Chlorite-rich ultramafic reaction zones in Colorado Plateau xenoliths: recorders of sub-Moho hydration

 Three chlorite-rich and one garnet-pyroxenite xenolith from the diatreme at Moses Rock, Utah, document storage and transport of water and consequent metasomatism in the mantle within the stability field of garnet peridotite, probably at depths of at least 75 km. Three mineral assemblages are present in zones in one chlorite-rich xenolith: in that xenolith, an assemblage of chlorite+enstatite+diopside+ ilmenite+titanian chondrodite is separated by diop- side+“talc” from an assemblage of chlorite+diopside+ilmenite+pyrite. Euhedral grains of enstatite (0.02% Al₂O₃, 0.05% CaO)+diopside record low temperatures, and high Mn/Fe in these pyroxenes was caused by growth in chlorite-dominated rock. Derivation from garnet lherzolite is established by relict pyrope (Py₇₁Gr₁₁Alm₁₈). The “talc” has Fe/Mg unusually high relative to that of associated chlorite, and electron probe analyses of the “talc” sum low, consistent with excess water; the unusual composition may be due solely to alteration and consequent submicroscopic intergrowths of other phases, but the “talc” could be an analogue of the high-pressure synthetic 10-Å phase. Garnet pyroxenite has a retrograde assemblage of chlorite-garnet-omphacite. The chlorite-rich rocks formed at contacts between garnet peridotite and other mantle rock in response to fluid flow. Pressures ≥2.2 GPa are consistent with stability of enstatite + aqueous fluid and of diopside + talc, with the occurrence of titanian chondrodite, and with the stability of garnet lherzolite. A chlorite separate has δ¹⁸O=6.9, consistent with mantle hydration. The small-scale reaction zones could have formed in a geologically brief time, plausibly just before eruption at about 25 Ma, and the responsible fluids probably also catalyzed recrystallization of associated eclogites. The hydration may have been restricted to shear zones that traversed the lower crust and the mantle to at least 75 km depth. The chlorite-rich rocks may be from the deepest part of the mantle that was sampled by the diatreme eruption. Chlorite-garnet pairs in garnet pyroxenites and pyrope megacrysts yield temperatures in the range 410–510^° C. Low temperatures in the mantle of the Colorado Plateau are consistent with an unusually low mantle heat flux and with cooling of lithosphere by an underlying subducted slab. Received: 14 April 1994/Accepted: 23 December 1994     

Composition of aqueous fluid coexisting with mantle minerals at high pressure and its bearing on the differentiation of the Earth’s mantle

In order to understand the role of aqueous fluid on the differentiation of the mantle, the compositions of aqueous fluids coexisting with mantle minerals were investigated in the system MgO-SiO₂-H₂O at pressures of 3 to 10 GPa and temperatures of 1000 to 1500°C with an MA8-type multianvil apparatus. Phase boundaries between the stability fields of forsterite + aqueous fluid, forsterite + enstatite + aqueous fluid, and enstatite + aqueous fluid were determined by varying the bulk composition at constant temperature and pressure. The composition of aqueous fluid coexisting with forsterite and enstatite can be defined by the intersection of these two phase boundaries. The solubility of silicate components in aqueous fluid coexisting with forsterite and enstatite increases with increasing pressure up to 8 GPa, from about 30 wt% at 3 GPa to about 70 wt% at 8 GPa. It becomes almost constant above 8 GPa. The Mg/Si weight ratio of these aqueous fluids is much higher than at low pressure (0.2 at 1.5 GPa) and almost constant (1.2) at pressures between 3 and 8 GPa. At 10 GPa, it becomes about 1.4. Aqueous fluid migrating upward through the mantle can therefore dissolve large amounts of silicates, leaving modified Mg/Si ratios of residual materials. It is suggested that the chemical stratification of Mg/Si in the Earth may have been formed as a result of aqueous fluid migration.     

Preferential dissolution of SiO<Subscript>2</Subscript> from enstatite to H<Subscript>2</Subscript> fluid under high pressure and temperature

Stability and phase relations of coexisting enstatite and H₂ fluid were investigated in the pressure and temperature regions of 3.1–13.9 GPa and 1500–2000 K using laser-heated diamond-anvil cells. XRD measurements showed decomposition of enstatite upon heating to form forsterite, periclase, and coesite/stishovite. In the recovered samples, SiO₂ grains were found at the margin of the heating hot spot, suggesting that the SiO₂ component dissolved in the H₂ fluid during heating, then precipitated when its solubility decreased with decreasing temperature. Raman and infrared spectra of the coexisting fluid phase revealed that SiH₄ and H₂O molecules formed through the reaction between dissolved SiO₂ and H₂. In contrast, forsterite and periclase crystals were found within the hot spot, which were assumed to have replaced the initial orthoenstatite crystals without dissolution. Preferential dissolution of SiO₂ components of enstatite in H₂ fluid, as well as that observed in the forsterite H₂ system and the quartz H₂ system, implies that H₂-rich fluid enhances Mg/Si fractionation between the fluid and solid phases of mantle minerals.     

Phase relations of a serpentine composition between 5 and 14 GPa: significance of clinohumite and phase E as water carriers into the transition zone

Run products from high pressure experiments at 800-1,200 °C and 5-14 GPa (corresponding to depths of 150 to 420 km) on a serpentine bulk composition [close to Mg₃Si₂O₅(OH)₄] were analysed by optical microscopy, micro-Raman spectroscopy and electron microprobe. All charges exhibit strong chemical zoning. Fluid, melt and hydrous solids were mostly concentrated at the top, bottom and along the wall of the capsules. The central part of the charge was devoid of H₂O. Both fluid and hydrous magnesian phases exhibit a Mg/Si ratio higher than forsterite. In contrast, the centre of the capsule was enriched in SiO₂. The observed zoning can neither be explained by gravitational settling nor by a thermal gradient alone. Most likely the fluid was separated from the solids by surface forces and thereby established the chemical gradient by preferentially dissolving MgO. If strong chemical zoning is taken into account, the occurrence of more phases than allowed by the phase rule can be explained by separating the bulk into several domains of different bulk compositions. Results indicate that small amounts of F increase the stability field of clinohumite, Mg₉Si₄O₁₆(OH,F)₂, compared to OH-clinohumite in pure MSH previously reported. Clinohumite coexists with enstatite up to 975 °C at 5 GPa, and up to 1,100 °C at 12 GPa. At 14 GPa (close to the !/#-Mg₂SiO₄ transition) phase E becomes the most important water carrier. The new results indicate that clinohumite could be an important mantle mineral for transporting water into the Earth's transition zone due to its high thermal stability compared to other important water carriers such as serpentine and phase A.     

Experimentally Determined Phase Relations in Hydrous Peridotites to 6{middle dot}5 GPa and their Consequences on the Dynamics of Subduction Zones

Fluid-saturated subsolidus experiments from 2·0 to 6·5GPa, and from 680 to 800°C have been performed on threemodel peridotites in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O(NCFMASH). Amphibole and chlorite coexist up to 2·4 GPa,700°C. Chlorite persists to 4·2 GPa at 680°C.Starting from 4·8 GPa, 680°C a 10 Å phase structurereplaces chlorite in all compositions. The 10 Å phasestructure contains significant Al₂O₃ (up to 10·53 wt%) deviating from the MgO–SiO₂–H₂O 10 Å phase(MSH 10 Å phase). A mixed layered structure (chlorite–MSH10 Å phase) is proposed to account for aluminium observed.In the Tinaquillo lherzolite amphibole breakdown occurs viathe reaction Thermal stabilityof chlorite (chlorite + orthopyroxene = forsterite + garnet+ H₂O) is shifted towards lower temperatures, compared withthe system MASH. Furthermore, the chlorite thermal breakdownis also related to the degenerate reaction Chlorite and the Al-10 Å phase structurecontribute significantly to the water budget in subduction zonesin the depth range relevant for arc magmatism, whereas amphibole-relatedfluid release is restricted to the forearc region. Chloriteand Al-10 Å phase breakdowns might explain the occurrenceof a double seismic zone by dehydration embrittlement. KEY WORDS: amphibole; chlorite; high pressure; peridotites; subduction zones     

Sapphirine+Forsterite and Sapphirine+Humite-Group Minerals in an Ultra-Magnesian Lens from Kuhi-lal, SW Pamirs, Tajikistan: Are these Assemblages Forbidden?

Sapphirine occurs with humite-group minerals and forsteritein Precambrian amphibole-facies rocks at Kuhi-lal, SW PamirMountains, Tajikistan, a locality also for talc+kyanite magnesiohornblendewhiteschist. Most of these sapphirine-bearing rocks are graphiticand sulfidic (pyrite and pyrrhotite) and contain enstatite,clinohumite or chondrodite, spinel, rutile, gedrite, and phlogopite.A phlogopite schist has the assemblage with X_Fe = Fe/(Fe+Mg)increasing as follows: chlorite (0-003)<phlogopite (0.004–0.005)sapphirine (0.004–0.006) enstatite (0-006)forsterite (0-006–0-007)<spinel (0-014). This assemblage includes the incompatiblepair sapphirine+forsterite, but there is no textural evidencefor reaction. In one rock with clinohumite, X_Fe increases asfollows: clinohumite (0-002) <sapphirine (0-003) <enstatite(0-004–0-006) <spinel (0-010). Ion microprobe and wet-chemicalanalyses give 0-57–0-73 wt.% F in phlogopite and 0-27wt.% F in chlorite in the phlogopite schist; 0-04, 1.5–1.9,and 4.4 wt.% F in forsterite, clinohumite, and chondrodite,respectively; and 0-0-09 wt.% BeO and 0-05–0-21 wt.% B₂O₃in sapphirine. Stabilization of sapphirine+clinohumite or sapphirine+chondroditeinstead of sapphirine+phlogopite is possible at high F contentsin K-poor rocks, but minor element contents appear to be toolow to stabilize sapphirine as an additional phase with forsterite+enstatite+spinel.Although sapphirine+forsterite is metastable relative to spinel+enstatitein experiments conducted at a_H2O=1 in the MgO-Al₂O₃-SiO₂-H₂Osystem, it might be stabilized at a_H2O0.5, P4 kbar, T650–700C.Textures in the Kuhi-lal whiteschists suggest a polymetamorphicevolution in which the rocks were originally metamorphosed atT650C, P 7 kbar, conditions under which sapphirine+clinohumiteand sapphirine+chondrodite are inferred to have formed, andsubsequently affected by a later event at lower P, similar T,and lower a_H2O. The latter conditions were favorable for sapphirine+forsteriteto form in a rock originally containing chlorite+forsterite+spinel+enstatite.     

Reactions Leading to the Disappearance of Pumpellyite in Low-grade Metamorphic Rocks of the Sanbagawa Metamorphic Belt in Central Shikoku, Japan

The major mineral assemblages of the metabasites of the Omoiji-Nagasawaarea in central Shikoku are hematite+epidote+chlorite+actinolite,riebeckitic actinolite+epidote+chlorite, epidote+chlorite+actinolite,and pumpellyite+epidote+chlorite+actinolite. The constituentminerals are often heterogeneous and assemblages in the fieldof a thin section sometimes do not obey the phase rule, butif grains apparently in non-equilibrium with others are excludedand domains of chemical equilibrium are appropriately chosenthe assemblages approximately obey the phase rule. The stability of hematite, pumpellyite, and epidote associatedwith chlorite and actinolite can be dealt with in terms of aternary system with appropriate excess phases. By fixing theFe²⁺/(Fe²⁺ +Mg) ratio of chlorite, it is dealt with in termsof stability relations in the system Ca₂Al₃Si₃O₁₂(OH)–Ca₂AlFe₂Si₃O₁₂(OH)with excess chlorite, actinolite, quartz, and controlled P_H2O.The maximum and minimum Fe³⁺ contents of epidote in this modelsystem are determined by hematite+epidote+chlorite+actinoliteand pumpellyite+epidote+chlorite+actinolite assemblages. Themaximum Fe³⁺ of the three phase assemblage epidote+chlorite+actinoliteis insensitive to temperature, but the minimum Fe³⁺ contentof epidote is sensitive to temperature and can be used to definethe metamorphic grade by a continuous quantity related to temperature.The phase relations expected for the model system are in goodagreement with the parageneses of the Sanbagawa terrain in centralShikoku and offer an explanation to the rule of Miyashiro &Seki (1958a) that the compositional range of epidote enlargeswith increasing temperature. The model also makes it possibleto estimate semi-quantitatively the temperature range in whichthe assemblage pumpellyite+epidote+chlorite+actinolite is stable.The possible maximum range is about 120 ?C, but the assemblageis stable in metabasite only for about 90 ?C. The higher temperaturelimit of the pumpellyite-actinolite facies defined by the disappearanceof pumpellyite in metabasite corresponds to the temperatureat which epidote with Fe³⁺/(Fe³⁺ +Al) = 0.10 0.15 coexistswith pumpellyite, actinolite, and chlorite. The compositions of epidotes in the metabasites of the Omoiji-Nagasawaarea cluster around Fe³⁺/(Fe³⁺ +Al) = 0.33. The grade of thisarea is close to the lower temperature stability limit of thepumpellyite+epidote+chlorite+actinolite assemblage.     

Petrogenesis of Carbonate-orthopyroxenites (Sagvandites) and related rocks from Troms, Northern Norway

Carbonate-orthopyroxenites from Troms consist of enstatite andmagnesite with variable amounts of olivine, talc, serpentine,chlorite, and phlogopite and include the ore minerals chromite,magnetite, pentlandite, pyrite, and in some cases pyrrhotite,heazlewoodite, millerite, and maucherite. Related rocks compriseolivine-magnesite-, talc-magnesite and olivine-orthopyroxene(saxonite)-assemblages. Allochemical replacement reactions,involving mobile CO₂, H₂O, and SiO₂, are shown to comprise themain petrogenetic mechanism. Saxonite, however, may representa possible source material. Discussion of the model system MgO-SiO₂-CO₂-H₂O for P_flukl =2 and 7 kb, respectively, indicates that best agreement withpetrographic evidence is reached assuming elevated pressuresand both gas-excess and gas-deficiency conditions by means oflocal equilibria. The gas-deficient assemblage enstatite+talc+forsterite+magnesiteis presumed to be stable at pressures above 5 kb. Recalculationof whole-rock analyses to a CO₂-free basis by several alternativemethods suggests that rock evolution could have followed thetrend dunite saxonite orthopyroxenite sagvandite+related rocks.A simple geometric method is used to outline possible schemesof rock evolution, involving gas-deficient phase assemblages.     

The upper thermal stability of clinochlore,Mg5Al[AlSi3O10](OH)8, at 10–35 kb P_{{\text{H}}_{\text{2}} {\text{O}}}

Clinochlore, which is, within the limits of error, the thermally most stable member of the Mg-chlorites, breaks down at = P _tot to the assemblage enstatite+forsterite+spinel+H₂O along a univariant curve located at 11 kb, 838 ° C; 15kb, 862 ° C; and 18 kb, 880 ° C (±1 kb ±10 ° C). At water pressures above that of an invariant point at 20.3 kb and 894 ° C involving the phases clinochlore, enstatite, forsterite, spinel, pyrope, and hydrous vapor, clinochlore disintegrates to pyrope+forsterite+spinel+H₂O. The resulting univariant curve has a steep, negative dP/dT slope of –930 bar/ °C at least up to 35 kb.Thus, given the proper chemical environment, Mg-chlorites have the potential of appearing as stable phases within the earth's upper mantle to maximum depths between about 60 and 100 km depending on the prevailing undisturbed geotherm, and to still greater depths in subduction zones. However, unequivocal criteria for mantle derived Mg-chlorites are difficult to find in ultrabasic rocks.     

The high-pressure stability of chlorite and other hydrates in subduction mélanges: experiments in the system Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O

The solubility of chromium in chlorite as a function of pressure, temperature, and bulk composition was investigated in the system Cr₂O₃–MgO–Al₂O₃–SiO₂–H₂O, and its effect on phase relations evaluated. Three different compositions with X _Cr = Cr/(Cr + Al) = 0.075, 0.25, and 0.5 respectively, were investigated at 1.5–6.5 GPa, 650–900 °C. Cr-chlorite only occurs in the bulk composition with X _Cr = 0.075; otherwise, spinel and garnet are the major aluminous phases. In the experiments, Cr-chlorite coexists with enstatite up to 3.5 GPa, 800–850 °C, and with forsterite, pyrope, and spinel at higher pressure. At P > 5 GPa other hydrates occur: a Cr-bearing phase-HAPY (Mg_2.2Al_1.5Cr_0.1Si_1.1O₆(OH)₂) is stable in assemblage with pyrope, forsterite, and spinel; Mg-sursassite coexists at 6.0 GPa, 650 °C with forsterite and spinel and a new Cr-bearing phase, named 11.5 Å phase (Mg:Al:Si = 6.3:1.2:2.4) after the first diffraction peak observed in high-resolution X-ray diffraction pattern. Cr affects the stability of chlorite by shifting its breakdown reactions toward higher temperature, but Cr solubility at high pressure is reduced compared with the solubility observed in low-pressure occurrences in hydrothermal environments. Chromium partitions generally according to \(X_{\text{Cr}}^{\text{spinel}}\) ? \(X_{\text{Cr}}^{\text{opx}}\) > \(X_{\text{Cr}}^{\text{chlorite}}\) ≥ \(X_{\text{Cr}}^{\text{HAPY}}\) > \(X_{\text{Cr}}^{\text{garnet}}\). At 5 GPa, 750 °C (bulk with X _Cr = 0.075) equilibrium values are \(X_{\text{Cr}}^{\text{spinel}}\) = 0.27, \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.08, \(X_{\text{Cr}}^{\text{garnet}}\) = 0.05; at 5.4 GPa, 720 °C \(X_{\text{Cr}}^{\text{spinel}}\) = 0.33, \(X_{\text{Cr}}^{\text{HAPY}}\) = 0.06, and \(X_{\text{Cr}}^{\text{garnet}}\) = 0.04; and at 3.5 GPa, 850 °C \(X_{\text{Cr}}^{\text{opx}}\) = 0.12 and \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.07. Results on Cr–Al partitioning between spinel and garnet suggest that at low temperature the spinel- to garnet-peridotite transition has a negative slope of 0.5 GPa/100 °C. The formation of phase-HAPY, in assemblage with garnet and spinel, at pressures above chlorite breakdown, provides a viable mechanism to promote H₂O transport in metasomatized ultramafic mélanges of subduction channels.     

Stability of Yoderite in the Absence and in the Presence of Quartz: an Experimental Study in the System MgO-Al2O3-Fe2O3-SiO2-H2O

The water-pressure temperature stability field of yoderite,ideally Mg₂Al_5.6Fe^{3 +} _0.4Si₄O₁₈(OH)₂, was determined at highoxygen fugacities by high-pressure bracketing runs on eightpossible breakdown reactions involving the phases chlorite,kyanite, talc, staurolite, pyrope, enstatite, boron-free kornerupine,cordierite, quartz, and invariably an excess of hematite. Yoderitewas found to be stable over the surprisingly large PT rangefrom 6 to 25 kbar water pressure and 590 to 795 C. It is thusa high-pressure mineral covering the upper amphibolite and portionsof the eclogite facies. In the presence of quartz its upperpressure stability is reduced to some 15 kbar, and its uppertemperature stability to 715 C. Two of the yoderite-producingreactions are anomalous as they show dehydration in the directiontowards lower temperatures. Importantly, this is also true forthe reaction kyanite + talc + hematite+H₂O=yoderite+quartz whichis responsible for the only yoderite occurrence in nature atMautia Hill, Tanzania. Preliminary thermodynamic calculationsindicate that—owing to this unusual dehydration behavior—thestability field for the assemblage yoderite+quartz disappearsfor water activities lower than 0.5. The rarity of yoderitein natural rocks, which is in contrast to its large PT stabilityfield, must be explained on chemical rather than on physicalgrounds. Yoderite can only occur in whiteschist-type bulk compositionsrich in MgO, Al₂O₃, SiO₂, and containing some iron, but poorin alkalis and CaO. Oxygen fugacities must be unusually highto keep Fe trivalent, and—at least for rocks with excessquartz—the water activity must be high as well. In anenvironment of this kind, yoderite formation in the Mautia Hillwhiteschist may have occurred even at constant total pressureand temperature simply by an influx of hydrous fluid duringthe late stages of metamorphism under amphibolite facies conditions.     

The low-pressure stability of phase A,Mg7Si2O8(OH)6

 Phase A, Mg₇Si₂O₈(OH)₆, is a dense hydrous magnesium silicate whose importance as a host of H₂O in the Earth’s mantle is a subject of debate. We have investigated the low-pressure stability of phase A in experiments on the reaction phase A=brucite+forsterite. Experiments were conducted in piston-cylinder and multi-anvil apparatus, using mixtures of synthetic phase A, brucite and forsterite. The reaction was bracketed between 2.60 and 2.75 GPa at 500° C, between 3.25 and 3.48 GPa at 600° C and between 3.75 and 3.95 GPa at 650^° C. These pressures are much lower than observed in the synthesis experiments of Yamamoto and Akimoto (1977). At 750^° C the stability field of brucite + chondrodite was entered. The enthalpy of formation and entropy of phase A at 1 bar (10⁵ Pa), 298 K, were derived from the experimental brackets on the reaction phase A=brucite+forsterite using a modified version of the thermodynamic dataset THERMOCALC of Holland and Powell (1990), which includes a new equation of state of H₂O derived from the molecular dynamics simulations of Brodholt and Wood (1993). The data for phase A are: ΔH ^o _f =−7126±8 kJ mol^-1, S ^o=351 J K^-1 mol^-1. Incorporating these data into THERMOCALC allows the positions of other reactions involving phase A to be calculated, for example the reaction phase A + enstatite=forsterite+vapour, which limits the stability of phase A in equilibrium with enstatite. The calculated position of this reaction (753° C at 7 GPa to 937° C at 10 GPa) is in excellent agreement with the experimental brackets of Luth (1995) between 7 and 10 GPa, supporting the choice of equation of state of H₂O used in THERMOCALC. Comparison of our results with calculated P-T paths of subducting slabs (Peacock et al. 1994) suggests that, in the system MgO–SiO₂–H₂O, phase A could crystallise in compositions with Mg/Si>2 at pressures as low as 3 GPa. In less Mg rich compositions phase A could crystallise at pressures above approximately 6 GPa. Received: 3 July 1995/Accepted: 14 December 1995     

High-pressure and high-temperature stability of chlorite and 23-Å phase in the natural chlorite and synthetic MASH system

A series of experiments was conducted on the decomposition of natural and chemically mixed chlorites to examine the stable hydrous phases in the MgO–FeO–Al₂O₃–SiO₂–H₂O (MFASH) system under 5–12 GPa and 700–1100 °C. The upper pressure and temperature limits of the stability region of chlorite are consistent with those observed in previous studies. The hydrous aluminum bearing pyroxene (phase HAPY) and Mg-sursassite (Sur) were observed just above the temperature stability region of chlorite (Chl); clinohumite (cHm) was observed coexisting with phase HAPY at 6 GPa and 800 °C and coexisting with the 23-Å phase at 7 GPa and 800 °C, which may suggest the transportation of water through Chl → (HAPY → cHm) → 23-Å phase along a relatively warm slab. The 23-Å phase has a wider stability region in the pure MASH system (up to 12 GPa and 1100 °C) than it does in the MFASH system (7–10 GPa, up to 1000 °C). The stability of the 23-Å phase beyond the chlorite breakdown pressure indicates that it may play an important role in transporting water into the deep Earth and even into the mantle transition zone.     

Contact Metamorphism of Serpentinite, Chloritic Blackwall and Rodingite at Paddy-Go-Easy Pass, Central Cascades, Washington

The 2 km wide contact aureole produced from serpentinite bythe intrusion of the Mount Stuart Batholith into the IngallsComplex at Paddy-Go-Easy Pass contains the following ultramaficassemblages, in order of increasing grade: serpentine-forsterite-diopside,serpentine-forsterite-tremolite, forsterite-talc, forsterite-anthophyllite,forsterite-enstatite-anthophyllite, forsterite-enstatite-chlorite,forsterite-enstatite-spinel. Associated metarodingites displayfive metamorphic zones, the diagnostic assemblages of whichare, in increasing grade: grossular-idocrase-chlorite, grossular-diopside-chlorite,epidote-diopside-chlorite, epidotediopside-spinel, plagioclase-grossular-diopside.Mafic hornfels in the aureole contains no orthopyroxene, indicatingthat the conditions of pyroxene hornfels facies were not reached. The breakdown of chlorite is best displayed in aluminous blackwallreaction zones around mafic inclusions in the peridotite. Attemperatures above those of the anthophyllite-out isograd, butwithin the field of forsterite+tremolite, these chlorite-richrocks react to form the assemblage: forsterite-enstatite-spinel.Calculations show that cordierite did not form as a result ofchlorite breakdown in the natural system because impurities,such as iron and chromium, displaced the equilibrium: forsterite+cordierite= enstatite+spinel to much lower pressures than the three kilobarsfound in the pure system. The primary chromite of the peridotite has been altered to chrome-magnetitein the serpentinite. This alteration seems to be isochemicalover the whole rock, as true chromite, formed by metamorphism,occurs at grades above that of the forsterite-enstatite-anthophylliteassemblage. Calcic amphibole in high-grade metaperidotite is tremolite,even in the presence of aluminous chromite, whereas that inmetamorphosed blackwall rock grades from tremolite into hornblende.The pattern of substitution appears to be: Mg₂Si₃rlhar2;(Na,K)(Al^VI)₂(Al^IV)₃.     

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 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 involving humite minerals in impure dolomitic limestones

The natural occurrence of critical assemblages among the phases clinohumite, calcite, dolomite, tremolite, forsterite, diopside, chlorite, and spinel in metamorphosed impure limestones, together with experimental and thermodynamic data, permits the calculation of phase equilibria governing the stability of clinohumite in terms of the variables P, T, and composition of a CO₂-H₂O-HF fluid. Equilibrium constant expressions are given for 23 equilibria that describe the stable phase relations between the above phases. Pure OH-clinohumite is considered to be metastable at relatively low pressures. The occurrence of clinohumite in natural marbles is the result of nonideal fluorine substitution which increases the stability of clinohumite. The stability field for clinohumite +calcite, governed primarily by the equilibrium 4forsterite+dolomite+H₂O = clinohumite+calcite +CO₂, expands to more CO₂-rich fluid compositions with increasing fluorine contents and decreasing total pressure. The F/(F+OH) ratio of clinohumite coexisting with calcite, dolomite, and forsterite is a sensitive indicator of the composition of the mixedvolatile fluid phase. The thermodynamic model is in good agreement with observed phase relations and can be used to gain useful information concerning the P-T-X _fluid conditions responsible for the formation of clinohumite.     

Solubility and partitioning of water in synthetic forsterite and enstatite in the system MgO–SiO2–H2O±Al2O3

The solubility of water in coexisting enstatite and forsterite was investigated by simultaneously synthesizing the two phases in a series of high pressure and temperature piston cylinder experiments. Experiments were performed at 1.0 and 2.0 GPa at temperatures between 1,100 and 1,420°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on orientated single crystals of each phase. Phase water contents were estimated using the calibration of Libowitzky and Rossman (Am Mineral 82:1111–1115, 1997). Enstatite crystals, synthesized in equilibrium with forsterite and an aqueous phase at 1,350°C and 2.0 GPa, contain 114 ppm H₂O. This is reduced to 59 ppm at 1,100°C, under otherwise identical conditions, suggesting a strong temperature dependence. At 1,350°C and 1.0 GPa water solubility in enstatite is 89 ppm, significantly lower than that at 2.0 GPa. In contrast water solubility in forsterite is essentially constant, being in the range 36–41 ppm for all conditions studied. These data give partition coefficients in the range 2.28–3.31 for all experiments at 1,350°C and 1.34 for one experiment at 1,100°C. The incorporation of Al₂O₃ in enstatite modifies the OH stretching spectrum in a systematic way, and slightly increases the water solubility.     

Contact Metamorphism of Serpentinite, Chloritic Blackwall and Rodingite at Paddy-Go-Easy Pass, Central Cascades, Washington

The 2 km wide contact aureole produced from serpentinite bythe intrusion of the Mount Stuart Batholith into the IngallsComplex at Paddy-Go-Easy Pass contains the following ultramaficassemblages, in order of increasing grade: serpentine-forsterite-diopside,serpentine-forsterite-tremolite, forsterite-talc, forsterite-anthophyllite,forsterite-enstatite-anthophyllite, forsterite-enstatite-chlorite,forsterite-enstatite-spinel. Associated metarodingites displayfive metamorphic zones, the diagnostic assemblages of whichare, in increasing grade: grossular-idocrase-chlorite, grossular-diopside-chlorite,epidote-diopside-chlorite, epidote-diopside-spinel, plagioclase-grossular-diopside.Mafic hornfels in the aureole contains no orthopyroxene, indicatingthat the conditions of pyroxene hornfels facies were not reached. The breakdown of chlorite is best displayed in aluminous blackwallreaction zones around mafic inclusions in the peridotite. Attemperatures above those of the anthophyllite-out isograd, butwithin the field of forsterite+tremolite, these chlorite-richrocks react to form the assemblage: forsterite-enstatite-spinel.Calculations show that cordierite did not form as a result ofchlorite breakdown in the natural system because impurities,such as iron and chromium, displaced the equilibrium: forsterite+cordierite=enstatite+spinelto much lower pressures than the three kilobars found in thepure system. The primary chromite of the peridotite has been altered to chrome-magnetitein the serpentinite. This alteration seems to be isochemicalover the whole rock, as true chromite, formed by metamorphism,occurs at grades above that of the forsterite-enstatite-anthophylliteassemblage. Calcic amphibole in high-grade metaperidotite is tremolite,even in the presence of aluminous chromite, whereas that inmetamorphosed blackwall rock grades from tremolite into hornblende.The pattern of substitution appears to be: Mg₂Si₃(Na,K)(Al^VI)₂(Al^IV)₃.     

The role of fluids in the metamorphism of komatiites,Agnew nickel deposit,western Australia

The Agnew nickel sulfide deposit is spatially associated with a lenticular body of ultramafic rocks which shows a concentric zonation in metamorphic mineralogy. Olivine + tremolite + chlorite + cummingtonite ±enstatite assemblages occur at the margin of the ultramafic lens, giving way to olivine + anthophyllite, olivine + talc and olivine + antigorite assemblages successively inwards. These rocks are interpreted as having crystallized from komatiitic lavas, and exhibit a spectrum of compositions from those of original flow tops to pure olivine adcumulates. The relative modal abundances of metamorphic olivine, tremolite and chlorite reflect original proportions of cumulus olivine and komatiite liquid in the protolith. Peak metamorphic conditions are estimated at 550° C, based on garnet-biotite thermometry, at a maximum pressure of 3 kb. This temperature falls within the narrow range over which metamorphic olivine may co-exist with enstatite, anthophyllite, talc or antigorite depending upon the fugacity of water in the metamorphic fluid. The observed mineralogical zonation is therefore attributed to infiltration by CO₂-rich fluids, generated by decarbonation of talc-carbonate rocks formed during pre-metamorphic marginal alteration of the ultramafic lens. Metamorphic fluids were essentially binary mixtures of water and CO₂, with minor H₂S having a maximum partial pressure less than 1 percent of total pressure. Enstatite-bearing assemblages formed in the presence of CO₂-rich fluids at fluid: rock volume ratios close to one, while anthophyllite, talc and antigorite bearing assemblages formed in the presence of progressively more water-rich fluids at progressively lower fluid-rock ratios.