Diffuse radiation,twilight, and photochemistry — I

A photochemical scheme which includes a detailed treatment of multiple scattering up to solar zenith angles of 96° (developed for use in a GCM) has been used to study partitioning within chemical families. Attention is drawn to the different zenith angle dependence of diffuse radiation for the two spectral regions <310 nm and >310 nm. The effect that this has on the so-called 40 km ozone problem is discussed. The importance of correctly including multiple scattering for polar ozone studies is emphasised.     

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.     

Flow directions in ash-flow tuffs: a comparison of geological and magnetic susceptibility measurements, Tshirege member (upper Bandelier Tuff), Valles caldera, New Mexico, USA

This study concludes that the elongation axis (K ₁) of the ellipsoid of anisotropic magnetic susceptibility (AMS) is a suitable proxy for flow axis in ashflow tuffs. 153 oriented samples (176 specimens) were studied from 18 sites in the 1.1 Ma Tshirege member of the Bandelier Tuff. These sites are distributed around the Valles caldera at distances of 5–25 km outside of the rim.K ₁ axes correlate well with postulated radial flow axes at 13 sites.K ₁ also agrees with measured geological flow indicators, mainly imbricated larger clasts, at 7 sites. At 2 of the 5 sites where significant disagreement is seen between theoretical radial flow directions and measuredK ₁ axes, theK ₁ axes correspond well with geological flow indicators, indicating that the divergence of flow from the predicted radial flow pattern is real. Two major topographic buttresses are suggested as the cause of flow divergence for the Tshirege ash flows: the San Pedro buttress northwest of the caldera, and the San Miguel buttress in the southeast. In situK ₁ axes plunge about 7° toward the source at two-thirds of the sites; therefore the plunge ofK ₁ is a plausible in situ indicator for thedirection of flow. Multiple flow zones in sections of several meters thickness indicate changes of flow direction that are both rapid and large during ash-flow emplacement. These observations raisre the question of how best to represent mean flow directions in ash-flow sheets: by eigenvector methods, by vector-sum methods, or by modes. A method for measuring imbrication of larger clasts using apparent dips in vertical joints is outlined. Imbrication, determined in this way at one-third of the sites, dips toward the source, i.e., up-flow. The minimum (K ₃) axis of the AMS ellipsoid correlates with the flow foliation rather than with the larger clast imbrication. The flow axes of ash flows correspond with theK ₁ axes, not with the declination ofK ₃ axes as suggested by some authors. Initial dip of the sampled ash flows is not large and does not affect the paleomagnetic remanence direction, which is reversed with a mean ofD=173.5°,I=-38.4°, ₉₅=3.4°N=18. This mean is not different at the 95% confidence level from that of earlier workers. The mean pole, at 098.0°E, 74.8°N,A ₉₅=3.3°,N=18, is about 15° far-sided relative to the expected time-averaged geomagnetic pole, suggesting a history of emplacement too short to adequately average secular variation.     

Anelasticity of the crust and upper mantle beneath north and central India from the inversion of observed Love and Rayleigh wave attenuation data

The fundamental mode Love and Rayleigh waves generated by earthquakes occurring in Kashmir, Nepal Himalaya, northeast India and Burma and recorded at Hyderabad, New Delhi and Kodaikanal seismic stations are analysed. Love and Rayleigh wave attenuation coefficients are obtained at time periods of 15–100 seconds, using the spectral amplitude of these waves for 23 different paths along northern (across Burma to New Delhi) and central (across Kashmir, Nepal Himalaya and northeast India to Hyderabad and Kodaikanal) India. Love wave attenuation coefficients are found to vary from 0.0003 to 0.0022 km^–1 for northern India and 0.00003 km^–1 to 0.00016 km^–1 for central India. Similarly, Rayleigh wave attenuation coefficients vary from 0.0002 km^–1 to 0.0016 km^–1 for northern India and 0.00001 km^–1 to 0.0009 km^–1 for central India. Backus and Gilbert inversion theory is applied to these surface wave attenuation data to obtainQ ^–1 models for the crust and uppermost mantle beneath northern and central India. Inversion of Love and Rayleigh wave attenuation data shows a highly attenuating zone centred at a depth of 20–80 km with lowQ for northern India. Similarly, inversion of Love and Rayleigh wave attenuation data shows a high attenuation zone below a depth of 100 km. The inferred lowQ value at mid-crustal depth (high attenuating zone) in the model for northern India can be by underthrusting of the Indian plate beneath the Eurasian plate which has caused a low velocity zone at this shallow depth. The gradual increase ofQ ^–1 from shallow to deeper depth shows that the lithosphere-asthenosphere boundary is not sharply defined beneath central India, but rather it represents a gradual transformation, which starts beneath the uppermost mantle. The lithospheric thickness is 100 km beneath central India and below that the asthenosphere shows higher attenuation, a factor of about two greater than that in the lithosphere. The very lowQ can be explained by changes in the chemical constitution taking place in the uppermost mantle.     

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.     

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: