where k (M− 2 s− 1) can be determined from the
in the pH range 2 to 5, from 5 to 40 °C and 0.01 to 1 M.The effect of pH and ionic strength on the reaction suggest that the rates are due to
where H2A = H2CrO4, HA = HCrO4, H2B = H2SO3 and HB = HSO3. The overall rate expression over the investigated pH range can be determined from
k=kH2A–H2B(αH2A)(αH2B)2+kHA–H2B(αHA)(αH2B)2+kH2A–HB(αH2A)(αHB)2
with kH2A−H2B = 5.0 × 107, kHA–H2B = 1.5 × 106 and kH2A–HB = 6.7 × 107.Fe(III) in the range 1.5 to 20 μM exerts a small catalytic effect on the reaction and significantly lowers the initial concentration of Cr(VI) compared to the nominal value. Contrary to Fe(III), formaldehyde (20 to 200 μM) reacts with S(IV) to form the hydroxymethanesulfonate adduct (CH2OHSO3), which does not react with Cr(VI). Major cations Mg2+ and some minor elements such as Ba2+ and Cu2+ did not affect the rates. The application of this rate law to environmental conditions suggest that this reaction may have a role in acidic solutions (aerosols and fog droplets). This reaction becomes more important in the presence of high Fe(III) and low HMS concentrations, contributing to affect the atmospheric transport of chromium species and the distribution of redox species of chromium, which reach surface water from atmospheric depositions.  相似文献   
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61.
62.
Abstract– The oxygen fugacities recorded in the nakhlites Nakhla, Yamato‐000593 (Y‐000593), Lafayette, and NWA998 were studied by applying the Fe,Ti‐oxide oxybarometer. Oxygen fugacities obtained cluster closely around the FMQ (Fayalite–Magnetite–Quartz) buffer (NWA998 = FMQ ? 0.8; Y‐000593 = FMQ ? 0.7; Nakhla = FMQ; Lafayette = FMQ + 0.1). The corresponding equilibration temperatures are 810 °C for Nakhla and Y‐000593, 780 °C for Lafayette and 710 °C for NWA998. All nakhlites record oxygen fugacities significantly higher and with a tighter range than those determined for Martian basalts, i.e., shergottites whose oxygen fugacities vary from FMQ ? 1 to FMQ ? 4. It has been known for some time that nakhlites are different from other Martian meteorites in chemistry, mineralogy, and crystallization age. The present study adds oxygen fugacity to this list of differences. The comparatively large variation in fO2 recorded by shergottites was interpreted by Herd et al. (2002) as reflecting variable degrees of contamination with crustal fluids that would also carry a light rare earth element (REE)‐enriched component. The high oxygen fugacities and the large light REE enrichment of nakhlites fit qualitatively in this model. In detail, however, it is found that the inferred contaminating phase in nakhlites must have been different from those in shergottites. This is supported by unique 182W/184W and 142Nd/144Nd ratios in nakhlites, which are distinct from other Martian meteorites. It is likely that the differences in fO2 between nakhlites and other Martian meteorites were established very early in the history of Mars. Parental trace element rich and trace element poor regions (reservoirs) of Mars mantle ( Brandon et al. 2000 ) must have been kept isolated throughout Martian history. Our results further show significant differences in closure temperature among the different nakhlites. The observed range in equilibration temperatures together with similar fO2 values is attributable to crystallization of nakhlites in the same cumulate pile or lava layer at different burial depths from 0.5 to 30 m below the Martian surface in agreement with Mikouchi et al. (2003) and is further confirmed by similar crystallization ages of about 1.3 Ga ago (e.g., Misawa et al. 2003 ).  相似文献   
63.
A new analysis of the Doppler tracking data from the Lunar Prospector mission in 1999 revealed a number of previously-unseen gravity anomalies at spatial scales as small as 27 km over the nearside. The tracking data at low altitudes (50 km or below) were better analyzed to resolve the nearside features without dampening from a power law constraint, by partitioning the gravity parameters concentrated on either the nearside or farside. The resulting model presents gravity anomalies correlated with topography with a correlation coefficient of 0.7 or higher from degree 50 to 150, the widest bandwidth yet. The gravity-topography admittance of ∼70 mGal/km is found from numerous craters of which diameters are 60 km or less. In addition, the new model produces orbits that fit to independent radio tracking data from the Lunar Reconnaissance Orbiter and Kaguya (SELENE) better than previous gravity models. This high-resolution model can be of immediate use to geophysical analysis of small craters. Our technique could be applied to an upcoming mission, the Gravity Recovery And Interior Laboratory and useful to extract short wavelength signals from the MESSENGER Doppler data.  相似文献   
64.
65.
Abstract— Northwest Africa (NWA) 1500 is an ultramafic meteorite dominated by coarse (?100–500 μm) olivine (95–96%), augite (2–3%), and chromite (0.6–1.6%) in an equilibrated texture. Plagioclase (0.7–1.8%) occurs as poikilitic grains (up to ?3 mm) in vein‐like areas that have concentrations of augite and minor orthopyroxene. Other phases are Cl‐apatite, metal, sulfide, and graphite. Olivine ranges from Fo 65–73, with a strong peak at Fo 68–69. Most grains are reversezoned, and also have ?10–30 μm reduction rims. In terms of its dominant mineralogy and texture, NWA 1500 resembles the majority of monomict ureilites. However, it is more ferroan than known ureilites (Fo ≥75) and other mineral compositional parameters are out of the ureilite range as well. Furthermore, neither apatite nor plagioclase have ever been observed, and chromite is rare in monomict ureilites. Nevertheless, this meteorite may be petrologically related to the rare augite‐bearing ureilites and represent a previously unsampled part of the ureilite parent body (UPB). The Mn/Mg ratio of its olivine and textural features of its pyroxenes are consistent with this interpretation. However, its petrogenesis differs from that of known augite‐bearing ureilites in that: 1) it formed under more oxidized conditions; 2) plagioclase appeared before orthopyroxene in its crystallization sequence; and 3) it equilibrated to significantly lower temperatures (800–1000 °C, from two‐pyroxene and olivine‐chromite thermometry). Formation under more oxidized conditions and the appearance of plagioclase before orthopyroxene could be explained if it formed at a greater depth on the UPB than previously sampled. However, its significantly different thermal history (compared to ureilites) may more plausibly be explained if it formed on a different parent body. This conclusion is consistent with its oxygen isotopic composition, which suggests that it is an ungrouped achondrite. Nevertheless, the parent body of NWA 1500 may have been compositionally and petrologically similar to the UPB, and may have had a similar differentiation history.  相似文献   
66.
An extensive set of molecular hydrogen observations of centers of southern infrared galaxies is presented. Our data are combined with published infrared and radio observations to investigate the relationship between nuclear and circumnuclear activity. We convert the observational data to absolute luminosities, by applying the known distances. The resulting dataset covers several decades in luminosity for the various parameters, which observe fairly tight correlations. The parameters of our (power law) fits are, at the level of accuracy achieved, not dependent on the type of nuclear activity: while the dataset comprises a mixture of alleged Seyfert, Liner & starburst galaxies, single fits match the complete sample well enough. In particular, non-thermal nuclei (AGN) present in some of the galaxies in the current sample, do not stand out in the parameters we investigated. The absence of a significant dependence on the nuclear type is consistent with the idea that the ever present starbursts energetically dominate a possible ‘AGN in a dusty environment’-component in most galaxy nuclei with infrared excesses.The size of the H2 emitting region is found to be proportional to the square root of the 21 cm radio continuum luminosity. The excitation of the circumnuclear H2 is dominated by shocks. If the H2 extent marks the size of an inner cavity in the dense molecular material surrounding a galaxy nucleus and the radio luminosity is proportional to the mechanical luminosity of (circum)nuclear winds. This result then indicates that the cavity size occurs at constant pressure in the sample galaxies, in accordance with the superwind model by Heckman et al. (1990) [ApJS, 74, 833]. Our results, together with those obtained by others, thus suggest that luminosities and size scales of excited gas associated with active nuclei are dominated by the mechanical energy input. Given the difficulties of uniquely establishing the presence of an AGN, we cannot exclude that (a large fraction of the) infrared luminous galaxies procure part of their radiated energy through accretion onto a massive dark object.F. Duccio Macchetto  相似文献   
67.
ABSTRACT This paper presents high-precision U–Pb ages and initial Hf isotopic compositions of zircon from mafic to felsic rocks of the Kohistan Arc Complex, Pakistan. Three magmatic pulses tapping geochemically different reservoirs are distinguished. Partial melting of mantle with MORB-type isotopic characteristics generated 99–92-Ma-old magmas. Plutonism around 85 Ma tapped a more fertile mantle source, most likely consisting of a >600-Ma-old metasomatically enriched mantle, or of mantle contaminated by an old sedimentary component; 82-Ma-old felsic peraluminous dykes have MORB-type isotopic compositions considered to be inherited from remelting earlier magmas in the deep base of the arc. The isotopic results demonstrate several and rather rapid changes in melt source region during arc development. They also show that there was subordinate continental influence and negligible importance of slab components for the Hf budget during the generation of the Kohistan Arc Complex.  相似文献   
68.
69.
Lake Van is the fourth largest terminal lake in the world (volume 607 km3, area 3570 km2, maximum depth 460 m), extending for 130 km WSW–ENE on the Eastern Anatolian High Plateau, Turkey. The sedimentary record of Lake Van, partly laminated, has the potential to obtain a long and continuous continental sequence that covers several glacial–interglacial cycles (ca 500 kyr). Therefore, Lake Van is a key site within the International Continental Scientific Drilling Program (ICDP) for the investigation of the Quaternary climate evolution in the Near East (‘PALEOVAN’). As preparation for an ICDP drilling campaign, a site survey was carried out during the past years. We collected 50 seismic profiles with a total length of ~850 km to identify continuous undisturbed sedimentary sequences for potential ICDP locations. Based on the seismic results, we cored 10 different locations to water depths of up to 420 m. Multidisciplinary scientific work at positions of a proposed ICDP drill site included measurements of magnetic susceptibility, physical properties, stable isotopes, XRF scans, and pollen and spores. This core extends back to the Last Glacial Maximum (LGM), a more extended record than all the other Lake Van cores obtained to date. Both coring and seismic data do not show any indication that the deepest part of the lake (Tatvan Basin, Ahlat Ridge) was dry or almost dry during past times. These results show potential for obtaining a continuous undisturbed, long continental palaeoclimate record. In addition, this paper discusses the potential of ‘PALEOVAN’ to establish new results on the dynamics of lake level fluctuations, noble gas concentration in pore water of the lake sediment, history of volcanism and volcanic activities based on tephrostratigraphy, and paleoseismic and earthquake activities.  相似文献   
70.
The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔHapp of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression
−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]2
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