Experimental and theoretical study of hydration of halide ions     

Alexander Likholyot 《Geochimica et cosmochimica acta》2005,69(12):2949-2958

We have studied thermochemistry of the first hydration steps for Cl⁻, Br⁻, and I⁻ in the gas phase both experimentally using high-pressure mass spectrometry (HPMS) and theoretically using density functional theory (DFT) calculations. The highest hydration steps measured experimentally were n = 8 for Cl⁻, n = 7 for Br⁻, and n = 5 for I⁻, all of them being higher than previously reported. Both experimental and theoretical stepwise enthalpies and entropies of hydration for these halides exhibited non-monotonic behavior for successive hydration steps that was not reported in previous HPMS investigations of these reactions. This behavior can be successfully interpreted using halide water cluster geometries obtained from DFT calculations by considering the number of additional hydrogen bonds formed at each hydration step and simultaneous weakening of ion-solvent interaction with increasing cluster size. Results of DFT calculations for surface cluster geometries agree better with experimental results than do the results for interior cluster geometries. We conclude that predominantly surface clusters were observed in our experiments and that small surface clusters have larger number of possible isomers than the interior clusters of the same size. The results for enthalpies of hydration for the studied halide ions lead to the conclusion that ion-solvent interaction is stronger than solvent-solvent interaction for chloride-water clusters. The difference between the two types of interaction diminishes with increasing anion size. The ion-solvent and solvent-solvent interactions are of nearly equal magnitude for iodide.  相似文献   

High‐temperature gold‐copper extraction with chloride flux in lava tubes of Tolbachik volcano (Kamchatka)     

Vadim S. Kamenetsky  Alexander Belousov  Victor V. Sharygin  Liudmila M. Zhitova  Kathy Ehrig  Michael E. Zelenski  Ilya Chaplygin  Marina A. Yudovskaya  Pavel N. Nesterenko  Sergey M. Zakharov 《地学学报》2019,31(6):511-517

Subvolcanic environments in supra‐subduction zones are renowned for hosting epithermal deposits that often contain electrum and native gold, including bonanza examples. This study examined mineral assemblages and processes occurring in shallow‐crust volcanic settings using recent eruption (2012–2013) of the basaltic Tolbachik volcano in the Kamchatka arc. The Tolbachik eruptive system is characterized by an extensive system of lava tubes. After cessation of magma input, the tubes maintained the flow of hot oxidized gases that episodically interacted with the lava surfaces and sulphate‐chloride precipitates from volcanic gases on these surfaces. The gas‐rock interaction had strong pyrometamorphic effects that resulted in the formation of molten salt, oxidized (tenorite, hematite, Cu‐rich magnesioferrite) and skarn‐like silicate mineral assemblages. By analogy with experimental studies, we propose that a combination of these processes was responsible for extraction of metals from the basaltic wall rocks and deposition of Cu‐, Fe‐ and Cu‐Fe‐oxides and native gold.  相似文献   

Primary aragonite and high‐Mg calcite in the late Cambrian (Furongian). Potential evidence from marine carbonates in Oman          下载免费PDF全文

Joyce E. Neilson  Alexander T. Brasier  Colin P. North 《地学学报》2016,28(5):306-315

Transient aragonite seas occurred in the early Cambrian but several models suggest the late Cambrian was a time of calcite seas. Here, evidence is presented from the Andam Group, Huqf High, Oman (Gondwana) that suggests a transient Furongian (late Cambrian) aragonite sea, characterized by the precipitation of aragonite and high‐Mg calcite ooids and aragonite isopachous, fibrous, cements. Stable carbon isotope data suggest that precipitation occurred just before and during the SPICE (Steptoean Positive Carbonate Isotope Excursion). Aragonite and high‐Mg calcite precipitation can be accounted for if mMg:Ca ratios were around 1.2 given the very high atmospheric CO₂ at that time and if precipitation occurred in warm waters associated with the SPICE. This, together with reported occurrences of early Furongian aragonite ooids from various locations in North America (Laurentia), suggests that aragonite and high‐Mg calcite precipitation from seawater may have been more than just a local phenomenon.  相似文献   

Water source dynamics of high Arctic river basins          下载免费PDF全文

Phillip J. Blaen  David M. Hannah  Lee E. Brown  Alexander M. Milner 《水文研究》2014,28(10):3521-3538

Arctic river basins are amongst the most vulnerable to climate change. However, there is currently limited knowledge of the hydrological processes that govern flow dynamics in Arctic river basins. We address this research gap using natural hydrochemical and isotopic tracers to identify water sources that contributed to runoff in river basins spanning a gradient of glacierization (0–61%) in Svalbard during summer 2010 and 2011. Spatially distinct hydrological processes operating over diurnal, weekly and seasonal timescales were characterized by river hydrochemistry and isotopic composition. Two conceptual water sources (‘meltwater’ and ‘groundwater’) were identified and used as a basis for end‐member mixing analyses to assess seasonal and year‐to‐year variability in water source dynamics. In glacier‐fed rivers, meltwater dominated flows at all sites (typically >80%) with the highest contributions observed at the beginning of each study period in early July when snow cover was most extensive. Rivers in non‐glacierized basins were sourced initially from snowmelt but became increasingly dependent on groundwater inputs (up to 100% of total flow volume) by late summer. These hydrological changes were attributed to the depletion of snowpacks and enhanced soil water storage capacity as the active layer expanded throughout each melt season. These findings provide insight into the processes that underpin water source dynamics in Arctic river systems and potential future changes in Arctic hydrology that might be expected under a changing climate. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

An interhemispheric mechanism for glacial abrupt climate change     

Rubén Banderas  Jorge Alvarez-Solas  Alexander Robinson  Marisa Montoya 《Climate Dynamics》2015,44(9-10):2897-2908

  相似文献   

Cenozoic landscape evolution of the Kruger National Park as derived from cosmogenic nuclide analyses          下载免费PDF全文

Christoph Glotzbach  Alexander Paape  Jussi Baade  Bastian Reinwarth  Kate Rowntree  Jordan Miller 《地学学报》2016,28(5):316-322

In contrast to active tectonic settings, little is known about the potential feedback between surface processes and climate change in tectonically inactive cratonic regions. Here, we studied the driving forces of erosion and landscape evolution in the Kruger National Park in South Africa using cosmogenic nuclide dating. ¹⁰Be‐derived catchment‐wide erosion rates (~2 and ~10 mm ka^?1) are similar in magnitude to erosion and rock uplift elsewhere in South Africa, suggesting that (1) rock uplift is solely the isostatic response to erosion and (2) the first‐order topography is likely of Cretaceous age. The topographic maturity is promoted by widespread exposure of rocks resistant to erosion. Our data, however, suggest that local variations in rock resistance lead to transient landscape changes, with local increases in relief and erosion rates.  相似文献   

Spatially controlled Fe and Si isotope variations: an alternative view on the formation of the Torres del Paine pluton     

Norbert?A.?GajosEmail author  Craig?C.?Lundstrom  Alexander?H.?Taylor 《Contributions to Mineralogy and Petrology》2016,171(11):93

We present new Fe and Si isotope ratio data for the Torres del Paine igneous complex in southern Chile. The multi-composition pluton consists of an approximately 1 km vertical exposure of homogenous granite overlying a contemporaneous 250-m-thick mafic gabbro suite. This first-of-its-kind spatially dependent Fe and Si isotope investigation of a convergent margin-related pluton aims to understand the nature of granite and silicic igneous rock formation. Results collected by MC-ICP-MS show a trend of increasing δ⁵⁶Fe and δ³⁰Si with increasing silica content as well as a systematic increase in δ⁵⁶Fe away from the mafic base of the pluton. The marginal Torres del Paine granites have heavier Fe isotope signatures (δ⁵⁶Fe = +0.25 ± 0.02 2se) compared to granites found in the interior pluton (δ⁵⁶Fe = +0.17 ± 0.02 2se). Cerro Toro country rock values are isotopically light in both Fe and Si isotopic systems (δ⁵⁶Fe = +0.05 ± 0.02 ‰; δ³⁰Si = ?0.38 ± 0.07 ‰). The variations in the Fe and Si isotopic data cannot be accounted for by local assimilation of the wall rocks, in situ fractional crystallization, late-stage fluid exsolution or some combination of these processes. Instead, we conclude that thermal diffusion or source magma variation is the most likely process producing Fe isotope ratio variations in the Torres del Paine pluton.  相似文献   

Moving boulders in flash floods and estimating flow conditions using boulders in ancient deposits          下载免费PDF全文

Jan Alexander  Mark J. Cooker 《Sedimentology》2016,63(6):1582-1595

Boulders moving in flash floods cause considerable damage and casualties. More and bigger boulders move in flash floods than predicted from published theory. The interpretation of flow conditions from the size of large particles within flash flood deposits has, until now, generally assumed that the velocity (or discharge) is unchanging in time (i.e. flow is steady), or changes instantaneously between periods of constant conditions. Standard practice is to apply theories developed for steady flow conditions to flash floods, which are however inherently very unsteady flows. This is likely to lead to overestimates of peak flow velocity (or discharge). Flash floods are characterised by extremely rapid variations in flow that generate significant transient forces in addition to the mean‐flow drag. These transient forces, generated by rapid velocity changes, are generally ignored in published theories, but they are briefly so large that they could initiate the motion of boulders. This paper develops a theory for the initiation of boulder movement due to the additional impulsive force generated by unsteady flow, and discusses the implications.  相似文献   

Attribution of extreme temperature changes during 1951–2010     

Yeon-Hee Kim  Seung-Ki Min  Xuebin Zhang  Francis Zwiers  Lisa V. Alexander  Markus G. Donat  Yu-Shiang Tung 《Climate Dynamics》2016,46(5-6):1769-1782

  相似文献   

On the impact of airborne gravity data to fused gravity field models     

Dimitrios Bolkas  Georgia Fotopoulos  Alexander Braun 《Journal of Geodesy》2016,90(6):561-571

  相似文献