The upper stability limit of the assemblage paragonite + quartz and its natural occurrences

The assemblage paragonite + quartz is encountered frequently in low- to medium-grade metamorphic rocks. With rising grade of metamorphism they react mutually to yield the condensed assemblage albite + Al₂SiO₅.The univariant curve pertaining to the equilibrium paragonite + quartz=albite + andalusite + H₂O has been located experimentally. The reversed P _{H 2 O}-T data are: 1 kb: 470–490° C 2 kb: 510–530° C 3 kb: 540–560° C 4 kb: 560–580° C 5 kb: 590–600° C The univariant curve pertaining to the equilibrium paragonite + quartz=albite + kyanite + H₂O runs through the following P _{H 2 O}-T-intervals: 5 kb: 570–625° C 6 kb: 600–630° C 7 kb: 620–640° C Thermodynamic calculations of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of the phase paragonite from the experimental data presented above and those obtained from the equilibria of the reaction paragonite=albite + corundum + H₂O (Chatterjee, 1970), agree within the limits of uncertainty. This prompts the idea that Zen's (1969) suggestion of a possible error of approximately 7 kcal in G _f,298 ⁰ of the Al₂SiO₅ polymorphs may in fact be due to an error of similar magnitude in G _f,298 ⁰ of corundum.A best estimate of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of paragonite based on these considerations yield: S ₂₉₈ ⁰ : 67.61±3.9 cal deg^–1 gfw^–1 H _f,298 ⁰ : –1411.4±2.7 kcal gfw^–1 G _f,298 ⁰ : –1320.9±4.0 kcal gfw^–1 These numbers will be subject to change when better thermochemical data on corundum and albite are available.In medium-grade metamorphic rocks the assemblage paragonite + quartz is commonly found in stable coexistence with such other phases as muscovite, staurolite, andalusite, kyanite, but not with cordierite or sillimanite. However, the assemblage paragonite-sillimanite has been reported to be stable in the absence of quartz. All these petrologic observations can be explained on the basis of the stability data of the phases and phase assemblages concerned.     

Mean and turbulent velocity measurements of supersonic mixing layers

The behavior of supersonic mixing layers under three conditions has been examined by schlieren photography and laser Doppler velocimetry. In the schlieren photographs, some largescale, repetitive patterns were observed within the mixing layer; however, these structures do not appear to dominate the mixing layer character under the present flow conditions. It was found that higher levels of secondary freestream turbulence did not increase the peak turbulence intensity observed within the mixing layer, but slightly increased the growth rate. Higher levels of freestream turbulence also reduced the axial distance required for development of the mean velocity. At higher convective Mach numbers, the mixing layer growth rate was found to be smaller than that of an incompressible mixing layer at the same velocity and freestream density ratio. The increase in convective Mach number also caused a decrease in the turbulence intensity ( _u /U).List of Symbols a speed of sound - b total mixing layer thickness betweenU ₁ – 0.1U andU ₂ + 0.1U - f normalized third moment ofu-velocity,f u ³/(U)³ - g normalized triple product ofu ² v,g u ² v/(U)³ - h normalized triple product ofu v ², h uv' ²/(U)³ - l _u axial distance for similarity in the mean velocity - l _u axial distance for similarity in the turbulence intensity - M Mach number - M _c convective Mach number (for ₁=₂),M _c (U ₁–U ₂)/(a ₁+a ₂) - P static pressure - r freestream velocity ratio,rU ₂/U ₁ - Re unit Reynolds number,Re U/ - s freestream density ratio,s ₂/ ₁ - T _t total temperature - u instantaneous streamwise velocity - u deviation ofu-velocity,u u–U - U local mean streamwise velocity - U ₁ primary freestream velocity - U ₂ secondary freestream velocity - U average of freestream velocities, ¯U (U ₁ +U ₂)/2 - U freestream velocity difference,U U ₁ –U ₂ - v instantaneous transverse velocity - v deviation ofv-velocity,v v – V - V local mean transverse velocity - x streamwise coordinate - y transverse coordinate - y ₀ transverse location of the mixing layer centerline - ensemble average - ratio of specific heats - boundary layer thickness (y-location at 99.5% of free-stream velocity) - similarity coordinate, (y –y ₀)/b - compressible boundary layer momentum thickness - viscosity - density - standard deviation - dimensionless velocity, (U –U ₂)/U - 1 primary stream - 2 secondary stream A version of this paper was presented at the 11th Symposium on Turbulence, October 17–19, 1988, University of Missouri-Rolla     

Petrology of ultramafic nodules from West Kettle River,near Kelowna,Southern British Columbia

A basanitoid flow of Miocene age, exposed near the West Kettle River, 25 km southeast of Kelowna, British Columbia, contains abundant ultramafic and mafic nodules. The subangular nodules are 1–20 cm across and typically show granular textures. A study of 250 nodules indicates that spinel lherzolite (60%) is the dominant type with subordinate olivine websterite (10%), websterite (7%), clinopyroxenite (4%), wehrlite (4%), pyroxene gabbro (4%), dunite (2%), harzburgite (1%) and granitic rocks (8%). Ultramafic nodules are of two types. Most of the wehrlites and clinopyroxenites belong to the black pyroxene (aluminous clinopyroxene) series, whereas the other clinopyroxene-bearing nodules belong to the green pyroxene (chromian diopside) series. Some spinel lherzolite nodules have distinctive pyroxene- and olivine-rich bands. Microprobe analyses of the constituent minerals of more than thirty nodules from the green pyroxene series indicate that grain to grain variations within individual nodules are small even when banding is present. Olivine, orthopyroxene, clinopyroxene and spinel in spinel lherzolite have average compositions of Fo₉₀, En₉₀, Wo₄₇Fs₅En₄₈, Cr/(Cr+ Al+Fe³)=0.1 and Mg/(Mg+Fe²⁺)=0.8. Equilibration temperatures, which were calculated using the two pyroxene geothermometer of Wells (1977), range between 920–980° C. Based on published phase stability experiments, pressures of equilibration are between 10–18 kbar. In summary, the upper mantle beneath southern British Columbia is dominated by spinel lherzolite but contains some banding on a scale of cm to meters. The temperature in the upper mantle is 950° C at a depth of 30–60 km.On leave from the Geological Institute, University of Tokyo, Japan     

Gibbs energy of aluminous minerals

The discrepancy between the tabulated Gibbs Energies of Formation for Al₂SiO₅ and corundum relative to muscovite and kaolinite is considered to lie principally with the latter two minerals. New values for heat of formation of gibbsite [Gbs] will affect the tabulated H _f ⁰ , G _f(298,1) ⁰ for the other aluminous minerals which are referred to gibbsite as calorimetric aluminum reference. Gibbs Energy Difference Functions, calculated from phase equilibria in the system CaO-Al₂O₃-SiO₂-(H₂O-CO₂), can be used to estimate consistent H _f ⁰ , G _f(298,1) ⁰ values for aluminous minerals. A self consistent data set is presented referred to G _f(298,1) ⁰ [Corundum]=–378.08 kcal mol^–1. Two independent values for G _f(298,1) ⁰ [Anorthite]=–961.52 and –960.29 kcal, from a recalculation of the H _f ⁰ [Anor] based upon the revised H _f(298,1) ⁰ [Gbs]=–309.325 kcal mol^–1 and from measurement of silica activity on the anorthite-saturated part of the CaO-Al₂O₃-SiO₂ liquidus, respectively, are considered to show the magnitude of the discrepancy and are used in the calculations.     

1Tc-Strontiohilgardit (Ca,Sr)2[B5O8(OH)2Cl] und seine Stellung in der Hilgarditgruppe X2/II[B5O8(OH)2Cl]

Zusammenfassung 1Tc-Strontiohilgardit (Ca, Sr)₂ [B₅O₈(OH)₂,Cl] mit Ca : Sr etwa 1 : 1 ist ein neues Mineral der Hilgarditgruppe. Fundpunkt: Reyersbausen (9° 59,7 E, 51° 36,6 N), Grube Königshall-Hindenburg, Flöz Staßfurt in sylvinitischer Ausbildung.Konstanten : triklin-pedial,a ₀=6,38 Å,b ₀=6,480 Å,c ₀=6,608 Å, =75,4°,=61,2°, =60,5°; tafelige-gestreckte Links- und Re chtskristalle, farblos, wasserunlöslich, piezoelektrisch. Härte 5–7, Dichte 2,99 g cm^–3;n =1,638,n =1,639,n =1,670; 2V =19°.Neue Daten für die Hilgarditgruppe : 2 M (Cc)-Calciumhilgardit (=Hilgardit) =4 Ca₂[B₅O₃(OH)₂Cl], Raumgruppe Cc.3Tc-Calciumhilgardit (=Parahilgardit) = 3 Ca₂[B₅O₃(OH)₂Cl]; trinklin-pedial, ₀=6,31 Å,b =6,484 Å,c ₀=17,50 Å; =84,0°,=79,6°, =60,9°.Die Polymorphiebeziehungen sind geometrisch deutbar durch eine spezielle Art der Polytropie (Stapelung von Links- und Rechtskristallen im Elementarbereich).     

Equation of state,structural behaviour and phase diagram of synthetic MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, as a function of pressure and temperature

The behaviour of synthetic Mg-ferrite (MgFe₂O₄) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K₀=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa^–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by _a0+_a1*(T–298)+_a2/(T–298)², where _a0=9.1(1) 10^–6 K^–1, _a1=4.9(2) 10^–9 K^–2 and _a2= 5.1(5) 10^–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol^–1 and =–17.6(± 1.2) kJ mol^–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe₂O₄, which shows that the high-pressure transition from spinel to orthorombic CaMn₂O₄-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe₂O₃.     

Relationships among Gibbs free energies and enthalpies of formation of phosphates,oxides and aqueous ions

Two parameters _GO^2– and _HO^2– are defined as the differences between respectively the Gibbs free energies and the enthalpies of formation of an oxide and its corresponding aqueous cation. The Gibbs free energies and enthalpies of formation of phosphates from their consituent oxides are shown to be linear functions of respectively _GO^2– and _HO^2– of their constituent cations.     

Textural and isotopic variations in graphite from plutonic rocks,South-Central New Hampshire

Graphite occurs in two distinct textural varieties in syntectonic granitoids of the New Hampshire Plutonic Series and in associated metasedimentary wall rocks. Textural characteristics indicate that coarse graphite flakes were present at an early stage of crystallization of the igneous rocks and thus may represent xenocrystic material assimilated from the wall rocks. The range of ¹³C values determined for flake graphite in the igneous rocks (–26.5 to –13.8) overlaps the range for flake graphite in the wall rocks (–26.0 to –16.7), and spatial correlation of some ¹³C values in the plutons and wall rocks supports the assimilation mechanism. The textures of fine-grained irregular aggregates or spherulites of graphite, on the other hand, indicate that they formed along with secondary hydrous silicates and carbonates during retrograde reactions between the primary silicates and a carbon-bearing aqueous fluid phase. Relative to coexisting flake graphite, spherulitic graphite shows isotopic shifts ranging from 1.9 higher to 1.4 lower in both igneous and metasedimentary samples.The observed isotopic shifts and the association of spherulitic graphite with hydrous silicates are explained by dehydration of C-O-H fluids initially on or near the graphite saturation boundary. Hydration of silicates causes dehydration of the fluid and drives the fluid composition to the graphite saturation surface. Continued dehydration of the fluid then requires coprecipitation of secondary graphite and hydrous silicates and drives the fluid toward either higher or lower CO₂/CH₄ depending upon the inital bulk composition. Isotopic shifts in graphite formed at successive reaction stages are explained by fractionation of ¹³C between secondary graphite and the evolving fluid because ¹³C is preferentially concentrated into CO₂ relative to CH₄.Epigenetic graphite in two vein deposits assiciated with the contacts of these igneous rocks is generally enriched in ¹³C (–15.7 to –11.6) relative to both the igneous and wall-rock ¹³C values. Values of ¹³C vary by up to 3.4 within veins, with samples taken only 3 cm apart differing by 2.0 These variations in ¹³C correlate with textural evidence showing sequential deposition of different generations of graphite in the veins from fluids which differed in proportions of carbon species or isotopic composition (or both).     

Late Hercynian U-vein mineralization in the Alps: fluid inclusion and C,O, H isotopic evidence for mixing between two externally derived fluids

Late Hercynian U-bearing carbonate veins within the metamorphic complex of La Lauzière are characterized by two parageneses. The first is dominated by dolomite or ankerite and the second by calcite and pitchblende. Fluids trapped in the dolomites and ankerites at 350–400° C are saline waters (20 to 15 wt % eq. NaCl) with D –34 to –49. In the calcite they are less saline (17 to 8 wt % eq. NaCl) and trapped at 300–350° C with D –50 to –65. All fluids contain trace N₂, CO₂ and probably CH₄. The carbonates have ¹³C –8 to –14. and derived their carbon from organic matter. Evolution of the physico-chemical conditions from dolomite (ankerite) to calcite deposition was progressive.H and O-isotope studies indicate the involvement of two externally derived fluids during vein development. A D-rich ( –35) low fO₂, saline fluid is interpreted to have come from underlying sediments and entered the hotter overlying metamorphic slab and mixed with more oxidizing and less saline U bearing meteoric waters during regional uplift. This evidence for a sedimentary formation water source for the deep fluid implies that the metamorphic complex overthrusted sedimentary formations during the Late-Hercynian.     

An experimental study of the diffusion of oxygen in quartz and albite using an overgrowth technique

Diffusion rates of¹⁸O tracer in quartz ( c, 1 Kb H₂O) and Amelia albite ( 001, 2 Kb H₂O) have been measured, using Secondary Ion Mass Spectrometry (SIMS). A new technique involving hydrothermal deposition of labelled materials has removed the possibility of pressure solution-reprecipitation processes adversely affecting the experiments. Reported diffusion constants are:-quartz ( c), ,Q=98±7 KJ mol^–1 (600–825° C, 1 Kb); Amelia albite ( 001), ,Q=85±7 KJ mol^–1, (400–600° C, 2 Kb). Measured quartz¹⁸O diffusivities decrease discontinuously at the- transition, reflecting strong structural influences. The reported albite data agree with previously recorded studies, but-quartz data indicate significantly lower activation energies. Possible causes of this discrepancy, and some geological consequences, are noted.     

Latest precambrian (Cadomian) zircon ages,Nd isotopic systematics and P-T evolution of granitoid orthogneisses of the Erzgebirge,Saxony and Czech Republic

Single zircons from two orthogneiss complexes, the Grey Gneiss and Red Gneiss, the lowermost tectonic units in the Erzgebirge, were dated. The grey Freiberg Gneiss is of igneous origin and has a ²⁰⁷Pb/²⁰⁶Pb emplacement age of 550±7 Ma. A quartz monzonite from Lauenstein contains idiomorphic zircons with a mean ²⁰⁷Pb/²⁰⁶Pb age of 555±7 Ma as well as xenocrysts ranging in age between 850 and 1910 Ma. Red gneisses from the central Erzgebirge contain complex zircon populations, including numerous xenocrysts up to 2464 Ma in age. The youngest, idiomorphic, zircons in all samples yielded uniform ²⁰⁷Pb/²⁰⁶Pb ages between 550±9 and 554±10 Ma. Nd isotopic data support the interpretation of crustal anatexis for the origin of both units. _Nd(t) values for the grey gneisses are –7.5 and –6.0 respectively, (mean crustal residence ages of 1.7–1.8 Ga). The red gneisses have a wider range in _Nd(t) values from –7.7 to –2.8 (T _DM ages of 1.4–1.8 Ga). The zircon ages document a distinct late Proterozoic phase of granitoid magmatism, similar in age to granitoids in the Lusatian block farther north-east. However, Palaeozoic deformation as well as medium pressure metamorphism ( 8 kbar/600–650° C) are identical in both gneiss units and distinguish these rocks from the Lusatian granitoids. The grey and red gneisses were overthrust by units with abundant high-pressure relicts and a contrasting P-T evolution. Zircon xenocryst and Nd model ages in the range 1000–1700 Ma are similar to those in granitoid rocks of Lusatia and the West-Sudetes, and document a pre-Cadomian basement in parts of east-central Europe that, chronologically, has similarities with the Sveconorwegian domain in the Baltic Shield.     

Oxygen isotope geochemistry of hydrothermally-altered synmetamorphic granitic rocks from South-Central Maine,USA

Hydrothermally-altered mesozonal synmetamorphic granitic rocks from Maine have whole-rock ¹⁸O (SMOW) values 10.7 to 13.8. Constituent quartz, feldspar, and muscovite have ¹⁸O in the range 12.4 to 15.2, 10.0 to 13.2, and 11.1 to 12.0, respectively. Mean values of _Q–F ( ¹⁸O_quartz– ¹⁸O_feldspar)=2.4 and _Q–M ( ¹⁸O_quartz– ¹⁸O_muscovite)=3.3 are remarkably uniform (standard deviations of both are 0.2). Measured _Q–F and _Q–M values demonstrate that the isotopic compositions of the minerals are altered from primary magmatic ¹⁸O values but that the minerals closely approached oxygen isotope exchange equilibrium at subsolidus temperatures. Analyzed muscovites have D (SMOW) values in the range –65 to –82.Feldspars in the granitic rocks are mineralogically altered to either (a) muscovite+calcite, (b) muscovite+calcite+epidote, (c) muscovite+epidote, or (d) muscovite only. A consistent relation exists between the assemblage of secondary minerals and the oxygen isotope composition of whole rocks, quartz, and feldspar. Rocks with assemblage (a) have whole-rock ¹⁸O>12.1 and contain quartz and feldspar with ¹⁸O>13.8 and >11.4, respectively. Rocks with assemblages (b), (c), and (d) have whole-rock ¹⁸O<11.4 and contain quartz and feldspar with ¹⁸O< 13.1 and <11.0, respectively. The correlation suggests that the mineralogical alteration of the rocks was closely coupled to their isotopic alteration.Three mineral thermometers in altered granite suggest that the hydrothermal event occurred in the temperature range 400°–150° C, 100°–150° C below the peak metamorphic temperature inferred for country rocks immediately adjacent to the plutons. Calculations of mineral-fluid equilibria indicate that samples with assemblage (a) coexisted during the event with CO₂-H₂O fluids of and ¹⁸O=10.8 to 12.2 while samples with assemblages (b), (c), or (d) coexisted with fluids of and ¹⁸O=9.4 to 10.1. Compositional variations of the hydrothermal fluids were highly correlated: fluids enriched in CO₂ were also enriched in ¹⁸O. Because CO₂ was added to the granites during hydrothermal alteration and because fluids enriched in CO₂ were enriched in ¹⁸O, some or all of the variation in ¹⁸O of altered granites may have been caused by addition of ¹⁸O to the rocks during the hydrothermal event. The source of both the CO₂ and ¹⁸O could have been high-¹⁸O metasedimentary country rocks. The inferred change in isotopic composition of the granites is consistent with depletion of the metacarbonate rocks in ¹⁸O close to the plutons and with large volumes of fluid that were inferred from petrologic data to have infiltrated the metacarbonate rocks during metamorphism.A close approach of minerals to oxygen isotope exchange equilibrium in altered mesozonal rocks from Maine is in marked contrast to hydrothermally-altered epizonal granites whose mineral commonly show large departures from oxygen isotope exchange equilibrium. The difference in oxygen isotope systematics between altered epizonal granites and altered mesozonal granites closely parallels a differences between their mineralogical systematics. Both differences demonstrate the important control that depth exerts on the products of hydrothermal alteration. Deeper hydrothermal events occur at higher temperature and are longer-lived. Minerals and fluid have sufficient time to closely approach both isotope exchange and heterogeneous chemical equilibrium. Shallower hydrothermal events occur at lower temperatures and are shorter-lived. Generally there is insufficient time for fluid to closely approach equilibrium with all minerals.     

Meteoric hydrothermal origin of calcites in “Green Tuff” formations,Miocene age,Japan

Oxygen and carbon isotope compositions were determined for calcites from the Green Tuff formations of Miocene age in Japan. Values of ¹⁸O from 24 calcites in altered rocks from 5 districts range from –2 to +16_SMOW, in most cases from 0 to +8_SMOW. The low ¹⁸O values rule out the possibility of their low-temperature origin or any significant contribution of magmatic fluid in the calcite precipitation. These values, coupled with their mineral assemblages, suggest that the calcites formed from meteoric hydrothermal solutions which caused propylitic alteration after the submarine strata became emergent.Values of ¹³C from the calcites show a wide variation from –17 to 0_PDB. Calcites from different districts have different ranges of ¹³C values, indicating that there was no homogeneous reservoir of carbon at the time the calcite formed, and that the carbon had local sources. Carbon isotopic compositions of calcite within ore deposits in the Green Tuff formations range from –19 to 0_PDB, similar to those of calcite in the altered rocks in the same district, suggesting that the carbon in ore calcites was likely supplied from the surrounding rocks through activity of meteoric hydrothermal solutions.     

Stable isotope geochemistry of the Archean Val-d‘Or (Canada) orogenic gold vein field

A systematic study of the auriferous quartz veins of the Val-dOr vein field, Abitibi, Quebec, Canada, demonstrates that the C, O, S isotope composition of silicate, carbonate, borate, oxide, tungstate and sulphide minerals have a range in composition comparable to that previously determined for the whole Superior Province. The oxygen isotope composition of quartz from early quartz–carbonate auriferous veins ranges from 9.4 to 14.4 whereas later quartz-tourmaline-carbonate veins have ¹⁸O_quartz values ranging from 9.2 to 13.8 . Quartz-carbonate veins have carbonate (¹⁸O: 6.9–12.5 ; ¹³C: –6.2– –1.9 ) and pyrite (³⁴S: 1.2 and 1.9 ) isotope compositions comparable to those of quartz-tourmaline-carbonate veins (¹⁸O: 7.9–11.7 ; ¹³C: –8.0 – –2.4 ; ³⁴S: 0.6–6.0 ). ¹⁸O_quartz values in quartz-tourmaline-carbonate veins have a variance comparable to analytical uncertainty at the scale of one locality, irrespective of the type of structure, the texture of the quartz or its position along strike, across strike or down-dip a vein. In contrast, the oxygen isotope composition of quartz in quartz-tourmaline-carbonate veins displays a regional distribution with higher ¹⁸O values in the south-central part of the vein field near the Cadillac Tectonic Zone, and which ¹⁸O values decrease regularly towards the north. Another zone of high ¹⁸O values in the northeast corner of the region and along the trace of the Senneville Fault is separated by a valley of lower ¹⁸O values from the higher values near the Cadillac Tectonic Zone. Oxygen isotope isopleths cut across lithological contacts and tectonic structures. This regional pattern in quartz-tourmaline-carbonate veins is interpreted to be a product of reaction with country rocks and mixing between (1) a deep-seated hydrothermal fluid of metamorphic origin with minimum ¹⁸O=8.5 , ¹³C=0.6 and ³⁴S=–0.4 , and (2) a supracrustal fluid, most likely Archean seawater with a long history of water-rock exchange and with maximum ¹⁸O=3.9 , ¹³ C=–5.6 and ³⁴S=5.0 .     

Contrasting serpentinization processes in the eastern Central Alps

Stable isotope compositions have been determined for serpentinites from between Davos (Arosa-Platta nappe, Switzerland) and the Valmalenco (Italy). D and ¹⁸O values (–120 to –60 and 6–10, respectively) in the Arosa-Platta nappe indicate that serpentinization took place on the continent at relatively low temperatures in the presence of limited amounts of metamorphic fluids that contained a component of meteoric water. One sample of chrysotile has a ¹⁸O value of 13 providing evidence of high W/R ratios and low formation temperature of lizardite-chrysotile in this area. In contrast, relatively high D values (–42 to –34) and low ¹⁸O values (4.4–7.4) for serpentine in the eastern part of the Valmalenco suggest a serpentinization process that took place at moderate temperatures in fluids that were dominated by ocean water. The antigorite in the Valmalenco is the first reported example of continental antigorite with an ocean water signature. An amphibole sample from a metasomatically overprinted contact zone to metasediments (D=-36) indicates that the metasomatic event also took place in the presence of ocean water. Lower D values (–93 to –60) of serpentines in the western part of the Valmalenco suggest a different alteration history possibly influenced by fluids associated with contact metamorphism. Low water/rock ratios during regional metamorphism (and metasomatism) have to be assumed for both regions.     

Der Strukturtyp von Emmonsit, {Fe2[TeO3]3·H2O}·xH2O (x=0−1)

Zusammenfassung Emmonsit kristallisiert triklin, RaumgruppeP , Gitterkonstanten:a ₀=7,90 Å,b ₀=8,00 Å,c ₀=7,62 Å, =96^o44, =95^o 0, =84^o 28,Z=2. Der Strukturtyp wurde aus 3-dimensionalen photographischen Röntgendaten ermittelt. Die Eisenatome werden je von 6 Sauerstoffen verzerrt oktaedrisch koordiniert. Jedes Telluratom wird von 3 Sauerstoffen in einem Abstand <2,0 Å umgeben. Ein vierter Sauerstoff hat bezüglich dieser drei einen um etwa 25–35% größeren Abstand, so daß jedes Telluratom im weiteren Sinne eine (3+1)-Koordination aufweist.

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The structure type of emmonsite, {Fe₂[TeO₃]₃·H₂O}·xxH₂O (x=0–1)

Summary Emmonsite is triclinic with space groupP , and lattice constantsa ₀=7.90 Å,b ₀=8.00 Å,c ₀=7.62 Å, =96^o 44, =95^o 0, =84⁰ 28,Z=2. The structure type is derived from 3-dimensional photographic X-ray data. The iron atoms are coordinated by six oxygens in the form of a distorted octahedron. Each tellurium atom is coordinated to 3 oxygens at a distance <2.0 Å. Compared with these 3 Te–O distance the distance of a fourth oxygen is only 25 to 35% greater; therefore each tellurium atom has a (3+1)-coordination of oxygens.

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Mit 2 Abbildungen     

Fluid-rock interaction between syenites and marbles at Stephen Cross Quarry,Québec,Canada: petrological and stable isotope data

Grenville dolomitic marbles and calc-silicates at Stephen Cross Quarry, Québec, underwent contact metamorphism and metasomatism associated with the intrusion of the Wakefield syenite at ambient pressures of 0.4GPa at 1090–1070Ma. Fluid infiltration produced exoskarns, calcite+periclase+forsterite±diopside±orthoclase assemblages in the marbles, and quartz±calcite±wollastonite±diopside±anorthite assemblages in the calc-silicates. Phase-equilibria in the CaO–MgO–Al₂O₃–SiO₂–H₂O–CO₂ system suggest that fluid infiltration occurred close to the thermal peak of contact metamorphism (715–815°C) and that the fluids hadXCO₂0.15. In the metasediments, ¹⁸O values of calcite (Cc) are as low as 8.6, suggesting that the fluids were in isotopic equilibrium with the syenites (¹⁸O =8.8–10.2). Marble ¹³C(Cc) values are-0.1 to-3.2; the lack of correlation between ¹³C(Cc) and ¹⁸O(Cc) is consistent with the infiltration of water-rich fluids. The resetting of stable isotopes and the mineralogical changes can be explained by time-integrated fluid fluxes of up to 110 m³/m² (4×10⁶ mol/m²), corresponding to actual fluxes of 3×10^-11 to 3×10^-12 m³/m²-s and intrinsic permeabilities of 10^-18 to 10^-20 m² for fluid flow lasting 0.1-1Ma. Marble ¹⁸O(Cc) values do not correlate well with distance from the syenite, and fluids were probably channelled across lithological layering. The correlation between the degree of resetting of marble ¹⁸O(Cc) values with the abundance of submillimetre-wide veins, suggests that fluid focussing may have resulted from variations in fracture density. Late, lower temperature (<500°C), fluid flow formed serpentine (Serp) and brucite (Br) from periclase and forsterite. ¹⁸O(Br) and ¹⁸O(Scrp) values correlate with ¹⁸O(Cc), suggesting that retrogression involved only limited volumes of fluid. The observation that ¹⁸O(Cc-Br) and ¹⁸O(Cc-Serp) values are higher in marbles that have lower ¹⁸O(Cc) values is interpreted as indicating that fluid flow persisted to lower temperatures in those rocks due to higher intrinsic permeabilities. Calcite in the syenite was also formed by the influx of fluids during cooling. Syenite ¹⁸O(Cc) values are approximately in isotopic equilibrium with the high-temperature silicate minerals, suggesting that again only minor volumes of fluid were involved. In detail fluid flow was prolonged and complex, creating problems for the application of quantitative fluid flow models.This paper is a contribution to IGCP 304, Lower Crustal Processes     

Basaltic glass with high-temperature equilibrated immiscible sulphide bodies with native iron from disko,central West Greenland

Immiscible sulphide bodies show eutectic quench textures in a basaltic glass rock (mg=66) from a native iron-bearing dyke chilled at T=1,200° C and P=250 bars. The sulphide bodies are composed of troilite (90–91%), iron (9–10%) and very scarce vanadium-rich chromite and approach a ternary cotectic in the Ni-poor part of the system Fe-Ni-S. Transition element partition between olivine (mg=83), silicate glass (mg=59) and sulphide blebs indicate that the phases were equilibrated at 1,200° C. D _{vanadium(olivine/glass)} is close to unity and reflect the reducing nature of the rock, for which estimates of f _O210^{–12 to –13} and f _S210^–5 have been made. D _{nickel, cobalt, copper (sulphide/glass)}=4,300, 230 and 380 respectively, are much higher than reported experimentally determined D's on_{monosulphide/basalt glass} at the same temperature and show increasing positive deviation (Ni>Co>Cu) with the increasingly siderophile character of the elements. K _{Dnickel-iron (sulphide/olivine)}=63 is much higher than an experimentally reported value (33) and comparison with published thermodynamic data on Ni-partition between olivine and iron metal suggests that the positive deviation is roughly proportional to the excess metal component in the sulphide melt. The occurrence of strongly Ni-depleted reduced basalts on Disko shows that fractionation of metal and sulphides was a common and geologically important process.     

Cell parameters of thermally treated anorthite. Al,Si configurations in the average structures of the high temperature calcic plagioclases

Thermal treatments of anorthite carried out at up to 1,547° C show that the unit cell parameter changes as a function of the treatment temperature. The best fit curve found by non-linear least squares analysis is: =91.419-(0.327·10^-6)T ²+(0.199·10^-12)T ⁴-(0.391·10)T ⁶. The results obtained support significant Al,Si disorder (Al0.10, where Al=t ₁(0)-1/3 [t ₁(m)+t ₂(0)+t ₂(m)], Ribbe 1975), in anorthite equilibrated near the melting point and confirm a high temperature series differentiated from the low temperature series for calcic plagioclases in the An₈₅–An₁₀₀ range also. In the plot vs. An-content the high and low temperature curves intersect at An₈₅ composition and progressively diverge in the An₈₅–An₁₀₀ range. The trends of the high and low temperature curves in this range are interpretable on the basis of the degree of Al, Si order in the average structures of calcic plagioclases.     

The olivine — clinopyroxene geobarometer: experimental results in the CaO-FeO-MgO-SiO2 system

The exchange of Ca and Mg between olivine and clinopyroxene has been studied in the CFMS system. Experiments were conducted in a piston-cylinder apparatus in the temperature range of 1,100–1,300° C and the pressure range 10–30 kbar. Results confirm the previous suggestion (Adams and Bishop 1982) that this reaction has a sufficiently large V° to be used as a geobarometer in several basic and ultrabasic systems. Experimental results were corrected for compositional effects using recent activity-composition models for quadrilateral pyroxenes and olivines. The corrected results indicate that the exchange reaction has aH _{1 bar} of 34,900 J, a S° of -7.25J/deg, and a V° of -0.489 J/bar. Corrected results agree well with calculations based on the thermodynamic properties of the endmembers.Application of the olivine-clinopyroxene geobarometer to many systems will require additional calibration of non CFMS components. Preliminary pressure estimates based on simple assumptions about the activity relations of these components have been made for spinel lherzolites from southwestern United States and coarse and porphyroclastic garnet lherzolites from southern Africa. A geotherm calculated from spinel lherzolites near the Rio Grande rift is consistent with a geophysical geotherm based on near-surface heat-flow measurements of 100 mW/m² or greater. Results on garnet lherzolites yield a southern African geotherm with no inflection which falls at somewhat higher temperatures than pyroxene geotherms calculated for the same area.