Laser combustion analysis of δS of sulfosalt minerals: determination of the fractionation systematics and some crystal-chemical considerations

Laser sulfur combustion in the presence of O₂ is the most commonly used method of in situ sulfur isotope analysis. Previous workers indicated that a small but reproducible fractionation of ³⁴S/³²S exists between the product SO₂ gas and the mineral. The magnitude of this fractionation varies with bond strength, as reflected in Gibbs free energy of formation at 298.15K. The correction factors are known for common sulfides and anhydrite but not, hitherto, for stibnite and the sulfosalt minerals, which are important constituents of many classes of ore deposits. We present the correction factors for the following chemically and crystallographically well-characterized minerals: stibnite (weighted mean = −1.2‰), bournonite (+0.6‰), tetrahedrite (+1.3‰), and boulangerite (+1.4‰). The Gibbs free energies of formation of these phases have been approximated by the sulfide summation method, and the correlation of ΔG₂₉₈⁰ with the correction factor for the sulfosalts fits well with the trend previously established for simple sulfides. There is an excellent correlation between the fractionation factor and mineral composition, a parameter that does result in bond strength variations (e.g., mol fraction of PbS in sulfosalts), allowing estimation of the correction factors for simple intermediate compositions. Finally, bond strength also varies with variation in interatomic distances, and we have, therefore, investigated the behaviour of stibnite, a strongly anisotropic mineral. Our results indicate that there is a significant variation in fractionation factor, depending on crystal orientation. The fractionation factor along the prismatic b-axis, which displays the strongest chemical bonds (as monitored by the shortest bond lengths), is more negative (−1.7‰) than along the other crystallographic directions (−0.7 to −1.0‰), which is in full agreement with theoretical predictions. We demonstrate the application of the technique in unravelling source- and process-related sulfur isotope systematics in two hydrothermal vein systems in the classic mining area of the NE Rhenish Massif, both studies requiring resolution beyond the scale of conventional sulfur isotope analysis.     

The structure of the polar ionosphere during exceptionally quiet periods

Knowledge of the structure of the polar ionosphere during exceptionally quiet periods is basic for studying complicated ionospheric behaviors during disturbances. On the basis of data from an airborne ionosonde as well as a meridian chain of ground-basedionosondes, the circumpolar structure of the E,-and F-regions is elucidated. There are two circumpolar zones of E-region ionization with differing characteristics. The first is an auroral E,-layer and/or retarded type sporadic E-band that has previously (Whalen et al., 1971) been found to be identical with the continuous aurora. The second is a zone of non-retarded type spora die E located poleward of the former band. In general, discrete auroras are co-located with the latter. The main trough, a prominent feature of the night sector F-region, is most pronounced in the early morning. The main trough is bounded on the poleward side by a well defined ‘wall’ of F-region ionization. The night sector poleward trough wall is located approximately three degrees of latitude equatorward of the auroral oval. A ‘plateau’ of F-region ionization extends from the poleward trough wall to the auroral oval.     

Observations of a post-flare radio burst in X-rays

More than six hours after the two-ribbon flare of 21 May 1980, the hard X-ray spectrometer aboard the SMM imaged an extensive arch above the flare region which proved to be the lowest part of a stationary post-flare noise storm recorded at the same time at Culgoora. The X-ray arch extended over 3 or more arc minutes to a projected distance of 95 000 km, and its real altitude was most probably between 110 000 and 180 000 km. The mean electron density in the cloud was close to 10⁹ cm^–3 and its temperature stayed for many hours at a fairly constant value of about 6.5 × 10⁶ K. The bent crystal spectrometer aboard the SMM confirms that the arch emission was basically thermal. Variations in brightness and energy spectrum at one of the supposed footpoints of the arch seem to correlate in time with radio brightness suggesting that suprathermal particles from the radio noise regions dumped in variable quantities into the low corona and transition layer; these particles may have contributed to the population of the arch, after being trapped and thermalized. The arch extended along the H = 0 line thus apparently hindering any upward movement of the upper loops reconnected in the flare process. There is evidence from Culgoora that this obstacle may have been present above the flare since 15–30 min after its onset.     

The High Altitude Observatory Coronagraph/Polarimeter on the Solar Maximum Mission

The High Altitude Observatory Coronagraph/Polarimeter, to be flown on the National Aeronautics and Space Administration's Solar Maximum Mission satellite, is designed to produce images of the solar corona in seven wavelength bands in the visible spectral range. The spectral bands have been chosen to specifically exclude or include chromospheric spectral lines, so as to allow discrimination between ejecta at high (coronal) and low (chromospheric) temperatures, respectively. In addition, the instrument features spectral filters designed to permit an accurate color separation of the F and K coronal components, and a narrow band (5.5 Å) filter to observe the radiance and polarization of the Fe xiv 5303 Å line. The effective system resolution is better than 10 arc sec and the instrument images a selected quadrant (or smaller field) on an SEC vidicon detector. The total height range that may be recorded encompasses 1.6 to more than 6.0R (from Sun center). The instrument is pointed independently of the SMM spacecraft, and its functions are controlled through the use of a program resident within the onboard spacecraft computer. Major experimental goals include: (a) Observation of the role of the corona in the flare process and of the ejecta from the flare site and the overlying corona; (b) the study of the direction of magnetic fields in stable coronal forms, and, perhaps, ejecta; and (c) examination of the evolution of the solar corona near the period of solar maximum activity.The National Center for Atmospheric Research is sponsored by the National Science Foundation.     

Melt/harzburgite reaction in the petrogenesis of tholeiitic magma from Kilauea volcano, Hawaii

We use the results of elevated pressure melting experiments to constrain the role of melt/mantle reaction in the formation of tholeiitic magma from Kilauea volcano, Hawaii. Trace element abundance data is commonly interpreted as evidence that Kilauea tholeiite is produced by partial melting of garnet lherzolite. We experimentally determine the liquidus relations of a tightly constrained estimate of primary tholeiite composition, and find that it is not in equilibrium on its liquidus with a garnet lherzolite assemblage at any pressure. The composition is, however, cosaturated on its liquidus with olivine and orthopyroxene at 1.4 GPa and 1425 °C, from which we infer that primary tholeiite is in equilibrium with harzburgite at lithospheric depths beneath Kilauea. These results are consistent with our observation that tholeiite primary magmas have higher normative silica contents than experimentally produced melts of garnet lherzolite. A model is presented whereby primary tholeiite forms via a two-stage process. In the first stage, magmas are generated by melting of garnet lherzolite in a mantle plume. In the second stage, the ascent and decompression of magmas causes them to react with harzburgite in the mantle by assimilating orthopyroxene and crystallizing olivine. This reaction can produce typical tholeiite primary magmas from significantly less siliceous garnet lherzolite melts, and is consistent with the shift in liquidus boundaries that accompanies decompression of an ascending magma. We determine the proportion of reactants by major element mass balance. The ratio of mass assimilated to mass crystallized (M_a/M_c) varies from 2.7 to 1.4, depending on the primary magma composition. We use an AFC calculation to model the effect of melt/harzburgite reaction on melt rare earth and high field strength element abundances, and find that reaction dilutes, but does not significantly fractionate, the abundances of these elements. Assuming olivine and orthopyroxene have similar heats of fusion, the M_a/M_c ratio indicates that reaction is endothermic. The additional thermal energy is supplied by the melt, which becomes superheated during adiabatic ascent and can provide more thermal energy than required. Melt/harzburgite reaction likely occurs over a range of depths, and we infer a mean depth of 42 km from our experimental results. This depth is well within the lithosphere beneath Kilauea. Since geochemical evidence indicates that melt/harzburgite reaction likely occurs in the top of the Hawaiian plume, the plume must be able to thin a significant portion of the lithosphere. Received: 4 February 1997 / Accepted: 27 August 1997     

Groundbased Doas UV/visible measurements at Kiruna (Sweden) during the sesame winters 1993/94 and 1994/95.

Zenith sky observations of O3, NO2, OClO and BrO are reported, which were performed at Kiruna (67.9°N, 21.1°E) within the SESAME winters 1993/1994 and 1994/95. For both winters large total amounts of OClO were observed inside the polar vortex at twilight, indicating the degree and the temporal variation of the halogen activation of the polar stratosphere. Occasionally OClO could also be observed outside the polar vortex, most likely due to export of halogen activated vortex air masses into the ambient stratosphere. BrO could also be detected in winter 1994/95, with the largest slant column amounts (5·1014/cm2) occuring in the polar vortex in mid-winter. Similar abundances of stratospheric BrO were observed at dusk and dawn, for both, air masses inside and outside the vortex. This observation is in reasonable agreement with previous studies on stratospheric BrO (observations and models) of Wahner et al. (1992), Arpag et al. (1994), Krug et al. (1996), and Lary et al. (1996a,b), but partly in disagreement with those of Solomon et al. (1989), Fish et al. (1995), and Sessler et al. (1996).     

Fission track ages of North American tektites

Fission track ages of North American tektites from Texas, Georgia and Martha's vineyard range widely between 0.8 my and 34.2 my with the tektites from Georgia giving the lowest ages. Size studies of the fission track etch pits reveal the thermal history of each individual tektite resulting in the partial loss of tracks. Therefore, the measured fission track ages can be understood as thermally lowered.

Based on annealing experiments, correction factors for the thermally lowered fission track ages are found. The weighted mean of the corrected fission track ages is 34.9 my for the bediasites and the Martha's Vineyard tektite. On the other hand, the corrected fission track ages of the Georgia tektites are much lower resulting from a more complex thermal history.

It may now be stated that North American tektites and Libyan Desert glasses cannot have had a simultaneous origin.     

15th order resonance terms using the decaying orbit of TETR-3

The orbit of TETR-3 (1971-83B), inclination: 33°, passed through resonance with 15th order geopotential terms in February 1972. The resonance caused the orbit inclination to increase by 0.015°. Analysis of 48 sets of mean Kepler elements for this satellite in 1971–1972 (across the resonance) has established the following strong constraint for high degree, 15th order gravitational terms (normalized):

$\text{10}{}^9\text{(}\text{C, S}\text{)}{}_{15}\text{= (28.3 ± 3.0, 7.4 ± 3.0) =}\text{0.001(}\text{C, S}\text{)}{}_{\mathrm{15,15}}\text{?0.015(}\text{C, S}\text{)}{}_{\mathrm{17,15}}\text{+0.073(}\text{C, S}\text{)}{}_{\mathrm{19,15}}\text{?0.219(}\text{C, S}\text{)}{}_{\mathrm{21,15}}\text{+0.477(}\text{C, S}\text{)}{}_{\mathrm{23,15}}\text{?0.781(}\text{C, S}\text{)}{}_{\mathrm{25,15}}\text{+1.000(}\text{C, S}\text{)}{}_{\mathrm{27,15}}\text{?0.0963(}\text{C, S}\text{)}{}_{\mathrm{29,15}}\text{+0.622(}\text{C, S}\text{)}{}_{\mathrm{31,15}}\text{?0.119(}\text{C, S}\text{)}{}_{\mathrm{33,15}}\text{?0.290(}\text{C, S}\text{)}{}_{\mathrm{35,15}}\text{+0.403(}\text{C, S}\text{)}{}_{\mathrm{37,15}}\text{?0.223(}\text{C, S}\text{)}{}_{\mathrm{39,15}}\text{?0.058(}\text{C, S}\text{)}{}_{\mathrm{41,15}}\text{+…}$

This result combined with previous results on high inclination 15th order and other resonant orbits suggests that the coefficients of the gravity field beyond the 15th degree are smaller than Kaula's rule ($\text{10}{}^{\mathrm{?5}}\text{l}{}^2$).