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.     

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.     

Na-rich carbonate inclusions in perovskite and calzirtite from the Guli intrusive Ca-carbonatite,polar Siberia

Carbonate phases, some rich in Na₂O and comparatively rich in SrO and BaO, occur as inclusions in perovskite and calzirtite (Ca₂Zr₅Ti₂O₁₆) in the carbonatite of the Guli complex, Siberia. This is the first record of alkali carbonates, akin to nyerereite [Na₂Ca(CO₃)₂], in plutonic igneous rocks. The inclusion populations suggest that the parental magma of the complex was Ca-rich but developed Na-rich differentiates during the latest stages. This points to the dominant calcic carbonatites of the complex not being derivatives of alkali-rich parental carbonatites. These alkali-rich carbonate inclusions (and rare inclusions of djerfisherite) have been preserved due to the resistance of perovskite and calzirtite to processes of leaching, hydrothermal alteration and weathering.     

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.     

Geochemical specialization of the tin-bearing granitoid massifs of NW Bohemia

The geochemistry of Hercynian tin-bearing granitoid massifs of the Krune hory Mts. (Erzgebirge), Slavkovský les Forest (Kaiserwald) and Smriny (eastern Fichtelgebirge) is compared by statistical processing of 270 analyses including a wide spectrum of major and trace elements. Seven different types of granites are distinguished. Out of these, five types represent the successive differentiation of the largest massif of NW Bohemia: the Karlovy Vary (Karlsbad) massif. This comprises strongly differentiated peraluminous granites evolving towards extreme Li-Rb-Cs-F-and Sn-enrichment in the youngest members, which are albite-topaz-zinwaldite lithium granites. The sixth and seventh types are different from the former by their location in the eastern Krune hory and tectonic setting, and they display geochemical features of anorogenic granites: they are metaluminous albite-zinwaldite granites with marked enrichment of Nb, Y, and HREE in addition to Li, Rb, Cs, F and Sn, indicating contamination by sub-crustal material. Sn-W mineralizations, including flat peri-contact greisen bodies, steep greisen veins and tourmalinized phyllites, are all intimately associated with the most strongly differentiated granites — the Li-granite and the Cinovec-granite respectively.     

Evaluation of ferrous and ferric Mössbauer fractions

The Mössbauer fractions f for various ferrous- and/or ferric-containing oxides and oxyhydroxides, silicates and carbonates were evaluated from the experimental temperature dependence of their center shifts, using the Debye approximation for the second-order Doppler shift. It is concluded that ferrous ions exhibit a lower fraction as compared to ferric ions. Using standard mixtures of -Fe₂O₃ with selected Fe²⁺ or Fe³⁺ compounds, it is found that the calculated Fe³⁺ f values are somewhat overestimated with respect to those of Fe²⁺. Possible explanations for this shortcoming are discussed and it is suggested that a different temperature dependence of the intrinsic isomer shift is the most likely reason. This suggestion is corroborated by analyses of hematite and hedenbergite data which are available for temperatures up to 900 K and 800 K respectively.     

Littoral '92

Reports

Littoral '92