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   
47.
Post-Last Glacial Maximum evolution of a “fjord-type” lake based on high-resolution seismic data: the Lago Roca/Acigami (southern Tierra del Fuego,Argentina/Chile)     
Donaldo Mauricio Bran  Jorge Gabriel Lozano  Dario Civile  Emanuele Lodolo  María E. Cerredo  Alejandro Tassone  Luca Baradello  Maurizio Grossi  Juan Vilas 《第四纪科学杂志》2020,35(3):396-409
Lago Roca/Acigami is a “fjord-type” lake located in the southernmost part of South America, in the proximity of the Beagle Channel. A high-resolution seismic survey was carried out to analyse the seismic stratigraphy of the lake and to shed some light on the post-Last Glacial Maximum history of the area. Six seismic units were recognised, and their nature and depositional context were interpreted using seismic stratigraphy and acoustic facies analysis. A buried large ridge was identified within the glacial unit (SU1), interpreted as a frontal moraine that indicates a stabilisation phase. After retreat of the glacier from the basin, the trough was flooded by meltwater and a lake developed (SU2). The seismic facies, from bottom to top, depict a transition from ice-contact (SU2; SU3) to ice-distal proglacial conditions (SU4). A thick draping unit (SU5) marks a marine transgressive event and the instauration of a fjord environment in the basin. The marine transgression was a rapid event preceded by a fall in the lake level that caused an erosional unconformity. During the fjord phase the sedimentation remained controlled by meltwater discharge. Sea level fall, and subsequent disconnection from the Beagle Channel was accompanied by a progradation of the glaciofluvial deltaic sediments and the occurrence of several mass-wasting deposits (SU6). © 2019 John Wiley & Sons, Ltd.  相似文献   
48.
The mafic-ultramafic complex near Finero (Ivrea-Verbano Zone), II. Geochronology and isotope geochemistry   总被引:1,自引:0,他引:1  
Meihua Lu  Albrecht W. Hofmann  Maurizio Mazzucchelli  Giorgio Rivalenti 《Chemical Geology》1997,140(3-4):223-235
Whole-rock Nd and Sr isotopic compositions of the mafic-ultramafic complex near Finero demonstrate that the magma was derived from a depleted, perhaps MORB-type mantle reservoir. The Sm-Nd data for the Amphibole Peridotite unit can be interpreted as an isochron with an apparent age of 533 ± 20 Ma, which is consistent with a 207Pb/206Pb evaporation age of 549 ± 12 Ma of a single zircon grain from the Internal Gabbro unit. However, the interpretation of these apparent ages remains open to question. We therefore retain the alternative hypotheses that the intrusion occurred either about 533 or 270 Ma ago, the latter being the most likely age of emplacement of the much larger magma body near Balmuccia (Val Sesia). The implication of the older emplacement age (if correct) would be that the igneous complex may be related to the numerous amphibolite units, which are intercalated with the metapelites of the overlying Kinzigite Formation, and together with them may constitute an accretionary complex. In this case, the mafic-ultramafic complex itself might also be part of such an accretionary complex (as has been proposed for the Balmuccia peridotite).

Internal Sm-Nd isochrons involving grt, cpx, plag and amph from the Internal Gabbro unit yield concordant ages of 231 ± 23, 226 ± 7, 223 ± 10, 214 ± 17, and 203 ± 13 Ma. These results confirm published evidence for a separate, regional heating event about 215 ± 15 Ma ago.

Initial Nd(533) values average +6.3 ± 0.4 for six samples of the Amphibole Peridotite unit and +6.0 ± 1.2 for ten samples of the External Gabbro unit. 87Sr/86Sr ratios require little or no age correction and range from 0.7026 to 0.7047 (with two outliers at 0.7053 and 0.7071). Strong correlations between 87Sr/86Sr and K2O and weaker correlations between initial Nd and K2O imply a comparatively minor (≤ 10%) contamination of the External Gabbro magma by crustal material and a later alteration by a crustal or seawater-derived fluid. These results contrast sharply with the isotopic composition (negative Nd and high 87Sr/86Sr values) of the associated mantle rocks, the Phlogopite Peridotite unit, which has been pervasively metasomatized by crustal fluids. This type of metasomatism and its isotopic signature are never seen in the magmatic complex. This evidence rules out any direct genetic relationship between the igneous complex and the mantle peridotite. The crust-mantle interaction is the opposite of that seen at Balmuccia, where the mantle peridotite is essentially ‘pristine’ and the magmatic body has been extensively contaminated by assimilation of crustal rocks.  相似文献   

49.
Mineralogy,chemistry, and grain size composition of recent sediments in the northern Tyrrhenian Sea: Contribution to the study of sediment transport and distribution     
Leonardo Leoni  Franco Sartori  Maurizio Saitta  Vincenzo Damiani  Ornella Ferretti  Monique Viel 《Environmental Geology》1991,17(1):23-46
As a contribution to an environmental study on Tuscany's marine shelf, textural, mineralogical, and chemical characteristics of recent sediments in the northern Tyrrhenian Sea between Elba Island and Livorno have been analyzed. The data provide clear information on sediment sources and movement patterns. The main sediment source appears to be the Cecina River; very subordinate is the contribution of the Fine River. As to sediment movement patterns, the surveyed basin appears to be divided into two subbasins: (1) a greater, southern subbasin, bounded by Tuscany mainland, Elba Island and Elba Ridge, and Capraia Isle, and Vada Shoals; and (2) a smaller, northern subbasin, enclosed between Vada Shoals and Meloria Shoals (off Livorno port).In the former the coarse-grade Cecina River sediments are transported southward along most of the mainland coast by littoral drift and coastal current; a northward flowing countercurrent seems to be active only in the southernmost part. Silts and clays are distributed in concentric belts around basin's central part, being transported mainly by slow circular water movements. In the marginal western zone, very little terrigenous influx is coupled with a high biologic productivity, and biogenic debris sedimentation prevails there.In the northern subbasin the sediment contribution from Fine River is more appreciable. Here the environmental energies are very low and the coarse sediments are restricted to a few small pocket beaches where they are deposited by local creeks. Most of the subbasin area is occupied by sapropelitic muds, again distributed by slow small-scale gyres.  相似文献   
50.
Geomaterials related to photovoltaics: a nanostructured Fe-bearing kuramite,Cu<Subscript>3</Subscript>SnS<Subscript>4</Subscript>     
Francesco Di Benedetto  Ilaria Bencistà  Francesco D’Acapito  Silvia Frizzera  Andrea Caneschi  Massimo Innocenti  Alessandro Lavacchi  Giordano Montegrossi  Werner Oberhauser  Maurizio Romanelli  Herbert Dittrich  Luca A. Pardi  Gerold Tippelt  Georg Amthauer 《Physics and Chemistry of Minerals》2016,43(8):535-544
The successful synthesis of nanoparticles of Fe-bearing kuramite, (Cu,Fe)3SnS4, is reported in this study. Nanocrystalline powders were obtained through a mild, environmentally friendly and scalable solvothermal approach, in a single run. The sample was the object of a multidisciplinary investigation, including X-ray diffraction and absorption, scanning electron microscopy and microanalysis, electron paramagnetic resonance, diffuse reflectance and Mössbauer spectroscopy as well as SQUID magnetometry. The nanoparticles consist of pure Fe-bearing kuramite, exhibiting tetragonal structure. The valence state of the metal cations was assessed to be Cu+, Sn4+ and Fe3+. The material presents a band gap value of 1.6 eV, which is fully compatible with solar cell applications. The uptake of Fe by nanokuramite opens a compositional field where the physical properties can be tuned. We thus foster the application of Fe-bearing nanokuramite for photovoltaics and energy storage purposes.  相似文献   
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41.
Mineralogy and Petrology - Limestone represents the main raw material for ordinary Portland cement clinker production. In this study eight natural limestones from different geological environments...  相似文献   
42.
A 1-D General Ocean Turbulence Model that includes the effects of sediment-induced stratification is shown to simulate the observed onshore and offshore migration of a nearshore sandbar. The only two free parameters of the model, the bed reference concentration and the sediment diffusivity, are taken from the literature, rather than tuned to the data used here. The model results suggest that predictions of onshore bar migration, in which wave-induced sediment transport confined to within a few centimeters of the bottom dominates, are not greatly affected by accounting for buoyancy effects. The model results also suggest that both mean flows and waves transport sediment during offshore bar migration, with different components of transport dominating at different cross-shore locations across the bar-trough bathymetry. Neglecting the effects of sediment-induced stratification results in higher model skill during the largest waves, likely because the excess turbulence production simulated by the non-stratified model is counterbalanced by neglected breaking-wave-generated turbulence. Considering both onshore and offshore migration, the model that includes sediment-induced stratification has higher skill than the model without stratification.  相似文献   
43.
A set of raw industrial materials, that is, pure quartz and quartz-rich mixtures, were investigated through electron paramagnetic resonance and electron spin echo-envelope modulation spectroscopies, with the aim of evaluating the effective role played by defect centres and of assessing whether they can be used to monitor changes in the physical properties of quartz powders with reference to their health effects. The obtained results point to two interactions of the Al defect centres with H+, hosted in sites within the channels parallel and perpendicular to the c axis of quartz, respectively. These two Al/H+ (hAl) centres exhibit a weak chemical bond, and their relative amounts appear to be modified/controlled by the thermo-mechanical processes underwent by powders. Indeed, a mechanically promoted inter-conversion between the two kinds of site is suggested. As a consequence, the hAl centres are effective in monitoring even modest activations of powders, through thermal or mechanical processes, and they are also supposed to play a specific, relevant role in quartz reactivity during the considered industrial processes.  相似文献   
44.
An extensive characterisation of the magnetic properties of synthetic powders of kuramite, with formal composition Cu3SnS4, was performed. Powders were investigated through superconducting quantum interference device (SQUID) magnetometry, electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM) and microanalysis. SEM and TEM reveal the presence of nanodimensioned particles. XRPD clearly shows that Cu3SnS4 crystallised in a cubic sphalerite-type structural model, in spite of the stannite-type tetragonal structure described for the natural phase. This difference arises from a full random distribution of cations. Synthetic kuramite nanopowders exhibit a marked paramagnetism, originated by the presence of Cu(II), definitely assessed by EPR measurements. Moreover, the overall magnetic behaviour of the sample cannot be simply ascribed to diluted paramagnetism, and this suggests the presence of strong superexchange interactions among Cu(II) ions even at room temperature. The main consequences of these results are the definitive assessment of the chemical formula Cu(I)2Cu(II)SnS4 and of a random distribution of Cu(II), Cu(I) and Sn(IV) ions within the available tetrahedral sites.  相似文献   
45.
 The study proposes a model by which a thick succession of volcanic tuffs can be zeolitized by alteration of pyroclastic material in the presence of sufficient eruptive water and at temperatures close to water vapour condensation. In the case of phreatomagmatic products, the model simplifies interpretation of problematic deposits that exhibit pronounced vertical and lateral variation in lithification grade. A major feature of the model is that thick zeolitized tuffs can be formed during emplacement of pyroclastic products, in marked contrast to later alteration in an open hydrologic system. Geological, volcanological and mineralogical data for the Neapolitan Yellow Tuff, a widespread trachytic pyroclastic deposit outcropping around Campi Flegrei (Southern Italy), have been used to infer the physico-chemical conditions that determined mineral genesis. This tuff shows a reduction in lithification grade towards the base, top and with distance from the vent and very variable zeolitization within the lithified portion. We suggest that during initial emplacement the erupted products chilled against the ground, inhibiting zeolite crystallization. During rapid deposition of the thick, wet succession thermal insulation allowed the persistence of elevated temperatures for a time sufficient for enhancement of hydration-dissolution processes in the volcanic glass. The highly reactive alkali-trachytic glass quickly buffered the acid pH of the system, favouring phillipsite crystallization followed by chabazite nucleation. The variable zeolite content reflects fluctuating emplacement conditions (e.g. changes in water content and temperature). Cooling of the upper and relatively thin distal deposits inhibited the zeolitization process, thereby preserving the primary unlithified deposit. Received: 25 May 1999 / Accepted: 28 October 1999  相似文献   
46.
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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