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   
54.
Potentially modified hydropower production under climate change in the Italian Alps     
Giovanni Martino Bombelli  Andrea Soncini  Alberto Bianchi  Daniele Bocchiola 《水文研究》2019,33(17):2355-2372
We present an assessment of the potential impacts of climate change on hydropower production within a paradigmatic, very highly exploited cryospheric area of upper Valtellina valley in the Italian Alps. Based on dependable and unique hydrological measures from our high‐altitude hydrometric network Idrostelvio during 2006–2015, we set up the Poly‐Hydro model to mimic the cryospheric processes driving hydrological flow formation in this high‐altitude area. We then set up an optimization tool, which we call Poly‐Power, to maximize the revenue of the plant manager under given hydrological regimes, namely, by proper operation of the hydroelectric production scheme (reservoirs, pipelines, and power plants) of the area. We then pursue hydrological projections until 2100, feeding Poly‐Hydro with the downscaled outputs of three general circulation models from the Intergovernmental Panel on Climate Change Fifth Assessment Report, under the scenarios Representative Concentration Pathway (RCP) 2.6, RCP 4.5, and RCP 8.5. We assess hydrological flows in two reference decades, that is, at half century (2040–2049), and end of century (2090–2099). We then feed the so obtained hydrological scenarios as inputs to Poly‐Power, and we project future production of hydroelectric power, with and without reoperation of the system. The average annual stream flows for hydropower production decreases along the century under our scenarios (?21 to +7%, on average ? 5% at half century; ?17 to ?2%, average ? 8%, end of century), with ice cover melting unable to offset such decrease. Reduction in snowfall and increase in liquid rainfall are the main factors affecting the modified hydrological regime. Energy production (and revenues) at half century may increase under our scenarios (?9 to +15%, +3% on average). At the end of century in spite of a projected increase on average (?7 to +6%, +1% on average), under the warmest scenario RCP 8.5 decrease of energy production is consistently projected (?4% on average). Our results provide an array of potential scenarios of modified hydropower production under future climate change and may be used for brain storming of adaptation strategies.  相似文献   
55.
High-Frequency Response of the Atmospheric Electric Potential Gradient Under Strong and Dry Boundary-Layer Convection     
Ricardo Conceição  Hugo Gonçalves Silva  Alec Bennett  Rui Salgado  Daniele Bortoli  Maria João Costa  Manuel Collares Pereira 《Boundary-Layer Meteorology》2018,166(1):69-81
The spectral response of atmospheric electric potential gradient gives important information about phenomena affecting this gradient at characteristic time scales ranging from years (e.g., solar modulation) to fractions of a second (e.g., turbulence). While long-term time scales have been exhaustively explored, short-term scales have received less attention. At such frequencies, space-charge transport inside the planetary boundary layer becomes a sizeable contribution to the potential gradient variability. For the first time, co-located (Évora, Portugal) measurements of boundary-layer backscatter profiles and the 100-Hz potential gradient are reported. Five campaign days are analyzed, providing evidence for a relation between high-frequency response of the potential gradient and strong dry convection.  相似文献   
56.
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   
57.
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59.
Tropicality,the unruly Atlantic and social utopias: the French explorer Henri Coudreau (1859 − 1899)          下载免费PDF全文
Federico Ferretti 《Singapore journal of tropical geography》2017,38(3):332-349
This paper addresses the works of Henri Coudreau, a little‐known French explorer of Guiana and Amazonia who was later forgotten by the ‘heroic’ histories of exploration because of his unruliness and nonconformist attitudes. Drawing on the literature of postcolonialism and tropicality as well as on recent studies of anti‐colonialist geographies, I address for the first time Coudreau's geography from the perspective of anarchist and critical thinking. My main argument is that Coudreau's work is a further example of the complexity and heterogeneity of the European intellectual field during the imperial age. Despite having come of age intellectually among all the European racist and ethnocentric prejudices of his day, Coudreau developed a different outlook thanks to two factors, viz., his personal experience in living for years with the indigenous communities of Amazonia, and his exposure to anarchist anti‐colonialist ideas through his collaboration with Elisée Reclus. Coudreau's tropical utopia of an independent Amazonia, and his endorsement of the stateless nature of local communities, ran counter to French imperial politics, occasioning Coudreau's dismissal from the French administration and his professional exile in Brazil at the time of the Franco‐Brazilian border dispute (1897?1900).  相似文献   
60.
Buckling of ring stiffened domes under external hydrostatic pressure     
Carl T. F. Ross  Andrew P. F. Little  Leonidas Chasapides  Jeff Banks  Daniele Attanasio 《Ocean Engineering》2004,31(2):239-252
The paper reports on the buckling of three ring-stiffened prolate domes under external hydrostatic pressure. The study was partly theoretical and partly experimental, where in the case of the latter, the finite element was used. Comparison between experiment and theory was good. The effect of ring stiffening the domes was to increase their buckling resistances by factors varying from 4.43 to 5.72.  相似文献   
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51.
Controls on event runoff coefficients in the eastern Italian Alps   总被引:3,自引:0,他引:3  
Analyses of event runoff coefficients provide essential insight on catchment response, particularly if a range of catchments and a range of events are compared by a single indicator. In this study we examine the effect of climate, geology, land use, flood types and initial soil moisture conditions on the distribution functions of the event runoff coefficients for a set of 14 mountainous catchments located in the eastern Italian Alps, ranging in size from 7.3 to 608.4 km2. Runoff coefficients were computed from hourly precipitation, runoff data and estimates of snowmelt. A total of 535 events were analysed over the period 1989–2004. We classified each basin using a “permeability index” which was inferred from a geologic map and ranged from “low” to “high permeability”. A continuous soil moisture accounting model was applied to each catchment to classify ‘wet’ and ‘dry’ initial soil moisture conditions. The results indicate that the spatial distribution of runoff coefficients is highly correlated with mean annual precipitation, with the mean runoff coefficient increasing with mean annual precipitation. Geology, through the ‘permeability index’, is another important control on runoff coefficients for catchments with mean annual precipitation less than 1200 mm. Land use, as indexed by the SCS curve number, influences runoff coefficient distribution to a lesser degree. An analysis of the runoff coefficients by flood type indicates that runoff coefficients increase with event snowmelt. Results show that there exists an intermediate region of subsurface water storage capacity, as indexed by a flow–duration curve-based index, which maximises the impact of initial wetness conditions on the runoff coefficient. This means that the difference between runoff coefficients characterised by wet and dry initial conditions is negligible both for basins with very large storage capacity and for basins with small storage capacity. For basins with intermediate storage capacities, the impact of the initial wetness conditions may be relatively large.  相似文献   
52.
The properties of the waters that move from the Pacific to the Indian Ocean via passages in the Indonesian archipelago are observed to vary with along-flow-path distance. We study an ocean model of the Indonesian Seas with reference to the observed water property distributions and diagnose the mechanisms and magnitude of the water mass transformations using a thermodynamical methodology. This model includes a key parameterization of mixing due to baroclinic tidal dissipation and simulates realistic water property distributions in all of the seas within the archipelago. A combination of air–sea forcing and mixing is found to significantly change the character of the Indonesian Throughflow (ITF). Around 6 Sv (approximately 1/3 the model net ITF transport) of the flow leaves the Indonesian Seas with reduced density. Mixing transforms both the intermediate depth waters (transforming 4.3 Sv to lighter density) and the surface waters (made denser despite the buoyancy input by air–sea exchange, net transformation?=?2 Sv). The intermediate transformation to lighter waters suggests that the Indonesian transformation contributes significantly to the upwelling of cold water in the global conveyor belt. The mixing induced by the wind is not driving the transformation. In contrast, the baroclinic tides have a major role in this transformation. In particular, they are the only source of energy acting on the thermocline and are responsible for creating the homostad thermocline water, a characteristic of the Indonesian outflow water. Furthermore, they cool the sea surface temperature by between 0.6 and 1.5°C, and thus allow the ocean to absorb more heat from the atmosphere. The additional heat imprints its characteristics into the thermocline. The Indonesian Seas cannot only be seen as a region of water mass transformation (in the sense of only transforming water masses in its interior) but also as a region of water mass formation (as it modifies the heat flux and induced more buoyancy flux). This analysis is complemented with a series of companion numerical experiments using different representations of the mixing and advection schemes. All the different schemes diagnose a lack of significant lateral mixing in the transformation.  相似文献   
53.
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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