A numerical investigation of the destruction of peroxy radical by Cu ion catalysed reactions on atmospheric particles

To determine if Cu mediated reactions on atmospheric particles are important to HO₂ chemistry in the ambient atmosphere, Cu molalities were calculated from measured Cu aerosol particle concentrations, mass and number size distribution data from a site in central Sweden. A comparison of characteristic times indicates that at low relative humidities the reaction is limited by the mass transport of gas phase HO₂ to the particle surface and not by the chemical kinetics of the aqueous reaction. Comparison of half-lives for particle reactions and the gas phase destruction of HO₂ to form H₂O₂ indicate that heterogeneous reactions on aerosol particles may have important consequences on the chemistry of HO₂ and H₂O₂ in the troposphere.     

Annual variation of atmospheric carbonyl sulfide in the marine atmosphere in the Southern Indian Ocean

Measurements of the concentrations of carbonyl sulfide (COS) in the marine atmosphere were made over a period of two years in the southern Indian Ocean (Amsterdam Island, 37°50 S–77°31 E; March 1987–February 1988 and April 1989–February 1990). The mean atmospheric COS concentration for the whole period was 475±48 pptv (n=544). Atmospheric COS concentrations show no significant seasonal variation with a summer to winter ratio of 1.05. Taking into account the observed variability of the atmospheric COS concentration (10%), a value of 1.4 yr is estimated as a lower limit for the atmospheric COS lifetime. A comparison of the COS data at Amsterdam Island with those obtained in the Southern Hemisphere in the past 12 yr does not reveal any significant trend in the tropospheric background COS mixing ratio.     

Model of geomagnetic paleosecular variations for the Northern Hemisphere

Summary A model of radial drifting and oscillating dipoles to represent geomagnetic palaeosecular variations, which showed to be appropriate for the Southern Hemisphere, is evaluated for the Northern Hemisphere. After a new fitting of some involved parameters, its theoretical results are compared with the palaeomagnetic data of Lake de Bouchet (France) and the Black Sea. A time lag between the declination and inclination profiles is observed in both cases. A good cross-correlation coefficient is obtained for the declination and inclination data.Presented at 2nd conference on New Trends in Geomagnetism, Castle of Bechyn, Czechoslovakia, September 24–29, 1990.     

Predicting ground-motion variations at the Turkey-flat test site,California

Results of a single group participating in an international experiment are analyzed. The experiment served to verify computational predictions of the ground-motion variations due to near-surface geological effects at a site established for that purpose by the California Department of Conservation. Based on an acceleration record at a rock location, and geotechnical model of medium, records at the other locations of a nearby sedimentary deposit were predicted. A 2-D finite-difference sensitivity analysis suggested that the lateral wave-propagation effects are negligibly small, and locally 1-D computations are sufficient for the present site. Those computations are compared with observations not available to the authors during the blind prediction. Peak accelerations, peak velocities and RMS accelerations were predicted with errors less than 159%, 114% and 62%, respectively. Maxima of the response spectra were fitted within a factor of 2. The predicted and observed Husid's plots (i.e., the normalized cumulative plots of the acceleration squared) have the correlation coefficients 0.98. The detected misfits do not show any simple relation to the instrument location, component, frequency, or time.     

Magma sources for Mesozoic anorogenic granites of the White Mountain magma series,New England,USA

The magma sources for granitic intrusions related to the Mesozoic White Mountain magma series in northern New England, USA, are addressed relying principally upon Nd isotopes. Many of these anorogenic complexes lack significant volumes of exposed mafic lithologies and have been suspected of representing crustal melts. Sm–Nd and Rb–Sr isotope systematics are used to evaluate magma sources for 18 felsic plutons with ages ranging from about 120 to 230 Ma. The possibility of crustal sources is further examined with analyses of representative older crust including Paleozoic granitoids which serve as probes of the lower crust in the region. Multiple samples from two representative intrusions are used to address intrapluton initial isotopic heterogeneities and document significant yet restricted variations (<1 in _Nd). Overall, Mesozoic granite plutons range in _Nd [T] from +4.2 to -2.3, with most +2 to 0, and in initial ⁸⁷Sr/⁸⁶Sr from 0.7031 to 0.709. The isotopic variations are roughly inversely correlated but are not obviously related to geologic, geographic, or age differences. Older igneous and metamorphic crust of the region has much lower Nd isotope ratios with the most radiogenic Paleozoic granitoid at _Nd [180 Ma] of -2.8. These data suggest mid-Proterozoic separation of the crust in central northern New England. Moreover, the bulk of the Mesozoic granites cannot be explained as crustal melts but must have large mantle components. The ranges of Nd and Sr isotopes are attributed to incorporation of crust by magmas derived from midly depleted mantle sources. Crustal input may reflect either magma mixing of crustal and mantle melts or crustal assimilation which is the favored interpretation. The results indicate production of anorogenic granites from mantle-derived mafic magmas.     

High pressure experimental calibration of the olivine-orthopyroxene-spinel oxygen geobarometer: implications for the oxidation state of the upper mantle

Synthetic spinel harzburgite and lherzolite assemblages were equilibrated between 1040 and 1300° C and 0.3 to 2.7 GPa, under controlled oxygen fugacity (f _{O 2}). f _{O 2} was buffered with conventional and open double-capsule techniques, using the Fe−FeO, WC-WO₂-C, Ni−NiO, and Fe₃O₄−Fe₂O₃ buffers, and graphite, olivine, and PdAg alloys as sample containers. Experiments were carried out in a piston-cylinder apparatus under fluid-excess conditions. Within the P-T-X range of the experiments, the redox ratio Fe³⁺/ΣFe in spinel is a linear function of f _{O 2} (0.02 at IW, 0.1 at WCO, 0.25 at NNO, and 0.75 at MH). It is independent of temperature at given Δlog(f _{O 2}), but decreases slightly with increasing Cr content in spinel. The Fe³⁺/ΣFe ratio falls with increasing pressure at given Δlog(f _{O 2}), consistent with a pressure correction based on partial molar volume data. At a specific temperature, degree of melting and bulk composition, the Cr/(Cr+Al) ratio of a spinel rises with increasing f _{O 2}. A linear least-squares fit to the experimental data gives the semi-empirical oxygen barometer in terms of divergence from the fayalite-magnetite-quartz (FMQ) buffer:

An Example of Island-Arc Petrogenesis: Geochemistry and Petrology of the Southern Luzon Arc, Philippines

Volcanism throughout the Luzon arc is associated with eastwardsubduction of the South China Sea floor along the Manila Trench.The southern section of the arc, the focus of this study, extendsfrom the Lingayen-Dingalan fault to the small islands just southof Luzon. Two segments appear to exist along this section ofthe arc the northern Bataan and southern Mindoro segments whichare separated by the Macolod Corridor. The volcanic rocks have typical arc phenocryst mineralogies:olivine, clinopyroxene, plagioclase, and titanomagnetite inthe most mafic rocks and clinopyroxene, plagioclase, orthopyroxene,titanomagnetite, ? amphibole in the more felsic samples. Complexzoning, sieve textures, and decoupling of incompatible traceelements suggest that processes such as assimilation have takenplace. The rocks from the study area range from basalts to rhyolitesand show typical calc-alkaline features. The rocks of the MacolodCorridor and Mindoro segment are particularly enriched in largeion lithophile elements (LILE), light rare earth elements (LREE),and radiogenic Sr compared with the Bataan segment. The datafall within the mantle array on Sr-Nd isotopic diagrams andgrade toward higher Sr and lower Nd isotopic values from northto south. A likely source for the volcanics of this study is either amid-ocean ridge basalt (MORB)-type mantle that undergoes higherdegrees of partial melting than regions involved in MORB generationor a previously depleted source. We suggest that the high fieldstrength element (HFSE) anomalies have been derived throughdifferential element partitioning during fluid transport fromthe subducted lithosphere to the mantle wedge. Continental crustal material seems to play a significant roleparticularly in the Macolod Corridor and the Mindoro segment,based on the high LILE, La/Sm ratios, radiogenic Sr isotopes,and ¹⁸O values. The Macolod Corridor and the Mindoro segmenthave undergone source contamination by crustal material fromthe North Palawan-Mindoro crustal block either during the collisionof this block with the Manila Trench or by subduction of sedimentsrich in this crustal material. A similar component has alsobeen detected in the Bataan segment but in minor amounts. Thetrace element and isotopic differences between the northernand southern sections of the arc are interpreted in terms ofvariable composition (i. e., variable amounts of a crustal componentintroduced from the Palawan-Mindoro crustal terrain) of themetasomatic fluids released into the source.     

Evolution of nappes in the eastern margin of the Bohemian Massif: a kinematic interpretation

The entire pile of nappes in the eastern margin of the Bohemian massif is characterized by two stages of Variscan nappe emplacement each exhibiting a different kinematic and metamorphic evolution.The older emplacement (D1) probably occurred around 350-340 Ma ago and was synmetamorphic. The nappes show a typical systematic superposition of higher grade metamorphic units over lower grade ones. Thus, the crystalline complexes showing a HT-MP Barrovian imprint (Svratka allochthonous unit and Moldanubicum) were thrust over an intermediate unit affected by MTMP recrystallization (Bíte orthogneiss and its country rock), and at the base of the D1 nappe pile the Inner Phyllite Nappe (Biý Potok Unit) is characterized by LT/LP metamorphism.The second stage of tectonic evolution (D2) is characterized by a thin-skinned northward-oriented nappe emplacement that occurred under LT-LP conditions dated at 320-310 Ma. The whole nappe sequence formed during the first tectonometamorphic period (D1) was transported northward over the autochthonous »Deblín polymetamorphic and granitic complex« of Upper Proterozoic age and its Devonian sedimentary cover with very low metamorphism. During this second tectonic event the Brno granite massif (580 Ma) was only marginally incorporated in the Variscan nappe tectonics which resulted in kilometer-scale cover and basement duplexes. The tectonic evolution of the nappe pile ended with stage D3, represented by large- to medium-scale east-vergent folds with limited displacement.

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Zusammenfassung Der Deckenbau am Ostrand der Böhmischen Masse erfolgte in zwei aufeinanderfolgenden Stadien, die sich sowohl in ihrer Kinematik als auch in ihrer Metamorphoseentwicklung deutlich voneinander unterschieden.Die ältere Phase (D1 ca. 350-340 Ma) ist durch synmetamorphe Überschiebungen charakterisiert. Sie führt zu einer metamorphen Inversion der überschobenen Deckeneinheiten, so daß generell hohe metamorphe Einheiten schwach metamorphe tektonisch überlagern. Der Svratka Komplex und das Moldanubikum als hangendste Decken sind durch MP/HT Paragenesen vom Barrow-Typ gekennzeichnet. Beide Einheiten sind auf den MP/MT-metamorphen Bite-Gneis und seine Rahmengesteine überschoben. Die Bílý potok Einheit als liegende Decke zeigt nur noch eine LP/ LT Regionalmetamorphose.Das jüngere Stadium (D2 ca. 320-310 Ma) ist durch eine Thin-skinned Tektonik mit nordvergentem Deckentransport unter LP/LT Bedingungen charakterisiert. Der gesamte, invers metamorphe D1-Deckenstapel wird dabei nach N über den autochtonen Deblín Komplex bzw. seine devonische Sedimenthülle überschoben.Das Brno Granit Massiv (580 Ma) wird nur randlich in diesen variszischen Deckenbau einbezogen. Die tektonische Entwicklung endet mit einem mittel bis großräumigen E-vergenten Faltenbau (D3 phase).

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Résumé L'empilement des nappes a la bordure orientale du Massif de Bohème est caractérisé par deux stades de mise en place présentant différentes évolutions cinématiques et métamorphiques.La tectonique majeure de mise en place des nappes crustales intervient lors d'un métamorphisme de type barrowien, calé autour de 350-340 Ma. L'empilement qui en résulte montre une superposition systématique d'unités à fort degré de métamorphisme sur des unités moins métamorphiques. Ainsi les complexes cristallins, montrant des reliques de métamorphisme de haute à moyenne pression-haute température (unités cristallines de Svratka et du Moldanubien), chevauchent une unité intermédiaire affectée par un métamorphisme de moyenne à basse pression-moyenne température (l'orthogneiss de Bíte et son encaissant). A la base de cette pile édifiée durant la tectonique D1, l'unité des phyllites internes (unité de Bílý potok) est caractérisée par un métamorphisme de basse témperature-basse pression.Le second stade D2 de l'évolution tectonique est caractérisé par une tectonique pelliculaire à vergence nord datée à 320-310 Ma. L'empilement résultant de D1 est ainsi transporté vers le nord, au dessus du complexe autochtone d'âge protérozoïque supérieur (groupe de Deblín) et sa couverture sédimentaire dévonienne très faiblement métamorphisée.Le massif granitique de Brno (580 Ma) n'est que marginalement incorporé à cette tectonique de nappe varisque. Ceci se traduit par des duplex socle-couverture d'échelle plurikilométrique. L'évolution tectonique s'achève lors d'une troisième phase, marquée par de grands plis à vergence est. Le déplacement associé est alors d'amplitude limitée.

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, . , 350-340 . . , , - ( ), , - ( ). , D 1, (- ) - . D 2 , 320-310 ., D 1, , , ( ) . (580 . ) , »« -, . , .

     

New compositional and optical data for antimonian and bismuthian varieties of hemusite from Japan

Summary New compositional and optical data are reported for antimonian and antimonianbismuthian varieties of hemusite from epithermal Au-Ag-Cu deposits in Japan. The empirical formula for the antimonian variety, from the Iriki mine is: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00(S_7.85Se_0.15)_8.00, and that of the Sb-Bi variety from the Kawazu mine is: (Cu_5.84Fe_0.14Ag_0.01)_5.99Mo_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07(S_7.80Se_0.12)_7.92. The theoretical formula of hemusite is Cu⁺ ₄Cu²⁺ ₂MO⁴⁺Sn⁴⁺S₈, whilst the most probable formula of the Iriki hemusite is Cu⁺ _4.5CU²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, with Sb⁵⁺ substituting for Sn⁴⁺ and forming (SbS₄)^3– tetrahedra as might be expected, given that the metal to sulphur ratio is 1, and given the sphalerite-like structure of the mineral. However Bi³⁺ cannot be so accommodated, resulting in a deficiency in (S + Se) for Kawazu hemusite. Reflectance spectra for both are compared with those of the tungsten analogue (compositional) of hemusite, kiddcreekite. The relationship between hemusitesensu stricto and these newly reported varieties is discussed in terms of simple and coupled chemical substitutions, and inferences are drawn on the valency of Sb, Bi, Mo and Cu in the hemusite structure.

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Neue chemische und optische Daten für antimon- und bismuthführende Varietäten von Hemusit aus Japan

Zusammenfassung Neue chemische und optische Daten für antimon- und bismuthführende Hemusite auf epithermalen Au-Ag-Cu Lagerstätten in Japan werden vorgelegt. Die empirische Formel für die antimon-führende Varietät aus der Iriki-Mine ist: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00 (S_7.85Se_0.15)_8.00, und die der Sb-Bi Varietät aus der Kawazu Mine ist: (Cu_5.84Fe_0.14Ag_0.01)_5.99M0_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07 (S_7.80Se_0.12)_7.92. Die theoretische Formel von Hemusit ist Cu⁺ ₄Cu²⁺ ₂Mo⁴⁺Sn⁴⁺S₈, während die wahrscheinlichere Formel für den Hemusit von Iriki Cu⁺ ₄Cu²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, mit Sb⁵⁺ an der Stelle von Sn⁴⁺, das(SbS₄)^3– Tetraeder bildet, wie zu erwarten ist, unter der Voraussetzung, da das Metall zu Schwefelverhältnis 1 und die Struktur sphaleritähnlich ist. Bi³⁺ kann jedoch nicht in dieser Weise untergebracht werden, und das führt zu einem Mangel an (S + Se) für den Hemusit von Kawazu. Die Reflektions-Spektren beider Minerale werden mit denen des Wolfram-Equivalents von Hemusit (Kiddcreekit) verglichen. Die Beziehung zwischen Hemusitsensu stricto und diesen jetzt beschriebenen Varietäten wird auf der Basis einfacher und gekoppelter chemischer Substitution diskutiert. Auf dieser Basis werden Schlüsse auf die Valenz von Sb, Bi Mo und Cu in der Hemusit-Struktur gezogen.