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.     

Improved Petrological Modal Analyses from X-ray Powder Diffraction Data by use of the Rietveld Method I. Selected Igneous, Volcanic, and Metamorphic Rocks

Mineral modes have been determined for specimens of eight rocktypes from CuK X-ray powder diffraction data using the Rietveldmethod. The samples include two granites, a granodiorite, adamellite,gabbro, basalt, trachyte, and two granulite-facies metamorphicrocks. Up to eight individual mineral components have been measuredin each sample (no glassy phases were observed), with a detectionlimit of {small tilde}1 wt.%, depending on the mineral assemblage.Marked variations in grain size (i.e., granite vs. trachyte)provide no difficulties for the X-ray method. The X-ray resultscompare very favourably with (1) optical modes determined forthe medium–coarse-grained samples by point counting, (2)normative calculations obtained using locally enhanced catanormand mesonorm software, and (3) corresponding Rietveld modesdetermined, for two samples, from neutron powder data. Wheredifferences occur, these are discussed in relation to the limitationsof each of the methods. The improved accuracy of the X-ray method is due primarily tothe incorporation of the full diffraction profile in the Rietveldanalysis calculations, and the elimination of preferred orientationby collecting the data from samples packed in glass capillaries(i.e., Debye–Scherrer mode). The good agreement of theX-ray and neutron modes shows that the usual problems encounteredwith microabsorption, extinction, and sampling are of littleconcern in these rocks. The results highlight one of the majoradvantages provided by Rietveld modal analysis over the moretraditional ‘reference intensity’ X-ray methods,namely, that the crystal chemistry (and thus the calibrationconstants) of the individual phases can be adjusted dynamicallyduring each individual analysis. This not only provides moreaccurate phase abundances, but also gives important supplementaryinformation about the mineralogy of the major components.     

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     

Corona textures in Proterozoic olivine melanorites of the Equeefa Suite,Natal Metamorphic Province,South Africa

Summary Olivine-plagioclase and phlogopite-plagioclase coronas have been identified from olivine melanorites of the Mid- to Late Proterozoic Equeefa Suite in southern Natal, South Africa. Olivine, in contact with plagioclase, is mantled by a shell of clear orthopyroxene, in turn rimmed by pale green (pargasitic) clinoamphibole. Locally a third rim, composed of a fine pargasite-spinel symplectite is developed adjacent to the plagioclase. The second corona reaction has produced greenish-brown pargasite at phlogopite-plagioclase interfaces. A third, less obvious reaction, between olivine and phlogopite is also noted. Analytical data of all the mineral phases present, along with the coronas, are given. Two-pyroxene thermometry yields magmatic core temperatures ( 1120°C), with rim compositions indicating equilibration at 850°C. Consistent with this, the modelled olivine-plagioclase reaction occurs between 830–1050°C with a_waterbetween 0.1 and 1.0 at 7 kbar. The three reactions took place during a prolonged history of cooling and partial hydration of the magmatic olivine melanorites from over 1000°C down to 600°C. The P-T conditions indicated by the reactions suggest this cooling process was essentially isobaric, indicating that the area was not subjected to rapid uplift or burial throughout this entire period.

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Korona-Texturen in proterozoischen Olivin-Melanoriten der Equeefa Suite, Natal Metamorphic Province, Südafrika

Zusammenfassung Aus Olivin-Melanoriten der mittel- bis spätproterozoischen Equeefa Suite im südlichen Natal, Südafrika, wurden Olivin-Plagioklas und Phlogopit-Plagioklas-Koronartexturen beobachtet. Olivin, der mit Plagioklas im Kontakt steht, wird von einem klaren Saum vom Orthopyroxen ummantelt, der seinerseits von blaßgrünem (pargasitischem) Klinoamphibol umsäumt wird. Stellenweise ist ein dritter Saum, bestehend aus feinkörnigem symplektitischem Pargasit-Spinell im Kontakt mit Plagioklas ausgebildet. Die zweite koronabildende Reaktion resultiert in Bildung eines grünbraunen Pargasites an Phlogopit-Plagioklas Kornkontakten. Eine dritte, weniger auffällige Reaktion zwischen Olivin und Phlogopit wurde ebenfalls beobachtet. Zwei-Pyroxen-Thermometrie ergab magmatische Temperaturen der Kernbereiche ( 1120°C) und belegt eine Gleichgewichtseinstellung in den Randzonen bei ca. 850°C. Olivin-Plagioklas-Modellreaktionen liegen ebenfalls in einem Temperaturbereich von 830–1050°C bei Wasseraktivitäten von 0.1 bis 1.0 und einem Druck von 7 kbar. Die drei Reaktionen liefen im Zuge einer länger andauernden Abkühlung unter teilweiser Hydratisierung der magmatischen Melanorite in einem Temperaturbereich von 1000°C bis ca. 600°C ab. Die aus den Reaktionen ableitbaren P-T-Bedingungen sprechen für eine im wesentlichen isobare Abkhlungsgeschichte und zeigen, daß dieses Gebiet wáhrend dieser gesamten Periode keiner raschen Hebung bzw. keiner Versenkung unterworfen worden ist.

     

Sea level and diagenesis: a case study on Pleistocene beaches,Whalebone Bay,Bermuda

Pleistocene fluctuations of sea level have left marine and aeolian limestones intercalated with glacial red soils on the Bermuda Carbonate Platform (Atlantic, 64°50W, 32°20N). Successive eustatic highstands of similar amplitude drowned the tectonically stable platform and piled up similar sets of sediments. Up to three Pleistocene beaches are stacked in shorelines sections. Post-depositional diagenetic histories of these beaches can be linked to repeated changes in sea level and pore waters.This paper presents field evidence and petrographic results (microscope, X-ray, cathodoluminescence, SEMEDAX) for the diagenetic histories of two superimposed Pleistocene beaches in Whalebone Bay, Bermuda North Shore. The younger beach was deposited during isotopic stage 5e, about 120 ka ago. The age of the older beach may be isotopic stage 9 or older.Diagenesis drastically altered the older beach before the stage 5e transgression. Primary high-Mg calcite (HMC) and aragonite were no longer present. Marine skeletal grains were instead leached or recrystallized to low-Mg calcite (LMC). Primary and secondary pore space were largely reduced by LMC cement. Lines of needle relics reminiscent of marine aragonite cement occur as inclusions within syntaxial rim cements around echinoderm grains, indicating that a marine influence had at least once interrupted this period of freshwater alteration. Finally, before the rocks became buried by the sediments of the younger beach, a crust of marine, bladed HMC cement was precipitated throughout the pore space.The younger beach consists of skeletal grains that are, apart from the effects of non-selective dissolution, essentially unaltered. The sediments are only weakly lithified by cryptocrystalline LMC showing an alveolar texture, tangential fibres and other features characteristic of calichification. A younger post-depositional marine influence is not recorded.These results suggest that, under favourable conditions, diagenetic processes can document sea-level fluctuations. The recorded fluctuations, however, are difficult to assess because even major sea-level highstands may not produce a diagenetic imprint. Correspondence to: R. Vollbrecht