On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.     

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.     

Diamondiferous eclogites from Yakutia,Siberia: evidence for a diversity of protoliths

Major-element and REE compositions of 14 diamondiferous eclogites from the Udachnaya kimberlite in Yakutia, Siberia have been determined by electron microprobe and secondary ion mass spectrometer (SIMS). Based on previous clinopyroxene classification schemes (e.g., Taylor and Neal 1989), all of these eclogite xenoliths belong to Group B/C, although some of the garnet compositions and mineral REE abundances are inconsistent with the indicated groups. This demonstrates the inadequacy of the classification scheme based on African eclogites for application to Siberian samples. Because of the coarse grain size of the Udachnaya nodules, meaningful modal abundances could not be obtained. However, reconstructed REE compositions using various garnet: clinopyroxene ratios demonstrate relative insensitivity to changes in mode for common eclogitic assemblages. Many of these reconstructed REE compositions show LREE depletions. Some depletions are consistent with an origin (either directly or through partial melting) as normal or Type-I ocean floor basalt. Others, however, require material of eclogitic or pyroxenitic affinities to undergo partial melting; this facilitates the depletion of LREE while leaving the HREE at nearly original levels. Many of the eclogites of South Africa are consistent with a protolith of anomalous or Type II ocean floor basalt. This fundamental difference between the two regions is the likely cause of the inconsistencies with the chemicallybased classification.     

Confirmation of radio absorption by the intergalactic medium

The conventional interpretation of the cosmic background radiation (CBR) as a relic of the Big Bang assumes that the intergalactic medium is highly transparent to radio frequency radiation. Previous work (Lerner, 1990) used the well-known correlation of IR and radio luminosities of spiral galaxies to test this assumption. That analysis, using 237 Shapley-Ames galaxies showed that radio luminosity (L _R ) for a given IR-luminosity, declines with distance, implying that the IGM strongly absorbs radio frequency radiation. That absorption has now been confirmed using a sample of 301 IR-bright galaxies. Using two independent methods of determining the correlation of IR and radio luminosities of spiral and interacting galaxies, the sample shows that for a givenL _IR ,L _R D ^{–0.32±0.04} over a range of distances from 0.7-300 Mpc. (H ₀ = 75 km s^–1 Mpc^–1). The correlation is significant at the 8 or 10^–14 level. Absorption by the IGM is the only reasonable explanation for this correlation. The existence of such absorption implies that neither the isotropy nor the spectrum of the CBR are primordial and that neither is evidence for a Big Bang.     

Discovery and rediscovery of Trojan asteroids

During 1987–1994, observational campaigns with different telescopes at several observatories have been initiated by the author in order to discover new Trojans. The importance of Trojan asteroids comes from celestial mechanics, where they represent the physical solution of the famous Lagrange triangular problem. Their importance lies also in the fact, that they may have some relation with comets. Furthermore, the Trojan belt may be as large as the belt of asteroids. Moreover, recently families have been discovered between the already well known Trojans. Enough reasons to continue to search for these interesting objects.     

On the problem of big bang nucleosynthesis

Supporters of the standard Big Bang theory point to the abundances of light elements, predicted by Big Bang Nucleosynthesis (BBN) as one of the main observational supports of the theory. However, current data no longer confirm BBN. Instead, measurements of the abundances of He³, He⁴, and D clearly contradict BBN at more than a 3 level, eliminating a key support of the Big Bang.     

Fossil-pollen evidence for abrupt climate changes during the past 18 000 years in eastern North America

A quantitative measure of the rate at which fossil-pollen abundances changed over the last 18 000 years at 18 sites spread across eastern North America distinguishes local from regionally synchronous changes. Abrupt regional changes occurred at most sites in late-glacial time (at 13700, 12 300, and 10000 radiocarbon yr BP) and during the last 1000 years. The record of abrupt late-glacial vegetation changes in eastern North America correlates well with abrupt global changes in ice-sheet volume, mountain snow-lines, North Atlantic deep-water production, atmospheric CO₂, and atmospheric dust, although the palynological signal varies from site to site. Changes in vegetation during most of the Holocene, although locally significant, were not regionally synchronous. The analysis reveals non-alpine evidence for Neoglacial/Little Ice Age climate change during the last 1000 years, which was the only time during the Holocene when climate change was of sufficient magnitude to cause a synchronous vegetational response throughout the subcontinent. During the two millennia preceding this widespread synchronous change, the rate of change at all sites was low and the average rate of change was the lowest of the Holocene.Contribution to Clima Locarno Past and Present Climate Dynamics; Conference September 1990, Swiss Academy of Sciences — National Climate Program     

Differential unroofing within the central metasedimentary Belt of the Grenville Orogen: constraints from 40Ar/39Ar thermochronology

An ⁴⁰Ar/³⁹Ar thermochronological investigation of upper greenschist to granulite facies gneiss, amphibolite and marble was conducted in the Central Metasedimentary Belt (CMB), Ontario, to constrain its cooling history. Incremental ⁴⁰Ar/³⁹Ar release spectra indicate that substantial differential unroofing occurred in the CMB between 1000 and 600 Ma. A consistent pattern of significantly older hornblende and phlogopite ⁴⁰Ar/³Ar cooling ages on the southeast sides of major northeast striking shear zones is interpreted to reflect late displacement due to extensional deformation. Variations in hornblende ⁴⁰Ar/³⁹Ar age plateaus exceeding 200 Ma occur over distances less than 50 km with major age discontinuities occurring across the Robertson Lake shear zone and the Sharbot Lake mylonite zone which separate the Sharbot Lake terrane from the Elzevir and Frontenac terranes. Extensional displacements of up to 14 km are inferred between the Frontenac and Elzevir terranes of the CMB. No evidence for significant post argon-closure vertical displacement is indicated in the vicinity of the Perth Road mylonite within the Frontenac terrane. Variations of nearly 100 Ma in phlogopite ⁴⁰Ar/³⁹Ar plateau ages occur in undeformed marble on either side of the Bancroft Shear Zone. Phlogopites from sheared and mylonitized marble within the shear zone yield ⁴⁰Ar/³⁹Ar diffusional loss profiles, but have older geologically meaningless ages thought to reflect incorporation of excess argon. By 900 Ma, southeast directed extension was occurring throughout the CMB, possibly initiated along previous zones of compressional shearing. An easterly migration of active zones of extension is inferred, possibly related to an earlier, overall easterly migration of active zones of regional thrusting and easterly migration of an ancient subduction zone. The duration of extensional shearing is not well constrained, but must have ceased before 600 Ma as required by the deposition of overlying undeformed Cambrian and/or Ordovician sedimentary rocks.Contribution No. 481 from the Mineralogical Laboratory, University of Michigan     

Low temperature volatile production at the Lost City Hydrothermal Field, evidence from a hydrogen stable isotope geothermometer

Although commonly utilized in continental geothermal work, the water-hydrogen and methane-hydrogen isotope geothermometers have been neglected in hydrothermal studies. Here we report δD-CH₄ and δD-H₂ values from high-temperature, black smoker-type hydrothermal vents and low-temperature carbonate-hosted samples from the recently discovered Lost City Hydrothermal Field. Methane deuterium content is uniform across the dataset at − 120 ± 12‰. Hydrogen δD values vary from − 420‰ to − 330‰ at high-temperature vents to − 700‰ to − 600‰ at Lost City. The application of several geothermometer equations to a suite of hydrothermal vent volatile samples reveals that predicted temperatures are similar to measured vent temperatures at high-temperature vents, and 20-60 °C higher than those measured at the Lost City vents. We conclude that the overestimation of temperature at Lost City reflects 1) that methane and hydrogen are produced by serpentinization at > 110 °C, and 2) that isotopic equilibrium at temperatures < 70 °C is mediated by microbial sulfate reduction. The successful application of hydrogen isotope geothermometers to low-temperature Lost City hydrothermal samples encourages its employment with low-temperature diffuse hydrothermal fluids.     

A geochemical approach to model periodically replenished magma chambers: Does oscillatory supply account for the magmatic evolution of EPR 17-19°S?

We propose a new approach to model the geochemical evolution of continuously replenished and tapped steady-state magma chambers. We use a sinusoidal function to model cyclic magma supply. The temporal evolution of a reservoir is described using differential equations, in which the amount of refilling magma does not depend on the size of the chamber. These equations can be used to calculate incompatible trace element concentrations and magma quantities. We examine the geochemical consequences of episodic injections, noises and wall-rock assimilation. We also explore possible variations in crystallization rate. To show its potential, the theoretical treatment has been applied to the EPR 17-19°S, a site with a strong magma budget which has been the subject of several geological/geophysical studies. The practical application requires geological parameters to be constrained, as well as the extreme values of the lava concentration range. A first step specifies the incompatible trace element composition of the replenishing melt, which corresponds in the EPR case to a magnesian liquid (MgO = 9.5 wt%). It is then possible to determine other parameters such as cycle period (∼750 years), magma residence time (∼300 years), and reservoir size (from 4.1 to 8.6 km³ per 20 km segment). Lastly, variations in crystallization rate do not significantly alter the results.