Experimental investigation and application of the equilibrium rutile + orthopyroxene = quartz + ilmenite

Equilibria in the Sirf (Silica-Ilmenite-Rutile-Ferrosilite) system: $${\text{SiO}}_{\text{2}} + ({\text{Mg,Fe}}){\text{TiO}}_{\text{3}} {\text{ + (Mg,Fe)SiO}}_{\text{3}} $$ have been calibrated in the range 800–1100° C and 12–26 kbar using a piston-cylinder apparatus to assess the potential of the equilibria for geobarometry in granulite facies assemblages that lack garnet. Thermodynamic calculations indicate that the two end-member equilibria involving quartz + geikielite = rutile + enstatite, and quartz + ilmenite = rutile + ferrosilite, are metastable. We therefore reversed equilibria over the compositional range Fs_40–70, using Ag₈₀Pd₂₀ capsules with \(f_{{\text{O}}_{\text{2}} } \) buffered at or near iron-wüstite. Ilmenite compositions coexisting with orthopyroxene are \(X_{{\text{MgTiO}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.06 to 0.15 and \(X_{{\text{Fe}}_{\text{2}} {\text{O}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.00 to 0.01, corresponding toK _D values of 13.3, 10.2, 9.0 and 8.0 (±0.5) at 800, 900, 1000 and 1100° C, respectively, whereK _D =(XMg/XFe)^Opx/(XMg/XFe)^Ilm. Pressures have been calculated using equilibria in the Sirf system for granulites from the Grenville Province of Ontario and for granulite facies xenoliths from central Mexico. Pressures are consistent with other well-calibrated geobarometers for orthopyroxeneilmenite pairs from two Mexican samples in which oxide textures appear to represent equilibrium. Geologically unreasonable pressures are obtained, however, where oxide textures are complex. Application of data from this study on the equilibrium distribution of iron and magnesium between ilmenite and orthopyroxene suggests that some ilmenite in deep crustal xenoliths is not equilibrated with coexisting pyroxene, while assemblages from exposed granulite terranes have reequilibrated during retrogression. The Sirf equilibria are sensitive to small changes in composition and may be used for determination of activity/composition (a/X) relations of orthopyroxene if an ilmenite model is specified. A symmetric regular solution model has been used for orthopyroxene in conjunction with activity models for ilmenite available from the literature to calculatea/X relations in orthopyroxene of intermediate composition. Data from this study indicate that FeSiO₃?MgSiO₃ orthopyroxene exhibits small, positive deviations from ideality over the range 800–1100°C.     

The concentration and isotopic composition of carbon in basaltic glasses from the Juan de Fuca Ridge, Pacific Ocean

The abundance and 13C/12C ratios of carbon were analyzed in basaltic glass from twenty locations along the Juan de Fuca Ridge using a 3-step combustion/extraction technique. Carbon released during the first two combustion steps at 400-500 degrees C and 600-650 degrees C is interpreted to be secondary, and only the carbon recovered during a final combustion step at approximately 1200 degrees C is thought to be indigenous to the samples. For carbon released at approximately 1200 degrees C, glasses analyzed as 1-2 mm chips contained 23-146 ppm C with delta 13C values of -4.8 to -9.3%, whereas samples crushed to 38-63 microns or 63-90 microns yielded 56-103 ppm C with delta 13C values of -6.1 to -9.2%. The concentrations and isotopic compositions of the primary carbon dissolved in the glasses and present in the vesicles are similar to those previously reported for other ocean-ridge basalts. The Juan de Fuca basaltic magmas were not in equilibrium with respect to carbon when they erupted and quenched on the sea floor. Evidence of disequilibrium includes (1) a large range of carbon contents among glasses collected at similar depths, (2) a highly variable calculated carbon isotopic fractionation between melt and vapor determined by comparing crushed and uncrushed splits of the same sample, and (3) a lack of correlation between vesicle abundance, carbon concentration, and depth of eruption. Variations in carbon concentration and delta 13C ratios along the ridge do not correlate with major element chemistry. The observed relationship between carbon concentrations and delta 13C values may be explained by late-stage, variable degrees of open-system (Rayleigh-like) degassing.     

Pressure Increases, the Formation of Chromite Seams, and the Development of the Ultramafic Series in the Stillwater Complex, Montana

This paper explores the hypothesis that chromite seams in theStillwater Complex formed in response to periodic increasesin total pressure in the chamber. Total pressure increased becauseof the positive V of nucleation of CO₂ bubbles in the melt andtheir subsequent rise through the magma chamber, during whichthe bubbles increased in volume by a factor of 4–6. Byanalogy with the pressure changes in the summit chambers ofKilauea and Krafla volcanoes, the maximum variation was 0•2–0•25kbar, or 5–10% of the total pressure in the Stillwaterchamber. An evaluation of the likelihood of fountaining andmixing of a new, primitive liquid that entered the chamber withthe somewhat more evolved liquid already in the chamber is basedupon calculations using observed and inferred velocities andflow rates of basaltic magmas moving through volcanic fissures.The calculations indicate that hot, dense magma would have oozed,rather than fountained into the chamber, and early mixing ofthe new and residual magmas that could have resulted in chromitecrystallizing alone did not take place. Mixing was an important process in the Stillwater magma chamber,however. After the new magma in the chamber underwent {smalltilde}5% fractional crystallization, its composition, temperature,and density approached those of the overlying liquid in thechamber and the liquids then mixed. If this process occurredmany times over the course of the development of the Ultramaficseries, a thick column of magma with orthopyroxene on its liquiduswould have been the result. Thus, the sequence of multiple injections,fractionation, and mixing with previously fractionated magmacould have been the mechanism that produced the thick bronzitecumulate layer (the Bronzitite zone) above the cyclic units.     

Electron paramagnetic resonance of Sc3+-stabilized CO 3 3− molecule-ion in natural calcite

Electron paramagnetic resonance (EPR) spectra of CO ₃ ^3– molecule-ions stabilized by Sc³⁺ in natural calcite were identified and studied at X-band frequencies and room temperature. The principal values of the g-tensor (g _xx= 1.9997, g _yy = 2.0030, g _zz = 1.9972) and the direction cosines of the g and A tensors for CO ₃ ^3– -Sc³⁺ center were found to be close to that for the well-known CO ₃ ^3– -Y³⁺ center. A quantitative comparison of different impurity contents in calcite samples and analysis of the intensities of forbidden transitions were used to identify Sc³⁺. An estimation of the unpaired electron spin density on the nuclei of paramagnetic centers confirms that both centers, CO ₃ ^3– -Sc³⁺ and CO ₃ ^3– -Y³⁺, have the same nature.     

Automatic equipment to monitor groundwater radon

Prototype instrumentation, able to automatically measure groundwater radon content variations, is presented. The equipment is made of stainless steel and has spherical valves with automatic and pneumatic control. The deemanation of the gases from the water is obtained by evacuating a suitable expansion chamber. The instrumentation can make discrete sampling ranging from 1 per hour to 1 per 99 hours. The equipment was tested in the laboratory: the efficiency was measured by means of a²⁶⁶Ra solution. A mean value of (0.65±0.07) count/s/Bq was obtained. A calibration test was carried out by comparing countings from the automatic equipment with those obtained by the standard laboratory cell. Results of an operational check over a period of approximately one year indicate that variations in radon at the calibration site are attributable more to meteorological than to tectonic causes.     

RADON DEPTH MIGRATION1

A depth migration method is presented that uses Radon-transformed common-source seismograms as input. It is shown that the Radon depth migration method can be extended to spatially varying velocity depth models by using asymptotic ray theory (ART) to construct wavefield continuation operators. These operators downward continue an incident receiver-array plane wave and an assumed point-source wavefield into the subsurface. The migration velocity model is constrained to have longer characteristic wavelengths than the dominant source wavelength such that the ART approximations for the continuation operators are valid. This method is used successfully to migrate two synthetic data examples:

• 1 a point diffractor, and
• 2 a dipping layer and syncline interface model.

It is shown that the Radon migration method has a computational advantage over the standard Kirchhoff migration method in that fewer rays are computed in a main memory implementation.     

Isotope and trace element evidence for three component mixing in the genesis of the North Luzon arc lavas (Philippines)

Post-3Ma volcanics from the N Luzon arc exhibit systematic variations in ⁸⁷Sr/⁸⁶Sr (0.70327–0.70610), ¹⁴³Nd/¹⁴⁴Nd (0.51302–0.51229) and ²⁰⁸Pb^*/²⁰⁶Pb^* (0.981–1.035) along the arc over a distance of about 500 km. Sediments from the South China Sea west of the Manila Trench also exhibit striking latitudinal variations in radiogenic isotope ratios, and much of the isotopic range in the volcanics is attributed to variations in the sediment added to the mantle wedge during subduction. However, Pb-Pb isotope plots reveal that prior to subduction, the mantle end-member had high 8/4, and to a lesser extent high 7/4, similar to that in MORB from the Indian Ocean and the Philippine Sea Plate. Th isotope data on selected Holocene lavas indicate a source with unusually high Th/U ratios (4.5–5.5). Combined trace element and isotope data require that three end-members were implicated in the genesis of the N Luzon lavas: (1) a mantle wedge end-member with a Dupal-type Pb isotope signature, (2) a high LIL/HFS subduction component interpreted to be a slab-derived hydrous fluid, and (3) an isotopically enriched end-member which reflects bulk addition (<5%) of subducted S China Sea terrigenous sediment. The ⁸⁷Sr/⁸⁶Sr ratios in the volcanics show a restricted range compared with that in the sediments, and this contrasts with ¹⁴³Nd/¹⁴⁴Nd and ²⁰⁸Pb^*/²⁰⁶Pb^*, both of which have similar ranges in the volcanics and sediments. Such differences imply that whereas the isotope ratios of Nd, Pb and Th are dominated by the component from subducted sediment, those of Sr reflect a larger relative contribution from the slab-derived fluid.     

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     

Alkaline and ultramafic carbonate lamprophyres in Central Bohemian carboniferous basins,Czech Republic

Summary Dykes of alkaline and ultramafic carbonate lamprophyres (monchiquite-ouachitite and aillikite) intrude the Carboniferous sediments of Central Bohemia. Their characteristic feature is the presence of substantial amounts of a sodalite group mineral (presumably haüyne), carbonate and barite. Isotopic compositions of ¹³C (–3.4 to –6.2) and ¹⁸O ( + 13.5 to + 15.9) indicate that the carbonate is of primary magmatic origin and that fluids were formed at temperatures of 500 to 350°C. High contents of CO₂ (3.6 to 17.6 wt.%) and incompatible elements, high LREE/HREE ratios (30.0 to 57.7), and low Rb/Sr (0.025 to 0.078) and⁸⁷Sr/⁸⁶Sr (0.7038 to 0.7042) ratios suggest the ultramafic lamprophyres are related to deep-seated carbonated magmas of mantle origin. Low degree of partial melting ( < 1%) of the mantle peridotite is envisaged, with additional transport of fluids rich in incompatible elements into the crustal chamber. Alkaline lamprophyres are fractionated derivatives which originated from the same source. Magma intrusion from different levels of a magma chamber into fracture zones under horizontal tension without a central intrusion could result in variability in lamprophyre composition (cumulates or evolved derivatives).

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Alkalische und ultramafische Karbonat-Lamprophyre der zentralen böhmischen Karbonbecken, Tschische Republik

Zusammenfassung Alkalische und ultramafische Karbonat-Lamprophyrgänge (Monchiquit-Ouachitit und Aillikit) intrudieren in karbonische Sedimente Zentralböhmens. Sie sind charakterisiert durch das Auftreten von beträchtlichen Mengen an Mineralen der Sodalith-Gruppe (v.a. Haüyn), Karbonaten und Baryt. Ihre Isotopenzusammensetzung von ¹³C (–3.4 bis –6.2) und ¹⁸O (13.5 bis 15.9) zeigt, daß die Karbonate primär magmatischen Ursprungs sind und daß assoziierte Fluide in einem Temperaturbereich von 350 bis 500°C gebildet wurden. Hohe Gehalte an CO₂ (3.6 bis 17.6 Gew. %), inkompatiblen Elementen, hohe LREE/HREE-Verhältnisse (30.0 bis 57.7), sowie niedrige Rb/Sr—(0.025 bis 0.078) und⁸⁷Sr/⁸⁶Sr-(0.7038 bis 0.7042) Verhältnisse lassen vermuten, daß die ultramafischen Lamprophyre mit karbonatischen Magmen des Mantels in Beziehung stehen. Eine niedrige Aufschmelzungsrate ( < 1%) von Mantelperidotit mit zusätzlichem Transport von, an inkompatiblen Elementen angereicherten Fluiden, in die krustale Magmenkammer wird diskutiert. Alkalische Lamprophyre sind als stärker fraktionierte Magmen, die derselben Quelle entstammen, zu verstehen. Die Intrusion der aus verschiedenen Bereichen der Magmenkammer stammenden Magmen in durch horizontale Dehnung verursachte Störungszonen könnte das Fehlen eines zentralen Intrusionskörpers und die unterschiedliche Zusammensetzung der Lamprophyre (Kumulate oder entwickelte Derivate) erklären.

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With 8 Figures     

Primitive island arc and oceanic lavas from the hunter ridge-hunter fracture zone. Evidence from glass,olivine and spinel compositions

Summary At its southernmost end, the main spreading centre of the North Fiji Basin is propagating into arc crust of the poorly-known Hunter Ridge. We define nine magmatic groups from major element glass chemistry and olivine and spinel compositions in samples dredged from twenty six sites in this area by the R/V Academician A. Nesmeyanov in 1990. These include groups of boninites, island arc tholeiites (IAT), mid-ocean ridge basalts (MORB), enriched mid-ocean ridge basalts (E-MORB), olivine porphyritic andesites and basaltic andesite and Na-rhyolites. Primitive lavas containing highly forsteritic olivine phenocrysts are common in all the groups, except for the rhyolites.We report over 100 glass analyses for dredged rocks from this region, and about 300 olivine-spinel pairs for representatives of all the magmatic groups identified, except the Na-rhyolites.The MORB in this region are probably produced at the propagating spreading centre in the southern part of the North Fiji Basin. Juxtaposition of shallow, hot MORB-source diapirs supplying the MORB in this area, and the sub-arc damp, refractory upper mantle beneath the Hunter Ridge, provides suitable petrogenetic conditions to produce a range of magma types, from island arc tholeiites through to high-Ca boninites. The latter were recovered in eleven dredges.The E-MORB lavas recovered from the extreme southern margin of the North Fiji Basin are shown to be essentially identical to those dredged from adjacent older South Fiji Basin crust. It is hypothesized that the former were either scraped off the South Fiji Basin crust during an episode of oblique subduction that may have generated the Hunter Ridge during the last 5 Myr, or alternatively, that slices of the South Fiji Basin crust were trapped and incorporated into the North Fiji Basin as the subduction zones fronting the Vanuatu arc stepped or propagated southward.

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Primitive Inselbogen- und ozeanische Laven von Hunter Rücken und der Hunter BruchZone: die Bedeutung der Zusammensetzung von Glas, Olivin und Spinell

Zusammenfassung Das spreading centre des Nord-Fidschi-Beckens setzt sich an seinem südlichsten Ende in die Inselbogen-Kruste des noch wenig bekannten Hunter-Rückens fort.Wir definieren 9 magmatische Gruppen auf der Basis der Hauptelement-Zusammensetzung von Gläsern und der Zusammensetzung von Olivin und Spinell in Proben die das Forschungsschiff R/V Akademiker A. Nesmeyanov von 26 Stellen im Jahr 1990 aufgesammelt hat. Zu diesen gehören Gruppen von Boniniten, Inselbogentholeiiten (IAT), Basalten zentralozeanischer Rücken (MORB), angereicherte zentralozeanische Rücken (E-MORB), Olivin-porphyritische Andesite und basaltische Andesite, sowie Na-Rhyolite. Primitive Laven mit Olivinkristallen, die reich an Forsterit-Komponenten sind, kommen in allen diesen Gruppen, mit Ausnahme der Rhyolite, vor.Wir legen über 100 Glas-Analysen von Gesteinen aus diesem Gebiet vor und über 300 Olivin-Spinell-Paare für Vertreter aller der hier identifizierten magmatischen Gruppen, mit Ausnahme der Natriumrhyolite.Die MORB in diesem Gebiet sind wahrscheinlich an dem aktiven Spreading Center im Südteil des Nord-Fidschi-Beckens entstanden. Das nebeneinander Vorkommen von seichten heißen MORB-Quellen Diapiren, die MORB in diesem Gebiet erzeugen, und der Sub-Inselbogen, wasserhaltige, refraktäre obere Mantel unter dem Hunter Rücken führen zu geeigneten petrogenetischen Bedingungen für die Entstehung einer Vielfalt von Magmatypen, von Inselbogentholeiiten bis zu sehr Kalziumreichen Boniniten. Die letzteren wurden in 11 Dredge-Proben gefunden.Die E-MORS Laven, die aus dem extremen Südteil des Nord-Fidschi-Beckens entnommen wurden, sind im wesentlichen mit jenen identisch, die aus der benachbarten älteren Kruste des Süd-Fidschi-Beckens stammen. Es wird vermutet, daß die letzteren entweder aus dem Süd-Fidschi-Becken während einer Episode obliger Subduktion, die in den letzten 5 Millionen Jahren zur Entstehung des Hunter Ridge geführt hat, abgeschert wurden, oder auch daß Teile der Kruste des Süd-Fidschi-Beckens in das Nord-Fidschi-Becken inkorporiert wurden als Subduktionszonen gegenüber dem Vanuato-Bogen sich nach Süden fortbewegten.