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   
86.
Dissociation constants of protonated cysteine species in seawater media     
Virender K. Sharma  Aurelie Moulin  Frank J. Millero  Concetta De Stefano 《Marine Chemistry》2006,99(1-4):52
The dissociation constants (pK1, pK2 and pK3) for cysteine have been measured in seawater as a function of temperature (5 to 45 °C) and salinity (S = 5 to 35). The seawater values were lower than the values in NaCl at the same ionic strength. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been compared to those calculated from the Pitzer ionic interaction model. The lower values of pK3 in the Na–Mg–Cl solutions have been attributed to the formation of Mg2+ complexes with Cys2− anions
Mg2+ + Cys2− = MgCys
The stability constants have been fitted to
after corrections are made for the interaction of Mg2+ with H+.The pK1 seawater measurements indicate that H3Cys+ interacts with SO42−. The Pitzer parameters β0(H3CysSO4), β1(H3CysSO4) and C(H3CysSO4) have been determined for this interaction. The formation of CaCys as well as MgCys are needed to account for the values of pK2 and pK3 in seawater.The consideration of the formation of MgCys and CaCys in seawater yields model calculated values of pK1, pK2 and pK3 that agree with the measured values to within the experimental error of the measurements. This study shows that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.  相似文献   
87.
Experimental impact cratering: A summary of the major results of the MEMIN research unit     
Thomas Kenkmann  Alex Deutsch  Klaus Thoma  Matthias Ebert  Michael H. Poelchau  Elmar Buhl  Eva-Regine Carl  Andreas N. Danilewsky  Georg Dresen  Anja Dufresne  Nathanaël Durr  Lars Ehm  Christian Grosse  Max Gulde  Nicole Güldemeister  Christopher Hamann  Lutz Hecht  Stefan Hiermaier  Tobias Hoerth  Astrid Kowitz  Falko Langenhorst  Bernd Lexow  Hanns-Peter Liermann  Robert Luther  Ulrich Mansfeld  Dorothee Moser  Manuel Raith  Wolf Uwe Reimold  Martin Sauer  Frank Schäfer  Ralf Thomas Schmitt  Frank Sommer  Jakob Wilk  Rebecca Winkler  Kai Wünnemann 《Meteoritics & planetary science》2018,53(8):1543-1568
This paper reviews major findings of the Multidisciplinary Experimental and Modeling Impact Crater Research Network (MEMIN). MEMIN is a consortium, funded from 2009 till 2017 by the German Research Foundation, and is aimed at investigating impact cratering processes by experimental and modeling approaches. The vision of this network has been to comprehensively quantify impact processes by conducting a strictly controlled experimental campaign at the laboratory scale, together with a multidisciplinary analytical approach. Central to MEMIN has been the use of powerful two-stage light-gas accelerators capable of producing impact craters in the decimeter size range in solid rocks that allowed detailed spatial analyses of petrophysical, structural, and geochemical changes in target rocks and ejecta. In addition, explosive setups, membrane-driven diamond anvil cells, as well as laser irradiation and split Hopkinson pressure bar technologies have been used to study the response of minerals and rocks to shock and dynamic loading as well as high-temperature conditions. We used Seeberger sandstone, Taunus quartzite, Carrara marble, and Weibern tuff as major target rock types. In concert with the experiments we conducted mesoscale numerical simulations of shock wave propagation in heterogeneous rocks resolving the complex response of grains and pores to compressive, shear, and tensile loading and macroscale modeling of crater formation and fracturing. Major results comprise (1) projectile–target interaction, (2) various aspects of shock metamorphism with special focus on low shock pressures and effects of target porosity and water saturation, (3) crater morphologies and cratering efficiencies in various nonporous and porous lithologies, (4) in situ target damage, (5) ejecta dynamics, and (6) geophysical survey of experimental craters.  相似文献   
88.
Multivariate analysis of fluorescence and source identification of dissolved organic matter in Jiaozhou Bay, China   总被引:1,自引:0,他引:1  
JIANG Fenghu  YANG Baijuan  LEE Frank Sen-Chun  WANG Xiaoru  CAO Xuan 《海洋学报(英文版)》2009,28(2):60-72
Hierarchical clustering analysis and principal component analysis (PCA) methods were used to assess the similarities and dissimilarities of the entire Excitation-emission matrix spectroscopy (EEMs) data sets of samples collected from Jiaozhou Bay, China. The results demonstrate that multivariate analysis facilitates the complex data treatment and spectral sorting processes, and also enhances the probability to reveal otherwise hidden information concerning the chemical characteristics of the dissolved organic matter (DOM). The distribution of different water samples as revealed by multivariate results has been used to track the movement of DOM material in the study area, and the interpretation is supported by the results obtained from the numerical simulation model of substance tracing technique, which show that the substance discharged by Haibo River can be distributed in Jiaozhou Bay.  相似文献   
89.
Designation of marine protected areas in Belgium: A legal and ecological success?     
Dirk Bogaert  An Cliquet  Frank Maes 《Marine Policy》2009,33(6):878
In Belgium a long process (1999–2005) led to the designation of several marine protected areas (MPAs). In order to analyse the designation process, the ‘policy arrangement approach’ was used as an analytical tool. Attention was given to four dimensions (actors and coalitions, arguments, rules and resources). Particular attention was paid to the switch from an authoritative to a more deliberated policy style in reaction to conflicts with stakeholders. This switch in policy style contributed to a successful legal designation, but does not guarantee the best protection of marine biodiversity. This case study linked science (setting ecological goals) to policy (analysis of a policy process) and led to some more general conclusions on the designation of MPAs and the role of participation in this process.  相似文献   
90.
History and sand budgets of the barrier island system in the Panama City,Florida, region     
Frank Stapor 《Marine Geology》1973,14(4):277-286
Shell Island and Crooked Island peninsulas comprise the Holocene barrier system in the Panama City, Florida, region. Both of these peninsulas have experienced a history of integration-fragmentation-integration superimposed on a net shoreward migration since 1779. Catastrophic events such as hurricanes are most probably responsible for the pass cutting which has fragmented these barriers. Both barrier peninsulas have very nearly segmented St. Andrew Sound into an eastern and western portion. This segmentation has been achieved through natural causes in the eastern or Crooked Island region, but an alternation in the tidal return pattern, effected by the cutting of a canal across Shell Island, is probably responsible for the ongoing segmentation of the western portion.Rates of erosion/deposition, determined by comparing bathymetries charted in 1877, 1930, and 1946, demand that these two peninsulas receive material by eastward transport. Furthermore, the long shore drift of both peninsulas is bidirectional, northwesterly and southeasterly. These two drift components are very nearly equal in magnitude immediately west of Shell Island; net easterly drift occurs on Shell Island peninsula. Crooked Island experiences net westerly and easterly drift; the easterly drift terminates in the Bell Shoal area and does not reach the adjacent St. Joe Spit.  相似文献   
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81.
We constrain the multistage tectonic evolution of the Palaeoproterozoic UHT metamorphic(P=0.9–1.0 GPa,T>1000℃,t=2088–2031 Ma)Bakhuis Granulite Belt(BGB)in Surinam on the Guiana Shield,using large-to small-scale structures,Al-in-hornblende thermobarometry and published fluid inclusion and zircon geochronological data.The BGB forms a narrow,NE–SW striking belt between two formerly connected,~E–W oriented granite-greenstone belts,formed between converging Amazonian and West African continental masses prior to collision and Transamazonian orogeny.Inherited detrital zircon in BGB metasediments conforms agewise to Birimian zircon of West Africa and suggests derivation from the subsequently subducted African passive margin.Ultrahigh-temperature metamorphism may have followed slab break-off and asthenospheric heat advection.Peak metamorphic structures result from layer-parallel shearing and folding,reflecting initial transtensional exhumation of the subducted African margin after slab break-off.A second HT event involves intrusion,at ca.0.49 GPa,of charnockites and metagabbros at 1993–1984 Ma and a layered anorthosite at 1980 Ma,after the BGB had already cooled to<400℃.The event is related to northward subduction under the greenstone belts,along a new active margin to their south.A pronounced syntaxial bend in the new margin points northward towards the BGB and is likely the result of indentation by an anticlinorial flexural bulge of the subducting plate.Tearing of the subducting oceanic plate along this bulge explains why the charnockites are restricted to the BGB.The BGB subsequently experienced doming under an extensional detachment exposed in its southwestern border zone.Exhumation was focused in the BGB as a result of the flexural bulge in the subducting plate and localised heating of the overriding plate by charnockite magmatism.The present,straight NE–SW long-side boundaries of the BGB are superimposed mylonite zones,overprinted by pseudotachylites,previously dated at ca.1200 Ma and 950 Ma,respectively.The 1200 Ma mylonites reflect transpressional popping-up of the BGB,caused by EW-directed intraplate principal compressive stresses from Grenvillian collision preserved under the eastern Andes.Further exhumation of the BGB involved the 950 Ma pseudotachylite decorated faulting,and Phanerozoic faulting along reactivated Meso-and Neoproterozoic lineaments.  相似文献   
82.
This paper provides an overview of the literature on fisheries economics related to uncertainty and asymmetric information. It is argued that uncertainty is relevant in connection with present and future stock sizes and prices, while asymmetric information is important for cost functions, catches, catch per unit of effort, and effort. The literature on uncertainty and asymmetric information can be seen as providing the basis of an argument for using taxes in fisheries management. It is, therefore, surprising that over 55 countries regulate their fisheries with individual quotas, while taxes are not used at all.  相似文献   
83.
The international legal framework for marine spatial planning   总被引:2,自引:1,他引:1  
Frank Maes   《Marine Policy》2008,32(5):797
Increasing demand for ocean resources, both living and non-living, have already lead to loss of biodiversity, habitat depletion and irreversible damage to the marine environment. Furthermore, introduction of new kinds of sea uses, spatial extension of ongoing sea uses and the need to better protect and conserve the marine biological diversity will result in increasing conflicts among the various users, as well as between the users and the environment. Marine spatial planning as a process to allocate space for specific uses can help to avoid user conflicts, to improve the management of marine spatial claims, and to sustain an ecosystem-based management of ocean and seas. This article explores the rights and duties towards exploitation and protection of the marine environment under the jurisdiction of coastal states as reflected in two important global conventions, the United Nations Convention on the Law of the Sea and the Convention on Biological Diversity. Both Conventions provide the main legal framework for marine spatial planning that have to be taken into account in planning at the regional and national level.  相似文献   
84.
Helium and neon distributions are reported for a variety of Stardust comet 81P/Wild 2 samples, including particle tracks and terminal particles, cell surface and subsurface slices from the comet coma and interstellar particle collection trays, and numerous small aerogel blocks extracted from comet cells C2044 and C2086. Discussions and conclusions in several abstracts published during the course of the investigation are included, along with the relevant data. Measured isotope ratios span a broad range, implying a similar range for noble gas carriers in the Wild 2 coma. The meteoritic phase Q‐20Ne/22Ne ratio was observed in several samples. Some of these, and others, exhibit 21Ne excesses too large for attribution to spallation by galactic cosmic ray irradiation, suggesting exposure to a solar proton flux greatly enhanced above current levels in an early near‐Sun environment. Still others display evidence for a solar wind component, particularly one C2086 block with large abundances of isotopically solar‐like helium and neon. Eighty‐nine small aerogel samples were cut from depths up to several millimeters below the cell C2044 surface and several millimeters away from the axis of major track T41. A fraction of these yielded measurable and variable helium and neon abundances and isotope ratios, although none contained visible tracks or carrier particle fragments and their locations were beyond estimated penetration ranges for small particles or ions incident on the cell surface, or for lateral ejecta from T41. Finding plausible emplacement mechanisms and sources for these gases is a significant challenge raised by this study.  相似文献   
85.
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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