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   
43.
Critical appraisal on the identification of Reference Conditions for the evaluation of ecological quality status along the Emilia-Romagna coast (Italy) using M-AMBI   总被引:1,自引:0,他引:1  
Paganelli D  Forni G  Marchini A  Mazziotti C  Occhipinti-Ambrogi A 《Marine pollution bulletin》2011,62(8):1725-256
According to the European Water Framework Directive, the ecological status (ES) of a water body is determined by comparing observation data with undisturbed Reference Conditions (RCs). Defining RCs is crucial when evaluating the ES of a water body as it strongly affects the final outcome of any index application. Identifying RCs by observing real sites is not feasible in many marine environments, such as the Emilia-Romagna coast (Italy, N-Adriatic Sea). We used a statistical approach on a large dataset to derive RCs for the application of the benthic index M-AMBI in this area. We then applied M-AMBI to samples collected along a gradient of presumed environmental disturbance. The results put 14.8% of the Emilia-Romagna samples in “High” ES, 60.2% in “Good”, 23.0% in “Moderate” and 2.0% in “Poor”, showing a spatial gradient of improving quality. These results are in agreement with the extensive ecological knowledge available for this area.  相似文献   
44.
Estimating free parameters in 2D inversion: example of gravity inversion in a rifted basement     
João B.C. Silva  Darcicléa F. Santos  Daniele P. Monteiro 《Geophysical Prospecting》2020,68(3):1057-1071
We advance a principle directed to assigning numerical values to free parameters usually present in inversion methods. It may be formulated as: ‘Optimum estimates of free parameters in an inversion procedure must lead, in tests using synthetic data, to solutions whose geometrical expression reflects the main qualitative or semiquantitative geological characteristic of the study area.’ To this end, the interpreter should (i) specify a typical anomalous source geometry which incorporates the most relevant geological information for the study area, (ii) compute the corresponding gravity anomaly and (iii) invert the anomaly for the source geometry finding the numerical values of the free parameters that lead to a solution closest to the typical source. Application of the above methodology to synthetic and real data from the basement relief of a rift basin has asserted its efficacy.  相似文献   
45.
Magnetic behavior of trioctahedral micas with different octahedral Fe ordering     
Stefano Pini  Maria Franca Brigatti  Marco Affronte  Daniele Malferrari  Augusto Marcelli 《Physics and Chemistry of Minerals》2012,39(8):665-674
This contribution is finalized at the discussion of the magnetic structure of two samples, belonging to phlogopite–annite [sample TK, chemical composition IV(Si2.76Al1.24) VI(Al0.64Mg0.72 $ {\text{Fe}}_{1.45}^{2 + } $ Mn0.03Ti0.15) (K0.96Na0.05) O10.67 (OH)1.31 Cl0.02] and polylithionite–siderophyllite joints [sample PPB, chemical composition IV(Si3.14Al0.86)VI(Al0.75Mg0.01 $ {\text{Fe}}_{1.03}^{2 + } $ $ {\text{Fe}}_{1.03}^{3 + } $ Mn0.01Ti0.01Li1.09) (K0.99Na0.01) O10.00 (OH)0.65F1.35]. Samples differ for Fe ordering in octahedral sites, Fe2+/(Fe2+?+?Fe3+) ratio, octahedral composition, defining a different environment around Fe cations, and layer symmetry. Spin-glass behavior was detected for both samples, as evidenced by the dependency of the temperature giving the peak in the susceptibility curve from the frequency of the applied alternating current magnetic field. The crystal chemical features are associated to the different temperature at which the maximum in magnetic susceptibility is observed: 6?K in TK, where Fe is disordered in all octahedral sites, and 8?K in PPB sample, showing a smaller and more regular coordination polyhedron for Fe, which is ordered in the trans-site and in one of the two cis-sites.  相似文献   
46.
47.
Low-pH waters discharging from submarine vents at Panarea Island (Aeolian Islands,southern Italy) after the 2002 gas blast: Origin of hydrothermal fluids and implications for volcanic surveillance     
Franco Tassi  Bruno Capaccioni  Giorgio Caramanna  Daniele Cinti  Giordano Montegrossi  Luca Pizzino  Fedora Quattrocchi  Orlando Vaselli 《Applied Geochemistry》2009
A geochemical survey of thermal waters collected from submarine vents at Panarea Island (Aeolian Islands, southern Italy) was carried out from December 2002 to March 2007, in order to investigate (i) the geochemical processes controlling the chemical composition of the hydrothermal fluids and (ii) the possible relations between the chemical features of the hydrothermal reservoir and the activity of the magmatic system. Compositional data of the thermal water samples were integrated in a hydrological conceptual model, which describes the formation of the vent fluid by mixing of seawater, seawater concentrated by boiling, and a deep, highly-saline end-member, whose composition is regulated by water-rock interactions at relatively high temperature and shows clear clues of magmatic-related inputs. The chemical composition of concentrated seawater was assumed to be represented by that of the water sample having the highest Mg content. The composition of the deep end-member was instead calculated by extrapolation assuming a zero-Mg end-member. The Na–K–Ca geothermometer, when applied to the thermal end-member composition, indicated an equilibrium temperature of approximately 300 °C, a temperature in agreement with the results obtained by gas-geothermometry.  相似文献   
48.
In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O     
Gennaro Ventruti  Giancarlo Della Ventura  Nicola Corriero  Daniele Malferrari  Alessandro F. Gualtieri  Umberto Susta  Maria Lacalamita  Emanuela Schingaro 《Physics and Chemistry of Minerals》2016,43(8):587-595
The thermal dehydration process of fibroferrite, FeOH(SO4)·5H2O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO4)·4H2O, appearing at about 80 °C due to release of one interstitial H2O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.  相似文献   
49.
Reliability of the automatic procedures for locating earthquakes in southwestern Alps and northern Apennines (Italy)     
Chiara Turino  Paola Morasca  Gabriele Ferretti  Davide Scafidi  Daniele Spallarossa 《Journal of Seismology》2010,14(2):393-411
Reliable automatic procedure for locating earthquake in quasi-real time is strongly needed for seismic warning system, earthquake preparedness, and producing shaking maps. The reliability of an automatic location algorithm is influenced by several factors such as errors in picking seismic phases, network geometry, and velocity model uncertainties. The main purpose of this work is to investigate the performances of different automatic procedures to choose the most suitable one to be applied for the quasi-real-time earthquake locations in northwestern Italy. The reliability of two automatic-picking algorithms (one based on the Characteristic Function (CF) analysis, CF picker, and the other one based on the Akaike’s information criterion (AIC), AIC picker) and two location methods (“Hypoellipse” and “NonLinLoc” codes) is analysed by comparing the automatically determined hypocentral coordinates with reference ones. Reference locations are computed by the “Hypoellipse” code considering manually revised data and tested using quarry blasts. The comparison is made on a dataset composed by 575 seismic events for the period 2000–2007 as recorded by the Regional Seismic network of Northwestern Italy. For P phases, similar results, in terms of both amount of detected picks and magnitude of travel time differences with respect to manual picks, are obtained applying the AIC and the CF picker; on the contrary, for S phases, the AIC picker seems to provide a significant greater number of readings than the CF picker. Furthermore, the “NonLinLoc” software (applied to a 3D velocity model) is proved to be more reliable than the “Hypoellipse” code (applied to layered 1D velocity models), leading to more reliable automatic locations also when outliers (wrong picks) are present.  相似文献   
50.
A model for the viscosity of rhyolite as a function of H2O-content and pressure: A calibration based on centrifuge piston cylinder experiments     
Paola Ardia  Daniele Giordano 《Geochimica et cosmochimica acta》2008,72(24):6103-6123
The Newtonian viscosity of synthetic rhyolitic liquids with 0.15-5.24 wt% dissolved water was determined in the interval between 580 and 1640 °C and pressures of 1 atm and 5-25 kbar. Measurements were performed by combining static and accelerated (up to 1000g) falling sphere experiments on water-bearing samples, with high temperature concentric cylinder experiments on 0.15 wt% H2O melts. These methods allowed viscosity determinations between 102 and 107 Pa s, and cover the complete range of naturally occurring magmatic temperatures, pressures, and H2O-contents for rhyolites.Our viscosity data, combined with those from previous studies, were modeled by an expression based on the empirical Vogel-Fulcher-Tammann equation, which describes viscosities and derivative properties (glass transition temperature Tg, fragility m, and activation volume of viscous flow Va) of silicic liquids as a function of P-T-X(H2O). The fitted expressions do not account for composition-dependent parameters other than X(H2O) and reproduce the entire viscosity database for silicic liquids to within 3.0% average relative error on log η (i.e. std. error of estimate of 0.26 log units).The results yield the expected strong decrease of viscosity with temperature and water content, but show variable pressure dependencies. Viscosity results to be strongly affected by pressure at low pressures; an effect amplified at low temperatures and water contents. Fragility, as a measure for the deviation from Arrhenian behavior, decreases with H2O-content but is insensitive to pressure. Activation volumes are always largely negative (e.g., less than −10 cm3/mol) and increase strongly with H2O-content. Variations in melt structure that may account for the observed property variations are discussed.  相似文献   
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41.
A solution to the fixed-time minimum-fuel two-impulse rendezvous problem for the general non-coplanar elliptical orbits is provided. The optimal transfer orbit is obtained using the constrained multiple-revolution Lambert solution. Constraints consist of lower bound for perigee altitude and upper bound for apogee altitude. The optimal time-free two-impulse transfer problem between two fixed endpoints implies finding the roots of an eighth order polynomial, which is done using a numerical iterative technique. The set of feasible solutions is determined by using the constraints conditions to solve for the short-path and long-path orbits semimajor axis ranges. Then, by comparing the optimal time-free solution with the feasible solutions, the optimal semimajor axis for the two fixed-endpoints transfer is identified. Based on the proposed solution procedure for the optimal two fixed-endpoints transfer, a contour of the minimum cost for different initial and final coasting parameters is obtained. Finally, a numerical optimization algorithm (e.g., evolutionary algorithm) can be used to solve this global minimization problem. A numerical example is provided to show how to apply the proposed technique.  相似文献   
42.
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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