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   
28.
29.
Cyclic geomagnetic changes in Mid-Cretaceous rhythmites, Italy     
Giovanni Napoleone  Maurizio Ripepe 《地学学报》1989,1(5):437-442
Magnetic secular variation is recorded as a quasi-rhythmical process of uncertain origin. Rhythmic changes recorded in the Scisti a Fucoidi in the central Apennines of Italy, pelagic sediments of Mid-Cretaceous (Late Albian) age, show strong correspondence to patterns of orbital variation. In the same strata cyclic magnetic variations are found with peaks in the same range (105, 40, 26,19 kyr). These results appear to support earlier suggestions that secular variations may be related to these astronomical patterns.  相似文献   
30.
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21.
The analysis procedure proposed by Auer et al. (1977) for deducing magnetic field vectors from Stokes profiles has been tested to investigate the influence of magneto-optical effects on the deduced field parameters. The quality of the fit between synthetic profiles generated with the inclusion of magneto-optical effects and the profiles returned by the inversion routine is also investigated. The results show that magneto-optical effects should be included in the inversion routine especially to increase the accuracy of the deduced, azimuth of the magnetic field.  相似文献   
22.
This article describes an update of the physical models that we use to reconstruct the FUV and EUV irradiance spectra and the radiance spectra of the features that at any given point in time may cover the solar disk depending on the state of solar activity. The present update introduces important modifications to the chromosphere–corona transition region of all models. Also, the update introduces improved and extended atomic data. By these changes, the agreement of the computed and observed spectra is largely improved in many EUV lines important for the modeling of the Earth’s upper atmosphere. This article describes the improvements and shows detailed comparisons with EUV/FUV radiance and irradiance measurements. The solar spectral irradiance from these models at wavelengths longer than ≈?200 nm is discussed in a separate article.  相似文献   
23.
An X-ray absorption spectroscopy (XAS) study of the Fe local environment in natural amethyst (a variety of α-quartz, SiO2) has been carried out. Room temperature measurements were performed at the Fe K-edge (7,112 eV), at both the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions. Experimental results were then compared with DFT calculations. XANES experimental spectra suggest Fe to occur mainly in the trivalent state, although a fraction of Fe2+ is identified. EXAFS spectra, on the other hand, reveal an unusual short distance for the first coordination shell:  = 1.78(2) Å, the coordination number being 2.7(5). These results allow to establish that Fe replaces Si in its tetrahedral site, and that numerous local distortions are occurring as a consequence of the presence of Fe3+ variably compensated by protons and/or alkaline ions, or uncompensated. The formal valence of Fe, on the basis of both experimental and DFT structural features, can be either 4+ or 3+. Taking into account the XANES evidences, we suggest that Fe mainly occurs in the trivalent state, compensated by protons, and that a minor fraction of Fe4+ is stabilised by the favourable local structural arrangement.  相似文献   
24.
Many rivers worldwide are undergoing severe man-induced alterations which are reflected also in changes of the degree of connectivity between surface waters and groundwater. Pollution, irrigation withdrawal, alteration of freshwater flows, road construction, surface water diversion, soil erosion in agriculture, deforestation and dam building have led to some irreversible species losses and severe changes in community composition of freshwater ecosystems. Taking into account the impact of damming and flow diversion on natural river discharge, the present study is aimed at (i) evaluating the effects of anthropogenic changes on groundwater/surface water interactions; (ii) analyzing the fate of nitrogenous pollutants at the floodplain scale; and (iii) describing the overall response of invertebrate assemblages to such changes. Hydrogeological, geochemical and isotopic data revealed short- and long-term changes in hydrology, allowing the assessment of the hydrogeological setting and the evaluation of potential contamination by nitrogen compounds. Water isotopes allowed distinguishing a shallow aquifer locally fed by zenithal recharge and river losses, and a deeper aquifer/aquitard system fed by surrounding carbonate aquifers. This system was found to retain ammonium and, through the shallow aquifer, release it in surface running waters via the hyporheic zone of the riverbed. All these factors influence river ecosystem health. As many environmental drivers entered in action offering a multiple-component artificial environment, a clear relationship between river flow alteration and benthic and hyporheic invertebrate diversity was not found, being species response driven by the combination of three main stressors: ammonium pollution, man-induced changes in river morphology and altered discharge regime.  相似文献   
25.
26.
We present a comprehensive analysis of the ability of current stellar population models to reproduce the optical ( ugriz ) and near-infrared ( JHK ) colours of a small sample of well-studied nearby elliptical and S0 galaxies. We find broad agreement between the ages and metallicities derived using different population models, although different models show different systematic deviations from the measured broad-band fluxes. Although it is possible to constrain simple stellar population models to a well-defined area in age–metallicity space, there is a clear degeneracy between these parameters even with such a full range of precise colours. The precision to which age and metallicity can be determined independently, using only broad-band photometry with realistic errors, is  Δ[Fe/H]≃ 0.18  and  Δlog Age ≃ 0.25  . To constrain the populations and therefore the star formation history further, it will be necessary to combine broad-band optical–IR photometry with either spectral line indices, or else photometry at wavelengths outside this range.  相似文献   
27.
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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