Outside the gold fields, higher grades are indicated by andalusite and kyanite near granitoid domes and later intrusions.
The temperatures during peak metamorphism and the abundance of pyrite provide ideal conditions to (re)mobilize gold and may explain its secondary textural features.     

Fluid flow and Al transport during quartz-kyanite vein formation, Unst, Shetland Islands, Scotland

Quartz‐kyanite veins, adjacent alteration selvages and surrounding ‘precursor’ wall rocks in the Dalradian Saxa Vord Pelite of Unst in the Shetland Islands (Scotland) were investigated to constrain the geochemical alteration and mobility of Al associated with channelized metamorphic fluid infiltration during the Caledonian Orogeny. Thirty‐eight samples of veins, selvages and precursors were collected, examined using the petrographic microscope and electron microprobe, and geochemically analysed. With increasing grade, typical precursor mineral assemblages include, but are not limited to, chlorite+chloritoid, chlorite+chloritoid+kyanite, chlorite+chloritoid+staurolite and garnet+staurolite+kyanite+chloritoid. These assemblages coexist with quartz, white mica (muscovite, paragonite, margarite), and Fe‐Ti oxides. The mineral assemblage of the selvages does not change noticeably with metamorphic grade, and consists of chloritoid, kyanite, chlorite, quartz, white mica and Fe‐Ti oxides. Pseudosections for selvage and precursor bulk compositions indicate that the observed mineral assemblages were stable at regional metamorphic conditions of 550–600 °C and 0.8–1.1 GPa. A mass balance analysis was performed to assess the nature and magnitude of geochemical alteration that produced the selvages adjacent to the veins. On average, selvages lost about −26% mass relative to precursors. Mass losses of Na, K, Ca, Rb, Sr, Cs, Ba and volatiles were −30 to −60% and resulted from the destruction of white mica. Si was depleted from most selvages and transported locally to adjacent veins; average selvage Si losses were about −50%. Y and rare earth elements were added due to the growth of monazite in cracks cutting apatite. The mass balance analysis also suggests some addition of Ti occurred, consistent with the presence of rutile and hematite‐ilmenite solid solutions in veins. No major losses of Al from selvages were observed, but Al was added in some cases. Consequently, the Al needed to precipitate vein kyanite was not derived locally from the selvages. Veins more than an order of magnitude thicker than those typically observed in the field would be necessary to accommodate the Na and K lost from the selvages during alteration. Therefore, regional transport of Na and K out of the local rock system is inferred. In addition, to account for the observed abundances of kyanite in the veins, large fluid‐rock ratios (10²–10³ m³_fluid m⁻³_rock) and time‐integrated fluid fluxes in excess of ∼10⁴ m³_fluid m⁻²_rock are required owing to the small concentrations of Al in aqueous fluids. It is concluded that the quartz‐kyanite veins and their selvages were produced by regional‐scale advective mass transfer by means of focused fluid flow along a thrust fault zone. The results of this study provide field evidence for considerable Al mass transport at greenschist to amphibolite facies metamorphic conditions, possibly as a result of elevated concentrations of Al in metamorphic fluids due to alkali‐Al silicate complexing at high pressures.     

Prediction of rock alteration patterns: A potential tool in mineral exploration

Hydrothermal alteration of a quartz‐K‐feldspar rock is simulated numerically by coupling fluid flow and chemical reactions. Introduction of CO₂ gas generates an acidic fluid and produces secondary quartz, muscovite and/or pyrophyllite at constant temperature and pressure of 300°C and 200 MPa. The precipitation and/or dissolution of the secondary minerals is controlled by either mass‐action relations or rate laws. In our simulations the mass of the primary elements are conserved and the mass‐balance equations are solved sequentially using an implicit scheme in a finite‐element code. The pore‐fluid velocity is assumed to be constant. The change of rock volume due to the dissolution or precipitation of the minerals, which is directly related to their molar volume, is taken into account. Feedback into the rock porosity and the reaction rates is included in the model. The model produces zones of pyrophyllite quartz and muscovite due to the dissolution of K‐feldspar. Our model simulates, in a simplified way, the acid‐induced alteration assemblages observed in various guises in many significant mineral deposits. The particular aluminosilicate minerals produced in these experiments are associated with the gold deposits of the Witwatersrand Basin.     

Garnet–chloritoid equilibria in eclogitic pelitic rocks from the Sesia zone (Western Alps): their bearing on phase relations in high pressure metapelites

Abstract A detailed study of garnet–chloritoid micaschists fom the Sesia zone (Western Alps) is used to constrain phase relations in high pressure (HP) metapelitic rocks. In addition to quartz, phengite, paragonite and rutile, the micaschists display two distinct parageneses, namely garnet + chloritoid + chlorite and garnet + chloritoid + kyanite. Talc has never been observed. Garnet and chloritoid are more magnesian when chlorite is present instead of kyanite. The distinction of the two equilibria results from different bulk rock chemistries, not from P–T conditions or redox state. Estimated P–T conditions for the eclogitic metamorphism are 550–600°C, 15–18 kbar.
The presence of primary chlorite in association with garnet and chloritoid leads us to construct two possible AFM topologies for the Sesia metapelites. The paper describes a KFMASH multisystem for HP pelitic rocks, which extends the grid of Harte & Hudson (1979) towards higher pressures and adds the phase talc. Observed parageneses in HP metapelites are consistent with predicted phase relations. Critical associations are Gt–Ctd–Chl and Gt–Ctd–Ky at relatively low temperatures and Gl–Chl–Ky and Gt–Tc–Ky at relatively high temperatures.     

Characteristic Features of REE and Pb–Zn–Ag Mineralizations in the Na Son Deposit,Northeastern Vietnam

The Na Son deposit is a small‐scale Pb–ZnPb–Zn–Ag deposit in northeast Vietnam and consists of biotite–chlorite schist, reddish altered rocks, quartz veins and syenite. The biotite–chlorite schist is intruded by syenite. Reddish altered rocks occur as an alteration halo between the biotite–allanite‐bearing quartz veins and the biotite–chlorite schist. Allanite occurs in the biotite–allanite‐bearing quartz veins and in the proximal reddish altered rocks. Rare earth element (REE) fluorocarbonate minerals occur along fractures or at rim of allanite crystals. The later horizontal aggregates of sulfide veins and veinlets cut the earlier reddish altered rocks. The earlier Pb–Zn veins consist of a large amount of galena and lesser amounts of sphalerite, pyrite and molybdenite. The later Cu veins cutting the Pb–Zn veins include chalcopyrite and lesser amounts of tetrahedrite and pyrite. The occurrences of two‐phase H₂O–CO₂ fluid inclusions in quartz from biotite–allanite‐bearing quartz veins and REE‐bearing fluorocarbonate minerals in allanite suggest the presence of CO₂ and F in the hydrothermal fluid. The oxygen isotopic ratios of the reddish altered rocks, biotite–chlorite schist, and syenite range from +13.9 to +14.9 ‰, +11.5 to +13.3 ‰, and +10.1 to +11.6 ‰, respectively. Assuming an isotopic equilibrium between quartz (+14.6 to +15.8 ‰) and biotite (+8.6 ‰) in the biotite–allanite‐bearing quartz vein, formation temperature was estimated to be 400°C. At 400°C, δ¹⁸O values of the hydrothermal fluid in equilibrium with quartz and biotite range from +10.5 to +11.7 ‰. These δ¹⁸O values are consistent with fluid that is derived from metamorphism. Assuming an isotopic equilibrium between galena (+1.5 to +1.7 ‰) and chalcopyrite (+3.4 ‰), the formation temperature was estimated to be approximately 300°C. The formation temperature of the Na Son deposit decreased with the progress of mineralization. Based on the geological data, occurrence of REE‐bearing minerals and oxygen isotopic ratios, the REE mineralization is thought to result from interaction between biotite–chlorite schist and REE‐, CO₂‐ and F‐bearing metamorphic fluid at 400°C under a rock‐dominant condition.     

Microfabric analyses applied to the Witwatersrand gold- and uranium-bearing conglomerates: constraints on the provenance and post-depositional modification of rock and ore components

Microfabrics of detrital quartz grains and quartz cement of four gold- and uranium-bearing conglomerates of various goldfields of the Witwatersrand Basin, South Africa, were investigated by optical and cathodoluminescence microscopy. The study revealed that the vast majority of quartz grains (<5 mm) originate from felsic magmatic source rocks. Cherts and polymineralic mineral grains, pointing to greenschist to amphibolite facies metasedimentary rocks, follow in abundance, whereas diagenetic to weakly metamorphosed quartzites are subordinate. Material from hydrothermal vein quartz is almost completely lacking, both in the sand and in the pebble fraction. No obvious relationships are discernible between the varying proportions of detrital siliciclastic components of the different reefs and their ore grades. Assuming a sedimentological control of gold distribution, this finding supports multiple sources for the detrital components, which were thoroughly mixed during transport. The post-depositional history of the sediments is characterized by a complex polyphase succession of deformation, cementation and hydrothermal alteration events. Both fragmentation and pressure solution features within detrital quartz, quartz cement and round grains of pyrite, zircon, chromite and uraninite demonstrate that these materials were present in the conglomerates during diagenesis, and, thus, are true detrital grains with abraded, rounded grain morphologies. By analogy, it is assumed that gold is also a detrital component, although most of the gold grains display characteristics of hydrothermal overprinting. During subsequent metamorphism, micro-shear zones are developed, and brittle-ductile crystal-plastic deformation and limited quartz recrystallization occur. Maximum temperatures of about 350 °C were reached on the prograde metamorphic path. Recrystallization and redistribution of detrital siliciclastic and ore minerals took place, and various hydrothermal/metamorphic minerals including chlorite, sericite, pyrophyllite and chloritoid were formed. These redistribution processes involved existing detrital minerals only and were generally isochemical because little evidence exists for the development of a secondary porosity and permeability that would allow major external inputs into the Witwatersrand conglomerates. Most of the gold grains have hydrothermal characteristics, as evidenced by their authigenic, crystalline shapes and their chemical compositions. However, these features are regarded to result from overprinting. Most likely, the gold grains experienced more drastic modifications relative to other ore components because of the ductile and mobile nature of gold. The retrograde metamorphic path is characterized by percolating radioactive fluids at T<300 °C, recorded by radiation damage indicated by cathodoluminescence alteration rims along quartz grain boundaries and microcracks. The degrees of radiation damage observed are proportional to the uranium contents of the conglomerate ores. The collective evidence of our study supports the modified placer model for the genesis of the Witwatersrand ores. This model explains most of the observations on the detrital mineral assemblage and its post-depositional modification elegantly and in a satisfactory manner.     

Genetic aspects of gold mineralization in the Southern Granulite Terrain,India

Gold mineralization in Southern Granulite Terrain (SGT) of India has close spatial relationship with the shear zones (Moyar–Bhavani) present in Cauvery Suture Zone. Gold is found to be associated with primary quartz veins, placers and laterites. The gold prospects in SGT can be broadly grouped into three provinces i) Wynad-Nilgiri, ii) Malappuram and iii) Attappadi. The auriferous quartz veins are within the deformed biotite/hornblende bearing gneisses and amphibolite. Wall rock alteration is conspicuous around the mineralized veins and gives an assemblage of muscovite–calcite–ankerite–chlorite–biotite–pyrite related to fluid–rock interaction at the time of vein formation. Fluid inclusion studies of vein quartz gives an idea of the nature of the ore forming fluids, the fluid involved in gold mineralization is of low saline and aqueous-carbonic in composition and quite similar to the orogenic lode gold deposits reported world-wide. Micro-thermometric data indicates fluid immiscibility (phase separation) during trapping of fluid inclusions and this must have played an important role in gold deposition. Geochronological studies of mineral separates from Wynad-Nilgiri province using Rb–Sr and Sm–Nd isochron methods of the auriferous quartz veins gave an age of approximately 450 Ma for the vein formation. The present studies on SGT gold mineralization indicate 1. During the Pan-African orogeny, extensive fluid influx from mantle and metamorphism extracted gold from a mafic source and were focused along major structural discontinuities of Moyar–Bhavani Shear Zone, 2. The aqueous–carbonic ore fluid interacted with rocks of the upper crust and triggered a set of metasomatic changes responsible for the dissolved components such as Ca, Si and Fe and finally precipitating in the veins and 3. The mineralizing fluid with dissolved gold in sulphide complex got destabilized due to fluid immiscibility and wall rock alteration leading to the deposition of gold with associated sulphide minerals in the vein system.     

Phase relations in andalusite-sillimanite type Fe-rich metapelites: Tono contact metamorphic aureole, northeast Japan

Mineral assemblages in metapelites of the contact aureole of the Tono granodiorite mass, northeast Japan, change systematically during progressive metamorphism along an isobaric path at 2-3 kbar. The bulk rock compositions of metapelites are aluminous with A' values on an AFM projection larger than that of the chlorite join. The metapelites commonly contain paragonite in the low-grade zone. With increasing temperatures, andalusite is formed by the breakdown of paragonite. The importance of pyrophyllite as a source of Al₂SiO₅ polymorphs is limited in typical pelitic rocks.
The most common type of metapelite in the study area has FeO/(FeO + MgO) = 0.5–0.6, and develops assemblages involving chlorite, andalusite, biotite, cordierite, K-feldspar, sillimanite and almandine, with paragenetic changes similar to other andalusite-sillimanite type aureoles. Rocks with FeO/(FeO + MgO) > 0.8 progressively develop chloritoid-bearing assemblages from Bt-Chl-Cld, And-Bt-Cld, to And-Bt at temperatures between the breakdown of paragonite and the appearance of cordierite in the more common pelitic rocks in the aureole. The paragenetic relations are explained by a KFMASH univariant reaction of Chl + Cld = And + Bt located to the low-temperature side of the formation of cordierite by the terminal equilibrium of chlorite. A P-T model depicting the relative stability of chloritoid and staurolite at low- and medium-pressure conditions, respectively, is proposed, based on the derived location of the Chl + Cld = And + Bt reaction combined with the theoretical phase relations among biotite, chlorite, chloritoid, garnet and staurolite.     

A petrogenetic grid for pelitic schists in the system SiO2-Al2O3-FeO-MgO-K2O-H2O

A quantitative petrogenetic grid for pelitic schists in the system KFMASH that includes the phases garnet, chlorite, biotite, chloritoid, cordierite, staurolite, talc, kyanite, andalusite, sillimanite, and pyrophyllite (with quartz, H₂O and muscovite or K-feldspar in excess) is presented. The grid is based on thermodynamic data of Berman et al. (1985) and Berman (1988) for endmember KFASH and KMASH equilibria and natural Fe-Mg partitioning for the KFMASH system. Calculation of P-T slopes and the change in Fe/(Fe+Mg) along reactions in the KFMASH system were made using the Gibbs method. In addition, the effect on the grid of MnO and CaO is evaluated quantitatively. The resulting grid is consistent with typical Buchan and Barrovian parageneses at medium to high grades. At low grades, the grid predicts an extensive stability field for the paragenesis chloritoid+biotite which arises because of the unusual facing of the reaction chloritoid+biotite + quartz+H₂O = garnet+chlorite+muscovite, which proceeds to the right with increasing T in the KFMASH system. However, the reaction proceeds to the left with increasing T in the MnKFASH system so the assemblage chloritoid + biotite is restricted to bulk compositions with high Fe/(Fe+Mg+Mn). Typical metapelites will therefore contain garnet+chlorite at low grades rather than chloritoid + biotite.     

Amphibole-derived evidence of medium <Emphasis Type="Italic">P/T</Emphasis> metamorphic ratio in Alpujárride and Federico “H<Emphasis Type="Italic">P</Emphasis>” units (Western Betic-Northern Rif,Spain and Morocco): possible interpretations

The significance of zoned Ca-amphibole found in metapelites, quartzites, and synfolial veins of the Internal Zone of the Betic-Rif range (Federico units from Northern Rif and Alpujárride units from Western Betic) in the Alpine tectono-metamorphic evolution of these units is discussed for first time. Typical Al-rich metapelites from both areas show assemblages consisting of white mica and chlorite, with sporadic kyanite and chloritoid. Nevertheless, in the Rif zone, phyllites and synfolial veins of Permo-Triassic units show the assemblage pumpellyite + epidote + actinolite. In the Jubrique area (Betic zone), Ca-rich phyllites, fine-grained quartzites, and quartz veins show assemblages consisting of Ca-amphibole, plagioclase, epidote, titanite, chlorite, and quartz. The Al-in-amphibole thermobarometer defines clockwise pressure–temperature paths with a range of prograde temperatures and pressures between 272°C-1.2 kbar and 484°C-3.2 kbar for the Federico unit and between 274°C-1.1 kbar and 620°C-6.1 kbar in the Jubrique unit. Amphiboles from both areas define prograde pressure–temperature paths typical of Barrovian-type metamorphism. This finding contrasts with previous estimates, which deduced high-pressure conditions in both areas. The described amphiboles indicate metamorphic conditions similar to those found in the tectonically deepest complex (Veleta complex) of the Betic Internal Zone and suggest formation during a medium P/T Alpine event, which has not been previously identified in the Alpujárride complex.     

Staurolite-forming reactions in the eastern Dalradian rocks of Scotland

Data on mineral and rock compositions along with textural relations are used to deduce the staurolite-forming reactions in eastern Dalradian rocks in Scotland. Initially staurolite is formed as a product of the breakdown of the assemblage chloritoid +quartz in iron-rich metapelites. With increase in grade the iron-rich rocks are succeeded by more magnesium-rich ones and staurolite is formed as a product of the breakdown of the assemblage chloritoid +chlorite+muscovite.     

Phase equilibrium, geothermobarometric and xenotime age dating constraints on the Alpine metamorphism recorded in chloritoid schists from the southern part of the Tisia Mega-Unit (Slavonian Mts., NE Croatia)

The chloritoid schists from the Slavonian Mts., which are attributed to the basal part of Devonian to Permian “Hercynian Semimetamorphic Complex,” represent a very rare lithology, not only in the Tisia Mega-Unit outcrops in Croatia, but also in the wider area. The investigated outcrop in the Kutjeva?ka Rijeka transect (Mt. Papuk) encompasses chloritoid-bearing metapelitic and metapsammitic lithologies. Both contain K-white mica, chlorite, chloritoid (10–15 vol.%), quartz and minor K-feldspar, plagioclase (albite), opaque minerals and pyrophyllite, together with accessory zircon, rutile, xenotime. The Th–U–Pb age dating on xenotime grains within the K-white mica + chlorite + quartz matrix and on inclusions found inside the chloritoids gave an average age 120 ± 36 Ma. Peak metamorphic conditions during the Alpine chloritoid-forming event reached 3.5–4 kbar and 340–380 °C, based on phengite barometry, chlorite–chloritoid thermometry and intersection of chlorite and chloritoid isopleths in the KFMASH quantitative phase diagram. The post-tectonic character of lath- and rosette-shaped chloritoids with respect to two foliations in the rock, together with the older age of 219 ± 81 Ma obtained on Yb-rich xenotime core domain(s), implies a possible existence of older low-grade metamorphic phase(s). The chemistry of the chloritoid schists bears the signature of upper continental crustal felsic rocks as potential protoliths, probably the felsic rocks of the nearby Papuk Complex of Slavonian Mts. The evidence presented here for the chloritoid-bearing low-grade metamorphic rocks from the Slavonian Mountains clearly show that the prograde Alpine metamorphic event had a more significant influence on the evolution of the southern part of Tisia Mega-Unit than previously considered.     

Prograde metamorphic sequence of REE minerals in pelitic rocks of the Central Alps: implications for allanite–monazite–xenotime phase relations from 250 to 610 °C

The distribution of REE minerals in metasedimentary rocks was investigated to gain insight into the stability of allanite, monazite and xenotime in metapelites. Samples were collected in the central Swiss Alps, along a well‐established metamorphic field gradient that record conditions from very low grade metamorphism (250 °C) to the lower amphibolite facies (～600 °C). In the Alpine metapelites investigated, mass balance calculations show that LREE are mainly transferred between monazite and allanite during the course of prograde metamorphism. At very low grade metamorphism, detrital monazite grains (mostly Variscan in age) have two distinct populations in terms of LREE and MREE compositions. Newly formed monazite crystallized during low‐grade metamorphism (<440 °C); these are enriched in La, but depleted in Th and Y, compared with inherited grains. Upon the appearance of chloritoid (～440–450 °C, thermometry based on chlorite–choritoid and carbonaceous material), monazite is consumed, and MREE and LREE are taken up preferentially in two distinct zones of allanite distinguishable by EMPA and X‐ray mapping. Prior to garnet growth, allanite acquires two growth zones of clinozoisite: a first one rich in HREE + Y and a second one containing low REE contents. Following garnet growth, close to the chloritoid–out zone boundary (～556–580 °C, based on phase equilibrium calculations), allanite and its rims are partially to totally replaced by monazite and xenotime, both associated with plagioclase (± biotite ± staurolite ± kyanite ± quartz). In these samples, epidote relics are located in the matrix or as inclusions in garnet, and these preserve their characteristic chemical and textural growth zoning, indicating that they did not experience re‐equilibration following their prograde formation. Hence, the partial breakdown of allanite to monazite offers the attractive possibility to obtain in situ ages, representing two distinct crystallization stages. In addition, the complex REE + Y and Th zoning pattern of allanite and monazite are essential monitors of crystallization conditions at relatively low metamorphic grade.     

Chloritoid stability in manganese rich low-grade metamorphic rocks,Venn-Stavelot Massif,Ardennes

The Southern Venn-Stavelot Massif is characterized by Ordovician and Devonian rocks very rich in manganese and aluminum, which are attacked by a low grade regional metamorphism. The assemblages 1 (phengite, paragonite, chlorite, chloritoid, garnet, quartz, hematite, rutile) and 2 (phengite, paragonite, chlorite, kaolinite (andalusite, pyrophyllite), garnet, quartz, hematite, rutile) are of basic interest for the formation of chloritoid. As the two rock types are isofaciell and quasi-identical in chemistry except for the iron oxides, there is clear evidence for the influence of on the chloritoid formation at its lower p-T stability limit. This can be shown by a discussion of the phase relations of chloritoid, garnet, kaolinite, chlorite and phengite in respect to the oxidation ratio mol 2 Fe₂O₃x 100/2 Fe₂O₃+ FeO of the host rocks. Especially chloritoid and chlorite change their chemistry in a characteristic way with rising oxidation ratio in getting richer and richer in manganese and magnesium (chloritoid) and magnesium (chlorite). A simultaneous increase in trivalent iron in these phases is supposed. At an oxidation ratio of 85–90 the stability limit of chloritoid is reached. The increasing substitution of manganese and magnesium up to this limit should have a stabilizing effect. In a rough estimate the oxygen partial pressure is supposed to be in the order of 10⁻¹⁰ atm at the stability limit of chloritoid assuming a temperature of metamorphism between 360–400° C. Rocks with oxidation ratios between 90 and 100 are characterized by the presence of kaolinite. If the oxidation ratio is still higher (all iron as Fe³⁺, parts of the manganese in the trivalent state), the rocks belong to assemblage 3 (phengite, paragonite, chlorite, viridine, (kaolinite), (garnet), quartz, hematite, braunite, rutile). Dedicated to Prof. Dr. K. Jasmund at his 60. birthday.     

Rosia Poieni copper deposit,Apuseni Mountains,Romania: advanced argillic overprint of a porphyry system

The Rosia Poieni deposit is the largest porphyry copper deposit in the Apuseni Mountains, Romania. Hydrothermal alteration and mineralization are related to the Middle Miocene emplacement of a subvolcanic body, the Fundoaia microdiorite. Zonation of the alteration associated with the porphyry copper deposit is recognized from the deep and central part of the porphyritic intrusion towards shallower and outer portions. Four alteration types have been distinguished: potassic, phyllic, advanced argillic, and propylitic. Potassic alteration affects mainly the Fundoaia subvolcanic body. The andesitic host rocks are altered only in the immediate contact zone with the Fundoaia intrusion. Mg-biotite and K-feldspar are the main alteration minerals of the potassic assemblage, accompanied by ubiquitous quartz; chlorite, and anhydrite are also present. Magnetite, pyrite, chalcopyrite and minor bornite, are associated with this alteration. Phyllic alteration has overprinted the margin of the potassic zone, and formed peripheral to it. It is characterized by the replacement of almost all early minerals by abundant quartz, phengite, illite, variable amounts of illite-smectite mixed-layer minerals, minor smectite, and kaolinite. Pyrite is abundant and represents the main sulfide in this alteration zone. Advanced argillic alteration affects the upper part of the volcanic structure. The mineral assemblage comprises alunite, kaolinite, dickite, pyrophyllite, diaspore, aluminium-phosphate-sulphate minerals (woodhouseite-svanbergite series), zunyite, minamyite, pyrite, and enargite (luzonite). Alunite forms well-developed crystals. Veins with enargite (luzonite) and pyrite in a gangue of quartz, pyrophyllite and diaspore, are present within and around the subvolcanic intrusion. This alteration type is partially controlled by fractures. A zonal distribution of alteration minerals is observed from the centre of fractures outwards with: (1) vuggy quartz; (2) quartz + alunite; (3) quartz + kaolinite ± alunite and, in the deeper part of the argillic zone, quartz + pyrophyllite + diaspore; (4) illite + illite-smectite mixed-layer minerals ± kaolinite ± alunite, and e) chlorite + albite + epidote. Propylitic alteration is present distal to all other alteration types and consists of chlorite, epidote, albite, and carbonates. Mineral parageneses, mineral stability fields, and alteration mineral geothermometers indicate that the different alteration assemblages are the result of changes in both fluid composition and temperature of the system. The alteration minerals reflect cooling of the hydrothermal system from >400 °C (biotite), to 300–200 °C (chlorite and illite in veinlets) and to lower temperatures of kaolinite, illite-smectite mixed layers, and smectite crystallization. Hydrothermal alteration started with an extensive potassic zone in the central part of the system that passed laterally to the propylitic zone. It was followed by phyllic overprint of the early-altered rocks. Nearly barren advanced argillic alteration subsequently superimposed the upper levels of the porphyry copper alteration zones. The close spatial association between porphyry mineralization and advanced argillic alteration suggests that they are genetically part of the same magmatic-hydrothermal system that includes a porphyry intrusion at depth and an epithermal environment of the advanced argillic type near the surface.Editorial handling: B. Lehmann     

Separate or shared metamorphic histories of eclogites and surrounding rocks? An example from the Bohemian Massif

Eclogite boudins occur within an orthogneiss sheet enclosed in a Barrovian metapelite‐dominated volcano‐sedimentary sequence within the Velké Vrbno unit, NE Bohemian Massif. A metamorphic and lithological break defines the base of the eclogite‐bearing orthogneiss nappe, with a structurally lower sequence without eclogite exposed in a tectonic window. The typical assemblage of the structurally upper metapelites is garnet–staurolite–kyanite–biotite–plagioclase–muscovite–quartz–ilmenite ± rutile ± silli‐manite and prograde‐zoned garnet includes chloritoid–chlorite–paragonite–margarite, staurolite–chlorite–paragonite–margarite and kyanite–chlorite–rutile. In pseudosection modelling in the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCKFMASH) using THERMOCALC, the prograde path crosses the discontinuous reaction chloritoid + margarite = chlorite + garnet + staurolite + paragonite (with muscovite + quartz + H₂O) at 9.5 kbar and 570 °C and the metamorphic peak is reached at 11 kbar and 640 °C. Decompression through about 7 kbar is indicated by sillimanite and biotite growing at the expense of garnet. In the tectonic window, the structurally lower metapelites (garnet–staurolite–biotite–muscovite–quartz ± plagioclase ± sillimanite ± kyanite) and amphibolites (garnet–amphibole–plagioclase ± epidote) indicate a metamorphic peak of 10 kbar at 620 °C and 11 kbar and 610–660 °C, respectively, that is consistent with the other metapelites. The eclogites are composed of garnet, omphacite relicts (jadeite = 33%) within plagioclase–clinopyroxene symplectites, epidote and late amphibole–plagioclase domains. Garnet commonly includes rutile–quartz–epidote ± clinopyroxene (jadeite = 43%) ± magnetite ± amphibole and its growth zoning is compatible in the pseudosection with burial under H₂O‐undersaturated conditions to 18 kbar and 680 °C. Plagioclase + amphibole replaces garnet within foliated boudin margins and results in the assemblage epidote–amphibole–plagioclase indicating that decompression occurred under decreasing temperature into garnet‐free epidote–amphibolite facies conditions. The prograde path of eclogites and metapelites up to the metamorphic peak cannot be shared, being along different geothermal gradients, of about 11 and 17 °C km^?1, respectively, to metamorphic pressure peaks that are 6–7 kbar apart. The eclogite–orthogneiss sheet docked with metapelites at about 11 kbar and 650 °C, and from this depth the exhumation of the pile is shared.     

'Forbidden zone' subduction of sediments to 150 km depth— the reaction of dolomite to magnesite + aragonite in the UHPM metapelites from western Tianshan, China

The solid‐state reaction magnesite (MgCO₃) + calcite (aragonite) (CaCO₃) = dolomite (CaMg(CO₃)₂) has been identified in metapelites from western Tianshan, China. Petrological studies show that two metamorphic stages are recorded in the metapelites: (1) the peak mineral assemblage of magnesite and calcite pseudomorphs after aragonite which is only preserved as inclusions within dolomite; and (2) the retrograde glaucophane‐chloritoid facies mineral assemblage of glaucophane, chloritoid, dolomite, garnet, paragonite, chlorite and quartz. The peak metamorphic temperatures and pressures are calculated to be 560–600 °C, 4.95–5.07 GPa based on the calcite–dolomite geothermometer and the equilibrium calculation of the reaction dolomite = magnesite + aragonite, respectively. These give direct evidence in UHP metamorphic rocks from Tianshan, China, that carbonate sediments were subducted to greater than 150 km depth. This UHP metamorphism represents a geotherm lower than any previously estimated for subduction metamorphism (< 3.7 °C km^?1) and is within what was previously considered a ‘forbidden’ condition within Earth. In terms of the carbon cycle, this demonstrates that carbonate sediments can be subducted to at least 150 km depth without releasing significant CO₂ to the overlying mantle wedge.     

云南墨江金厂金矿床含铬层状硅酸盐矿物成分标型特征

含铬绢云母类矿物在云南墨江金厂金矿床中广泛出现于黄铁铬绢英岩、黄铁硅质岩、黄铁铬云母岩和石英脉中。含铬绿泥石类矿物主要出现在石英脉、硅质岩、黄铁铬绢英岩中。蒙脱石出现于蚀变围岩中，而高岭石出现于富金石英脉中。本文通过对72个上述矿物电子探针数据的分析，确定了与其成因产状对应的含铬绢云母、含铬伊利石、含铬绿泥石、含铬蒙脱石、高岭石矿物的系列成分标型。研究表明，具最高铬含量的上述矿物样品均位于近金厂岩体穿脉的最北端。在铬铝云母SiO2-Cr2O3关系图上可以看出，不同成矿背景的铬铝绢云母，其Cr、Si离子数有分区特点，而本矿床的铬铝云母成分标型反映其富硅富铬的特点，与金厂超基性岩体的变质热液有关。