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   
42.
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   
43.
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   
44.
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   
45.
46.
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   
47.
The Ligurian Helminthoid flysch units of the Emilian Apennines: stratigraphic and petrographic features,paleogeographic restoration and structural evolution     
Giovanna Daniele 《Geodinamica Acta》2013,26(5):313-333
Abstract

This work deals with the Cretaceous-Tertiary Helminthoid flysch successions of the Emilian Apennines and related basal complexes (Mt. Caio, Val Baganza, Solignano, Mt. Venere-Monghidoro and Mt. Cassio Units): it is based on an integrated approach which included stratigraphic, petrographic and structural observations. Detailed stratigraphic sections measured in the various successions evidenced the specific features of the different flysch formations. The main framework composition analysis of the arenites pointed out a partly ‘oceanic’ alimentation for the Mt. Caio Flysch Fm; the Mt. Venere-Monghidoro, and Mt. Cassio Flysch Fms have been alimented exclusively by a terrigenous detritus mainly derived from continental basement source areas. The heavy mineral assemblage of the Mt. Caio Flysch Fm is characterized by picotite, that of the Mt. Venere-Monghidoro, Solignano and Mt. Cassio Flysch Fms commonly contains straurolite, garnet and chloritoid, generally considered to be typical products of the Adriatic continental margin. The calcareous nannofossils biostratigraphy indicated that the flysch sedimentation started during the Late Campanian and ended between the Paleocene (Mt. Cassio Flysch Fm and Mt. Venere-Monghidoro Fms) and the Middle Eocene (Mt. Caio Flysch Fm). We propose a schematic paleogeographic restoration for the External Ligurian Domain which implies a more internal position for the Mt. Caio succession and a more external one for the Mt. Venere-Monghidoro and Mt. Cassio successions. The Helminthoid flyschs sedimented after and during deformation and subduction phases in perched and fore-arc basins partly overlying the marginal part of the Adriatic plate. The External Ligurian nappes’ stacking consists, in the study area, from the bottom, of the following units: Caio Unit, Val Baganza Ophiolitic Unit, Monghidoro Unit, Cassio Unit. This pile of thrust-nappes, sealed by the Epiligurian succession, has been already realized before Late Eocene. In our opinion it was generated by a frontal west-verging frontal accretion process (offscraping), which let the flysch successions remain, in this phase, quite undeformed. This westverging thrusting phase, starting from the Middle-Late Eocene, has been followed by an important folding event which generated striking hectometric and kilometric ‘Apenninic’ reverse folds, sometimes associated with NE-verging thrust surfaces. The Oligocene and post-Oligocene evolution is characterized by a block-translation of the Ligurian staking over the Subligurian, Tuscan and Umbrian Domains, associated with a new generation of minor thrusts and thrust related Apenninic folds. © 2000 Éditions scientifiques et médicales Elsevier SAS  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.
Using a regional numerical weather prediction model for GNSS positioning over Brazil     
Daniele Barroca Marra Alves  Luiz Fernando Sapucci  Haroldo Antonio Marques  Eniuce Menezes de Souza  Tayná Aparecida Ferreira Gouveia  Jackes Akira Magário 《GPS Solutions》2016,20(4):677-685
The global navigation satellite system (GNSS) can provide centimeter positioning accuracy at low costs. However, in order to obtain the desired high accuracy, it is necessary to use high-quality atmospheric models. We focus on the troposphere, which is an important topic of research in Brazil where the tropospheric characteristics are unique, both spatially and temporally. There are dry regions, which lie mainly in the central part of the country. However, the most interesting area for the investigation of tropospheric models is the wet region which is located in the Amazon forest. This region substantially affects the variability of humidity over other regions of Brazil. It provides a large quantity of water vapor through the humidity convergence zone, especially for the southeast region. The interconnection and large fluxes of water vapor can generate serious deficiencies in tropospheric modeling. The CPTEC/INPE (Center for Weather Forecasting and Climate Studies/Brazilian Institute for Space Research) has been providing since July 2012 a numerical weather prediction (NWP) model for South America, known as Eta. It has yield excellent results in weather prediction but has not been used in GNSS positioning. This NWP model was evaluated in precise point positioning (PPP) and network-based positioning. Concerning PPP, the best positioning results were obtained for the station SAGA, located in Amazon region. Using the NWP model, the 3D RMS are less than 10 cm for all 24 h of data, whereas the values reach approximately 60 cm for the Hopfield model. For network-based positioning, the best results were obtained mainly when the tropospheric characteristics are critical, in which case an improvement of up to 7.2 % was obtained in 3D RMS using NWP models.  相似文献   
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41.
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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