A staurolite-talc assemblage in tourmaline-phlogopite-chlorite schist from northern Victoria Land,Antarctica, and its petrogenetic significance

Staurolite and corundum are found as inclusions in tourmaline in a talc-phlogopite-chlorite-albite chist near Mount Bernstein (71°37S, 163°07E), northern Victoria Land, Antarctica. These inclusions are interpreted as relics of a staurolite-talc-corundum-chlorite assemblage that was stable during an early stage in the metamorphic cycle and subsequently armored by tourmaline, probably during the middle stage. Pressures and temperatures during the middle stage are estimated to be 650–700°C and 5.5–6.4 kbar. The transition from the early to the middle stage represents a roughly isothermal decrease in pressure of 2–3 kbar. During a late retrograde stage (T=300–370°C, P=3–5 kbar), staurolite was partly replaced by a muscovitic aggregate containing clinozoisite, pumpellyite, and margarite.The staurolite is unusually Si-poor (26.77, 25.85 weight % SiO₂ or 7.275, 7.091 Si per formula unit for 46 oxygens anhydrous), Al-rich (58.00, 57.85% Al₂O₃, 18.579, 18.702 Al), low in divalent cations (Fe+Mg+Mn+Zn=3.301, 3.560) and magnesian (atomic Mg/(Mg+Fe)=0.42, 0.40). Ion microprobe analysis of the first grain indicates about 0.2% Li₂O (0.219 Li) is present. The following substitutions are proposed to explain the unusual chemistry of this staurolite (crystallographic site notation of Smith 1968, in bold letters): Al(Si)+Al(Al(3A,B))Si(Si)+Fe(Fe), Li(Fe)+Al(Al(3A,B))2 Fe(Fe), and 2 Al(Al(3A,B)) 3 Fe(Fe).According to a pressure-temperature diagram constructed by the method of Schreinemakers for the model system FeO-MgO-Al₂O₃-SiO₂ (H₂O in excess), the talc-staurolite assemblage should be stable only in quartz-free rocks at temperatures near 700° C and pressures of 8 kbar or more. The rarity of the staurolite-talc assemblage even in Mg-Al-rich rocks metamorphosed at the appropriate pressure-temperature conditions is attributed to the appearance of anthophyllite or, in Na₂O-bearing rocks, gedrite. Orthoamphibole-cordierite and orthoamphibolekyanite assemblages with chlorite or corundum are incompatible with staurolite-talc±albite. In rocks lacking corundum and formed at pressures above the stability limit of cordierite, staurolite-talc may be metastable relative to orthoamphibole-kyanite, while in corundum-bearing rocks, staurolite-talc may appear under certain conditions, possibly at higher water activities than the orthoamphibole-kyanite assemblage.     

Authigenic layer silicate minerals in borehole Elmore 1, Salton Sea Geothermal Field,California, USA

A combined petrographic/X-ray/electron microprobe and energy dispersive system investigation of sandstone cuttings from borehole Elmore # 1 near the center of the Salton Sea Geothermal Field has revealed numerous regular variations in the composition, texture, mineralogy and proportions of the authigenic layer silicate minerals in the temperature interval 185° C (411.5 m depth) to 361° C (2,169 m). At temperatures near 190° C, dolomite/ankerite+calcite-bearing sandstones contain an illite/mixed layer phase with 10% expandable layers (dolomite/ankerite zone). In shale, the percentage of expandable layers in the mixed layer phase changes from 10–15% at 185° C to 5% at 210° C (494 m). In the interval 250° C (620 m) to 325° C (1,135 m), the calcite+pyrite+epidote-bearing sandstones contain a layer silicate assemblage of chlorite and illite (chlorite-calcite zone). In the shallower portions of this metamorphic zone, the illite contains 0–5% expandable layers, while at depths greater than 725 m (275° C) it is completely free of expandable layers. On increasing temperature, the white mica shows regular decreases in Si^IV, Mg and Fe, and increase in Al^IV, Al^VI, and interlayer occupancy, as it changes gradually from fine-grained illite (=textural sericite) to coarse-grained recrystallized phengitic white mica. In the same interval, chlorite shows decreases in Al^VI and octahedral vacancies and an increase in total Mg+Fe. The sandstones range from relatively unmodified detrital-textured rocks with porosities up to 20% and high contents of illite near 250° C to relatively dense hornfelsic-textured rocks with trace amounts of chlorite and phengite and porosities near 5% at 325° C. Numerous complex reactions among detrital (allogenic) biotite, chlorite, and muscovite, and authigenic illite and chlorite, occur in the chlorite-calcite zone.Biotite appears, and calcite disappears, at a temperature near 325° C and a depth of 1,135m. The biotite zone so produced persists to 360° C in sandstone, at which temperature orthoclase disappears and andradite garnet appears at a depth near 2,155 m. Throughout the biotite zone and into the garnet zone, the biotite undergoes compositional changes that are very similar to those observed in illite/phengite in the chlorite-calcite zone, including increases in interlayer occupancy, Al^IV, Al^VI, and Ti, and decreases in F^–, Si^IV, and Mg/Fe_t+Mg, on increasing temperature. Biotite thus changes from a siliceous, K-deficient biotite at the biotite isograd to a typical low-grade metamorphic biotite at temperatures near 360° C. Minor amounts of talc appear with biotite at the biotite isograd in sandstone, while actinolite appears in both sandstone and shale at temperatures near 340° C (1,325 m). Chlorite completely disappears from sandstone at temperatures of approximately 350° C (1,500 m), and diminishes abruptly in amount in the more chloritic shales at the same depth.     

Mg-Fe partitioning between biotite and a supercritical chloride solution

An experimental study of the partitioning of Mg and Fe between synthetic biotite and an aqueous chloride solution in the supercritical region as a function of temperature, pressure and concentration of Mg and Fe is reported. In the temperature range 500°–700° C and the pressure range 25–200 MPa, the Mg-Fe distribution between biotite and the chloride solution can be described by distribution curves based on the ideal solution model within a data scattering of 8%. Mg is preferentially partitioned into biotite, and Fe prefers the solution. This tendency is enhanced with increasing temperature. The distribution constants for the Mg-Fe exchange reactions in the system K(Mg,Fe)₃AlSi₃O₁₀(OH)₂-(Mg,Fe)Cl₂-KCl-H₂O have been determined. The present data favor a model in which the activity of Fe and Mg in biotite is close to the mole fraction at temperatures above 500° C. Comparison of the Mg-Fe partitioning between biotite-chloride solution and olivine-chloride solution reveals a slight enrichment of Fe in olivine relative to biotite.     

Chloritoid-bearing pelitic rocks of the Horsethief Creek Group,Southeastern British Columbia

Aluminous pelitic rocks of the Late Precambrian Horsethief Creek Group of southeastern British Columbia contain the assemblage chloritoidmuscovite-paragonite-quartz-chlorite (biotite zone). Additional members of the assemblage may include graphite, Fe-Mg carbonate, rutile, ilmenite and pyrite. No albite was detected. Lower grade pelitic rocks (chlorite zone) contain muscovite-chlorite and rare paragonite.Chloritoids from carbonate-free assemblages show a narrow range of composition (85±5 mol % Fe-chtd) and most porphyroblasts are zoned with higher Mn in cores and higher Mg in rims. For eight chloritoid-chlorite pairs, K _D = (Mg/Fe chtd/Mg/Fe chl) = 0.188±0.0234.Correlation of these mineral assemblages with experimental and computed phase equilibria and oxygen isotope temperatures suggest a minimum pressure near 4.5 Kbar, a minimum temperature near 335 ° C and an upper limit on temperature near 460 ° C. Variation in X _{CO 2} content of fluids attending metamorphism is inferred from the alternate appearance of either Fe-Mg carbonate + rutile or ilmenite-bearing assemblages. The assemblage paragonite-chloritoid-quartz-Fe-Mg carbonate-rutile is inferred to be stable at a T near 360 ° C, an X _{CO 2} near 0.9 and P near 5 Kbar.     

Coexisting cummingtonite and calcic amphibole in amphibolites from the Schneeberg complex,Tyrol, Austria

Summary The formation of cummingtonite in two Ca and Al-poor and Mg-rich amphibolites from the Austroalpine Schneeberg complex occurred at a maximum temperature of about 550°C (5 kb). This is a result of the amphibolite facies Alpine overprint in this part of the Eastern Alps.Textural and chemical relations suggest (Mg_–1Si_–1Al₂)-continuous reactions in the bivariant CMASH-assemblageCam-Cum-Chl ^* followed by the discontinuous reactionCam+Chl+Qu=Cum+Plg+H₂O to be responsible for the formation of cummingtonite in these samples.The Mg–Fe distribution coefficient with values of 0.6–0.7 is similar to cummingtonite-Ca-amphibole pairs from amphibolites with oligoclase+quartz reported in the literature. The Mg/(Mg+Fe) ratio of the calcic amphiboles is lower (0.539–0.555) than the coexisting cummingtonites (0.648–0.662).

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Koexistierende Cummingtonite und Hornblenden in Amphiboliten des Schneeberger Zuges, Tirol, Österreich

Zusammenfassung In zwei Ca- und Al-armen Amphiboliten des nördlichen Schneebergerzuges (Rotmoostal) bildete sich Cummingtonit bei Maximaltemperaturen von 550°C (5 kb) bei der Altalpidschen Metamorphose.Texturelle und chemische Beziehungen lassen vermuten, daß sich Cummingtonite sowohl nach kontinuierlichen Reaktionen (in bezug auf den Tschermak-Vektor Mg_–1Si_–1Al₂) gebildet hat, als auch aus Hornblende und Chlorit nach der diskontinuierlichen ACF-ReaktionCam+Chl+Qu=Cum+Plg+H₂O hervorgegangen ist.Der Mg–Fe-Verteilungskoeffizient zwischen Hornblende und Cummingtonit entspricht den aus der Literatur bekannten Werten. Er beträgt zwischen 0.6–0.7 für die beginnende Amphibolitfazies. Die Mg/(Mg+Fe)-Verhältnisse sind höher in Cummingtonit (0.648–0.662) als in der koexistierenden Hornblende (0.539–0.555).

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With 4 Figures     

The transition from pyroxene granulite facies to garnet clinopyroxene granulite facies. Experiments in the system CaO-MgO-Al2O3-SiO2

The pressure-temperature curve for the equilibrium anorthite+2enstatite=pyrope+diopside+quartz has been determined in the system CaO-MgO-Al₂O₂-SiO₂ to be between 13.4 and 14.0 kbars at 900° C. The slope up to 1,240° C is 8.5 bar/K. The entropy change at 1,200 K is 20 kJ. These data, combined with data from the literature, lead to a geobarometer equation which, when applied to rocks from the Agto area (West Greenland), gives pressure estimates of 6–10 kbars at 800° C. The results are consistent for rocks of differing Fe/Mg ratios and are consistent with independent pressure estimates.     

Hydrothermal alterations in the Echassières granitic cupola (Massif central,france)

Detailed petrographic and mineralogic investigations of an albite-lepidolite granite at Echassières (Massif Central, France; scientific deep drill program) shows the existence of hydrothermal stages which are closely related to the magmatic and structural history. According to fluid inclusion data, K-Ar datations and ¹⁸O/¹⁶O-D/H compositions of secondary minerals, two successive hydrothermal periods have been recognized. The early one (273–268 million years) produced a series of aluminous phyllosilicates: muscovite, pyrophyllite, donbassite, tosudite, kaolinite which are observed as vein deposits (<10 mm wide) and alteration products of primary minerals in wall-rocks. The vein system was sealed by monomineralic assemblages during a cooling period (400–150°C). This early hydrothermal alteration stage was controlled by interactions of rock with low salinity (1–10 wt% NaCl equivalent) fluids expelled from the granitic body during the cooling processes. The chemical properties of these fluids were the following: low pH, very low Mg and Fe and high Li, Na and K contents. Thermodynamic calculations show that the sequence pyrophyllite, Li-bearing donbassite, tosudite is mostly temperature dependent. From the chemical composition of secondary minerals and isotopic data it can be deduced that these fluids, which have a meteoric origin, have been expelled from the granite body during its cooling period and after interaction with it at high temperature. The late hydrothermal stage corresponds to deposits of fluorite and Fe-Mg rich illite (151 million years) in subvertical fractures. Temperature conditions did not exceed 250° C and fluids came through the surrounding metamorphic rocks into the granitic body. IIlite/smectite mixed-layer minerals have been identified in subvertical fractures which were opened during Tertiary periods. In the host micaschists, successive hydrothermal alterations took place during the cooling of the Beauvoir granite. Early magmatic fluids interacted with these micaschists. Locally, the metamorphic assemblage is replaced by a metasomatic one. Secondary topaz and (F, Li)-rich mica crystals were formed over a range of 450 of 150°C. Later hydrothermal fluids reacted with the country rocks to form phengite-biotite, chlorite-illite and kaolinite over a range of 300 to 150°C. Illite/smectite mixed-layer minerals crystallized in the roof micaschists and within the Beauvoir granite during the Tertiary alteration period. Meteoric water invaded open fractures producing supergene alteration mineral assemblages.     

Sapphirine bearing granulites from the Sipiwesk Lake area of the late Archean Pikwitonei granulite terrain,Manitoba, Canada

Sapphirine occurs in the orthopyroxene-cordierite and feldspar-sillimanite granulites in the Sipiwesk Lake area of the Pikwitonei granulite terrain, Manitoba (97°40W, 55°05N). The orthopyroxene-cordierite granulites have extremely high Al₂O₃ (24.5 wt%) and MgO (24.6 wt%) contents and contain sapphirine (up to 69.2 wt% Al₂O₃), aluminous orthopyroxene (up to 8.93 wt% Al₂O₃), cordierite, spinel, phlogopite, and corundum. Sapphirine forms coronas mantling spinel and corundum. Corona sapphirine is zoned and its composition varies through the substitution (Mg, Fe, Mn) Si=2 Al as a function of the phases with which it is in contact. Textural and chemical relationships of sapphirine with coexisting phases indicate that spinel + cordierite reacted to form orthopyroxene + sapphirine under conditions of increasing pressure. Moreover, decreasing core to rim variation of Al₂O₃ in orthopyroxene porphyroblasts suggests decreasing temperature during sapphirine formation. On the basis of experimentally determined P-T stability of the assemblage enstatite + sapphirine + cordierite, and the Al content of hypothetical Fe²⁺-free orthopyroxene associated with sapphirine and cordierite, metamorphic temperatures and pressures are estimated to be 860–890° C and 3.0–11.2 kbar.In the feldspar-sillimanite granulites, sapphirine occurs as a relict phase mantled by sillimanite and/or by successive coronas of sillimanite and garnet. These textural relations suggest the reaction sapphirine + garnet + quartz = orthopyroxene + sillimanite with decreasing temperature. Compositions of minerals in the assemblage garnet-orthopyroxene-sillimanite-plagioclase-quartz, indicate metamorphic P-T conditions of 780–880° C and 9±1 kb.The metamorphic conditions estimated in this study suggest that the sapphirine bearing granulites in the Sipiwesk Lake area represent Archean lower crustal rocks. Their formation might be related to the crustal thickening processes in this area as suggested by Hubregtse (1980) and Weber (1983).     

Phengite geobarometry based on the limiting assemblage with K-feldspar,phlogopite, and quartz

Following and extending the early work of Velde (1965) the pressure-temperature dependence of the compositions of potassic white micas coexisting with K-feldspar, quartz, and phlogopite in the model system K₂O-MgO-Al₂O₃-SiO₂-H₂O was investigated up to fluid pressures of 24 kbar by synthesis experiments. There is a strong, almost linear increase of the Si content per formula unit (p.f.u.) of phengite, ideally KAl_2–xMg_x[Al_1–xSi_3+xO₁₀] (OH)₂ with pressure, as well as a moderate decrease of Si (or x) with temperature. The most siliceous phengite with Si near 3.8 p.f.u. becomes stable near 20 kbar depending on temperature. However, contrary to Velde's assumption, these phengites coexisting with the limiting assemblage are invariably not of an ideal dioctahedral composition (as given by the above formula) but have total octahedral occupancies as high as about 2.1 p.f.u.The stability field of the critical assemblage phengite — K-feldspar — phlogopite — quartz ranges, in the presence of excess H₂O, from at least 350° C to about 700° C but has an upper pressure limit in the range 16–22 kbar, when K-feldspar and phlogopite react to form phengite and a K, Mg-rich siliceous fluid.For the purpose of using these phase relationships as a new geobarometer for natural rocks, the influence of other components in the phengite (F, Fe, Na) is evaluated on the basis of literature data. Water activities below unity shift the Si isopleths of phengite towards higher pressures and lower temperatures, but the effects are relatively small. Tests of the new geobarometer with published analytical and PT data on natural phengite-bearing rocks are handicapped by the paucity of reliable values, but also by the obvious lack of equilibration of phengite compositions in many rocks that show zonation of their phengites or even more than one generation of potassic white micas with different compositions. From natural phengites that do not coexist with the limiting assemblage studied here but still with a Mg, Fe-silicate, at least minimum pressures can be derived with the use of the data presented.     

Hydrothermal alteration of Tertiary igneous rocks from the Isle of Skye,northwest Scotland

Hydrothermal alteration of Tertiary gabbros from Skye involved the reaction of igneous olivine, augite, hypersthene, plagioclase, magnetite, and ilmenite with aqueous fluid primarily to combinations of talc, chlorite, montmorillonite, calcic amphibole, biotite, and secondary magnetite. Lesser amounts of calcite, epidote, quartz, sphene, prehnite, and garnet also developed. During mineralogical alteration of gabbro there was a net addition to rock of K, Na, Sr, and H₂O and a net loss of Mg. Gabbro was oxidized early in the hydrothermal event and later reduced. Iron and silicon were probably initially lost and later added. There is no evidence for significant change in the Al or Ca content of the gabbros. Hydrothermal alteration of Skye gabbro involved not only large-scale migration of ¹⁸O, ¹⁶O, D and H but also of K, Na, Sr, Mg, and probably Fe and Si.Mineral thermometry indicates that pyroxenes in the gabbros crystallized at 1000° C–1150° C and were very resistent chemically as well as isotopically to later hydrothermal alteration. Hypothetical equilibrium between primary and secondary mafic silicates suggests that mineralogical alteration of gabbro occurred at 450°–550° C. The lack of correlation between mineralogical and isotopic alteration of gabbro requires that much isotopic alteration occurred at temepratures above those at which the secondary minerals developed, 550°–1000° C. The chemical alteration of gabbro is correlated with its mineralogical alteration and therefore occurred at 450°–550° C.Measured progress of the mineral-fluid reactions was used to estimate the amount of H₂O fluid that infiltrated the gabbro as primary olivine was converted to talc+magnetite at 525°–550° C. Calculated fluid-rock ratios are in the range 0.2–6 (volume basis) and are smaller than values estimated from isotopic data (fluid/rock 1–10, volume basis). Both isotopic and petrologic data point to pervasive flow of fluid through crystalline rock at elevated temperatures of 500°–1000° C. Isotopic fluid-rock ratios are larger than petrologic fluid-rock ratios because isotopic alteration of cooling gabbro began earlier and at higher temperatures than did the mineralogical alteration.     

Fe-rich cordierites from acid volcanic rocks,an optical and x-ray single-crystal structure study

Low-cordierites from volcanic rocks of Tuscany (Italy), Lipari (Italy), and of the Cerberean Cauldron (Australia) were investigated. Both single crystal structure refinements and optical data indicate that the Italian samples contain only low concentrations of volatiles (<0.3 wt.%), whereas in the crystals from the Cerberean Cauldron more than 50% of the structural channels are occupied, preferentially by H₂O (1.6–1.9 wt.%). This high volatile concentration is in qualitative agreement with the estimated p,T-conditions (4–4.5 kbar at 750–780° C) of the magma prior to eruption. In contrast, the Italian cordierites have formed at temperatures above 950° C and pressures below 2 kbars. Low-cordierites of volcanic origin reveal the same high degree of Si, Al-ordering as observed for low-cordierites from metamorphic rocks and pegmatites. The crystals studied possess F(mol)=(Fe+Mn)/(Fe+Mn+Mg)>0.4 and provide additional information about the crystal structure of Fe-rich cordierites. With increasing FeMg substitution the mean T₁1(Al)-O distance decreases slightly, which is probably not caused by substitution of smaller cations on t₁1 but by angular distortion of the tetrahedron.     

Diffusion of 40Ar in hornblende

Measured radiogenic ⁴⁰Ar loss from two compositionally contrasting hornblendes following isothermal-hydrothermal treatment have provided model diffusion coefficients in the temperature range of 750° C to 900° C. Eight experiments using a hornblende (77–600) with a Mg/(Mg +Fe) ratio of 0.72 yield a linear array on an Arrhenius plot with a slope corresponding to an activation energy of 66.1 kcal-mol^–1 and a frequency factor of 0.061 cm²-sec^–1, assuming spherical geometry for the mineral aggregate. Five experiments undertaken on a hornblende (M Mhb-1) with a Mg/(Mg+Fe) ratio of 0.36 show similar behavior to the Mgrich sample, suggesting that the diffusivity of Ar in hornblendes is not sensitive to the Mg/Fe ratio.These data are consistent with kinetic information obtained from a geological experiment using the thermal effect of a granitoid intrusion. Together these data yield an activation energy of 64.1±1.7 kcal-mol^–1 and a frequency factor of 0.024± _0.011 ^0.053 cm²-sec^–1. For a hornblende with an effective diffusion radius of 80 m, these diffusion parameters predict closure temperatures between 578° C and 490° C for cooling rates in the range 500 to 5° C-Ma^–1.     

High pressure metamorphism in the Scourian of NW Scotland: Evidence from garnet granulites

Ultramafic and mafic granulites from Archaean gneisses in N.W. Scotland (the Scourian) show evidence of two periods of granulite facies mineral growth. The first produced a high pressure clinopyroxene +garnet±plagioclase assemblage at an estimatedP-T of 12–15 kb and 1,000° C. Uplift of the complex caused partial breakdown of the garnet by reaction with clinopyroxene to produce orthopyroxene +plagioclase ±spinel±amphibole symplectites, at an estimatedP-T of 10–14 kb and 800°–900° C. Garnet stability is shown to depend on both whole-rock Fe/Mg ratios and onP-T conditions. The pressures imply crustal thicknesses in the Archaean of least 35–45 km.     

Diamondiferous peridotite xenoliths from the Argyle (AK1) lamproite pipe,Western Australia

This paper describes a suite of peridotite xenoliths. some carrying diamonds at high grades, from the richly diamondiferous early Proterozoic (1180 Ma) Argyle (AK1) lamproite pipe, in northwestern Australia. The peridotites are mostly coarse garnet lherzolites but also include garnet harzburgite, chromite — garnet peridotite, a garnet wehrlite, and an altered spinel peridotite with extremely Cr-rich chromite. In all cases the garnet has been replaced by a kelyphite-like, symplectic intergrowth of Alrich pyroxenes, Al-spinel and secondary silicates. The peridotites have refractory compositions characterized by high Mg/(Mg+Fe) and depletion in lithophile elements (Al₂O₃ and CaO < 1%, Na₂O0.03%) and high field strength cations such as Ti, Zr, Y, and Yb. Olivines have high Mg/(Mg+Fe) (Mg ^91–93 ) and, like olivine inclusions in diamonds from the Argyle pipe, contain detectable amounts of Cr₂O₃ (0.03%–0.07%) but have very low CaO contents (typically 0.04%–0.05%). Enstatites (Mg ^92–94 ) have comparatively high Cr₂O₃ (0.2%–0.45%) and Na₂O (up to 0.18%) but very low Al₂O₃ contents (0.5%–0.7%). Diopsides (Mg ^92–94 , Ca/(Ca+Mg+Fe)=0.37–0.43) are Cr-rich (0.7%–1.9% Cr₂O₃) and have low Al₂O₃ (0.7%–2.2%) and Na₂O (0.5%–1.6%) contents. Many have high K₂O contents, typically 0.1%–0.4% but up to 1.3% K₂O in one xenolith. The chromite coexisting with former garnet is Mg-and Cr-rich [Mg/(Mg+Fe²⁺)=0.68–0.72, Cr/(Cr+Al)=0.72–0.79] whereas chromite in the spinel peridotite is even more Cr-rich (65% Cr₂O₃, Cr/(Cr+Al)=0.85, resembling inclusions in diamond. One highly serpentinized former garnet peridotite contains a Cr-rich (up to 13% Cr₂O₃) titanate resembling armalcolite but containing significant K₂O (1%–2.5%), CaO (0.6%–2.2%), ZrO₂ (0.1%–0.8%), SrO (0.1%–0.3%), and BaO (up to 0.58%): this appears to have formed as an overprint of the primary mineralogy. Temperatures and pressures estimated from coexisting pyroxenes and reconstructed garnet compositions indicate that the garnet lherzolites equilibrated at 1140°–1290° C and 5.0–5.9 GPa (160–190 km depth), within the stability field of diamond. Oxygen fugacties within the diamond forming environment are estimated from spinel-bearing assemblages to be reducing, with f _O2 between MW and IW. The presence of significant K in the diopsides from the peridotite xenoliths and in diopsides from heavy mineral concentrate from the Argyle pipe implies metasomatic enrichment of the subcontinental lithosphere within the diamond stability field. The P-T conditions estimated for the Argyle peridotites demonstrate that diamondiferous lamproite magmas incorporate mantle xenoliths from similar depths to kimberlites in cratonic settings, and imply that Proterozoic cratonized orogenic belts can have lithospheric roots of comparable thickness to beneath Archaean cratons. These roots lie at the base of the lithosphere within the stability field of diamond. The xenoliths, the calcic nature of chrome pyropes from heavy mineral concentrate, and the diamond inclusion assemblage indicate that the lighosphere beneath the Western Australian lamproites is mostly depleted lherozolite rather than the harzburgite commonly found beneath Archaean cratons. Nevertheless, the dominance of eclogitic paragenesis inclusions in Argyle diamonds indicates a significant proportion of diamondiferous eclogite is also present. The form, mineral inclusion assemblage, and the C-isotopic composition of diamonds in the peridotite xenoliths suggest that disaggregated diamondiferous peridotites are the source of the planar octahedral diamonds which constitute a minor component of the Argyle production. These diamonds are believed to have formed from mantle carbon in reduced, refractory peridotite (Iherzolite-harzburgite) in contrast to the predominant strongly ¹³C-depleted eclogitic suite diamonds which contain a recycled crustal carbon component. The source region of the lamproites has undergone long-term (2 Ga) enrichment in incompatible elements.     

High-magnesium staurolite in a sapphirine-garnet rock from the Limpopo Belt,Southern Africa

Unusually Mg-rich staurolite with F=Fe/(Fe+ Mg) = 0.51 occurs in a peraluminous silica-deficient sapphirine-garnet-gedrite-spinel-corundum-phlogopite rock as relic inclusions within pyrope-almandine garnet (F=0.43–0.48), from which it is generally separated by sapphirine (F=0.19). Gedrite has F=0.24–0.27, phlogopite 0.19, and spinel 0.43. The gradual disappearance of staurolite is due to a shift of the 3-phase AFM assemblage staurolite-garnetsapphirine to more Fe-rich compositions according to probably prograde reactions between staurolite and garnet to form sapphirine together with either quartz or gedrite. Thus still more Mg-rich staurolite seems to have existed in the rock at earlier stages of metamorphism characterized by lower temperatures and perhaps higher pressures. The local equilibria now frozen in indicate minimum pressures of 7–8 kbar and temperatures in excess of about 800° C.Staurolite is free from Zn, very low in Si, and richer in Ti than any other staurolite found thus far. Most notable is the unique Mg/Fe fraction between staurolite and garnet with staurolite being the more Fe-rich phase (K_D=1.32).     

Experimental study of Fe-Mg- and Ca-distribution between coexisting ortho- and clinopyroxenes at P=294 MPa,T=750 and 800° C

The Fe-Mg-Ca-distribution was investigated in synthesis experiments and with the mineral assemblage orthopyroxene+clinopyroxene+quartz. The phase compositions were identified by X-ray diffraction and, where possible, by electron microprobe. The attainment of equilibrium in the run products was signalled by the compositions from control runs (different solutions) becoming closely similar, by recycling runs, by the attainment of equilibrium from different directions (depending on the composition of starting phases), and by special kinetic experiments.The study produced the following results: (1) the Ca content of the clinopyroxenes decreases with increasing Fe (mol%) from 48.4 at X _Cpx ^Fe =5 to 39.8 at X _Cpx ^Fe =45 (800° C); from 47.6 at X _Cpx ^Fe = 10 to 41.7 at X _Cpx ^Fe =45 (750° C); increasing temperature expands the stability field of the less calcic clinopyroxenes. (2) The Ca content of orthopyroxenes increases slightly with Fe content from 1.8 at X _Opx ^Fe =20.5 to 3.2 at X _Opx ^Fe =75; the temperature effect on the Ca content under the T, P conditions of the experiment was not large. (3) Fe and Mg distribution between the coexisting ortho-and clinopyroxenes is largely temperature-dependent, particularly in the compositional range X _Opx ^Fe =15–75 mol%; as T increases, Fe redistributes from the rhombic to monoclinic mineral.Preliminary estimates of rock formation temperatures using the obtained data show that most of the known two-pyroxene geothermometers overstate the actual values by 50–150° C.     

An experimental investigation of high-temperature interactions between seawater and rhyolite,andesite, basalt and peridotite

Natural seawater was allowed to react with rhyolite, andesite, basalt, and peridotite at 200°–500° C, and 1,000 bars at water/rock mass ratios of 5 and 50 in order to investigate the effects of rock type, water/rock ratio, and temperature on solution chemistry and alteration mineralogy. The results indicate that interactions of seawater with various igneous rocks are similar in the production of a hydrous Mg-silicate and anhydrite as major alteration products. Fluids involved in the interactions lose Mg to alteration phases while leaching Fe, Mn, and Si from the rocks. The pH of the solutions is primarily controlled by Mg-OH-silicate formation and therefore varies with Mg and Si concentration of the system. Other reactions which involve Mg (such as Mg-Ca exchange) or which produce free H⁺, cause major differences in fluid chemistry between different seawater/ rock systems. High water/rock ratio systems (50/1) are generally more acidic and more efficient in leaching than low ratio systems (5/1), due to relatively more seawater Mg available for Mgsilicate production. The experiments show that large-scale seawater/rock interaction could exert considerable control on the chemistry of seawater, as well as producing large bodies of altered rock with associated ore-deposits.Active plate margins of convergence or divergence are suitable environments for hydrothermal systems due to the concurrence of igneous activity, tectonism, and a nearby water reservoir (seawater or connate water). The experimental data indicate that seawater interactions with igneous host rocks could generate many of the features of ore-deposits such as the Kuroko deposits of Japan, the Raul Mine of Peru, the Bleida deposit of Morocco, and deposits associated with ophiolites. Serpentinization of peridotite and alteration of igneous complexes associated with plate margins can also be explained by seawater interaction with the cooling rock. Geothermal energy production could benefit from experimental investigations of hot water/rock systems by development of chemical, temperature, and pressure control systems to maximize the lifetime of hydrothermal flow.     

Genetic environment of germanium-bearing gold-silver vein ores from the Wolyu mine,Republic of Korea

The Wolyu mine is one of the largest vein-type gold-silver-bearing epithermal systems in the Youngdong district and is the first gold-silver deposit in Korea found to contain significant germanium, in the form of argyrodite (Ag₈GeS₆). Mineralized veins (78.9 ± 1.2 Ma) crosscutting Late Cretaceous hostrock tuff and quartz porphyry (81.5 ± 1.8 Ma) consist of three stages of quartz and carbonates, the first of which contains pyrite, basemetal sulfides and Au-Ag-minerals. Stage I Au-Ag-Ge-mineralized veins show a systematic variation of mineral assemblage with time: (1) quartz + pyrite; (2) quartz + pyrite + sphalerite + electrum + argentite; (3) carbonate + quartz + sphalerite + electrum + argentite; (4) carbonate + native silver + argentite + Ag-sulfosalts + argyrodite + sphalerite. Calculated values of temperature and sulfur activity are: assemblage (1), 360-280°C and 10^–7-10^–10; (2), 280-210°C and 10^–10-10^–14; (3), 210-180°C and 10^–14-10^–16; (4), 180-155°C and 10^–17-10^–18. These data, the frequent association of gold with sulfides, and the abundance of pyrite in alteration zones indicate that decreasing sulfur activity and cooling were important in triggering gold deposition. Hydrogen and oxygen isotope compositions of ore fluids display a systematic variation with increasing time. Within the main Ag-Au-Ge mineralization, D and ¹⁸O values decrease with the transition from quartz to carbonate deposition (from -78 and –2.8% to –90 and –8.7%., respectively), indicating increasing involvement (mixing) of less evolved meteoric water which resulted in progressive cooling and dilution of ore fluids in the shallow ( 370–600 m) Wolyu epithermal system.     

Contrasting parageneses in the manganese silicate-carbonate rocks from Parseoni,Sausar Group,India and their interpretation

Mn silicate-carbonate rocks at Parseoni occur as conformable lenses within metapelites and calc-silicate rocks of the Precambrian Sausar Group, India. The host rocks are estimated to have been metamorphosed at uppermost P-T conditions of 500–550°C and 3–4 kbar. The Mn-rich rocks contain appreciable Fe, reflected in the occurrence of magnetite₍₁₎ (MnO 1%), magnetite₍₂₎ (MnO 15%) and magnetite₍₃₎ (MnO 10%). Two contrasting associations of pyroxmangite, with and without tephroite, developed in the Mn silicate-carbonate rocks under isothermal-isobaric conditions. The former assemblage formed in relatively Fe-rich bulk compositions and equilibrated with a metamorphic fluid having a low X _{CO 2} (<0.2), and the latter equilibrated with a CO₂-rich fluid. Rhodochrosite+magnetite₍₁₎+quartz protoliths produced the observed mineral assemblages on metamorphism. Partitioning of major elements between coexisting phases is somewhat variable. Fe shows preference for tephroite over pyroxmangite at the ambient physical conditions of metamorphism. Oxygen fugacity during metamorphism was monitored at or near the QFM buffer in tephroite bearing domains, and the fluid composition was buffered by mineral reactions in respective domains. As compared to other metamorphosed Mn deposits of the Sausar Group, the Mn silicate-carbonate rocks at Parseoni were, therefore, metamorphosed at much lower f _{O 2} through complex mineral-fluid interactions.     

Peridotites from the Mid-Atlantic Ridge at 43° N and their petrogenetic relation to abyssal tholeiites

Whole-rock, major and trace element analyses and microprobe mineral analyses were conducted on serpentinized peridotites recovered from the walls of a MAR (Mid-Atlantic Ridge) 43° N fracture zone. These peridotites are extensively serpentinized; serpentine usually makes up 30–100 vol. percent of the bulk rocks. The relict minerals observed consist mainly of olivine and orthopyroxene with subordinate amounts of clinopyroxene and brown spinel. The range in olivine composition is very limited (Fo_91–92). Orthopyroxene forms large, anhedral crystals with clinopyroxene exsolution lamellae and shows undulose extinction with bent cleavages and lamellae. Broad beam microprobe analyses indicate that the composition range of orthopyroxene is also limited (En_89.1–87.6Fs_8.2-8.0Wo_2.7–4.4; Al₂O₃=1.82–2.64 wt%; Cr₂O₃=0.63–0.88 wt%). Clinopyroxene tends to fringe large orthopyroxene crystals or fills the interstices between them. The Mg/Fe ratios of clinopyroxene are practically constant; however, the Ca/(Ca + Mg + Fe) ratios range from 0.48 to 0.45. The Cr/(Cr+Al) and Mg/(Mg+ Fe²⁺) ratios of brown spinel range from 0.57 to 0.36 and 0.69 to 0.56, respectively. The geothermometers utilizing coexisting spinel lherzolite mineral assemblages suggest that the MAR 43° N peridotites attained equilibrium at temperatures from 1100° to 1250° C.Peridotites recovered from the ocean floor are generally considered to have been subjected to partial melting processes and are regarded as residues left after primary magma was removed. Major element chemistry of the MAR 43° N peridotites are compared with those of the ocean-floor ultramafic tectonites reported previously and used together with those published data to demonstrate that the major element abundances of the oceanfloor peridotites define an average trend which is compatible with removal of primary magma from these peridotites at moderate pressures (10–15 kb). Then, the most primitive abyssal tholeiite glasses could be produced by ca. 10% olivine fractionation of such primary magma. Extensive fractionation of olivine and/or orthopyroxene from picritic liquids which are in equilibrium with the lherzolitic or harzburgitic mantle sources at higher pressures (>20 kb) could not yield the majority of the most primitive abyssal tholeiite glasses.