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   
88.
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   
89.
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   
90.
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   
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81.
Loess–palaeosol sequences (LPS) represent important records of palaeoenvironmental dynamics throughout the Quaternary. During the Pleistocene's dry and cold phases, the Danube's riverbed was one of the major sources for loess sediments that built up LPS in southern Germany and southeastern Europe. Surprisingly, studies addressing Bavarian LPS along the Danube River often lack actuality. The Attenfeld site was one of them and is often cited as a typical LPS. Nevertheless, the site's previous interpretations are based on a few empirical data and field observations. Considering the site's closeness to the sediment's source area, the Alps, and the region's importance in Middle and Upper Palaeolithic migrational movements, those former renditions needed an evaluation. Therefore, we applied a multi-proxy approach (including analyses of grain-size distribution, element composition, and sediment colour attributes) combined with optically stimulated luminescence. Based on our findings, we conclude that the Attenfeld site's former interpretations might be too generalised. We identified units that were not mentioned by previous studies (e.g. Early Glacial dark greyish horizon). Field observations, sediment characteristics, and age estimates indicate sediment deposition of the dated units partly before MIS 4, which contrasts with previous interpretations. The results further demonstrate how sensitive LPS are to environmental settings and dynamics.  相似文献   
82.
Upper Permian to Lower Triassic coastal plain successions of the Sydney Basin in eastern Australia have been investigated in outcrop and continuous drillcores. The purpose of the investigation is to provide an assessment of palaeoenvironmental change at high southern palaeolatitudes in a continental margin context for the late Permian (Lopingian), across the end‐Permian Extinction interval, and into the Early Triassic. These basins were affected by explosive volcanic eruptions during the late Permian and, to a much lesser extent, during the Early Triassic, allowing high‐resolution age determination on the numerous tuff horizons. Palaeobotanical and radiogenic isotope data indicate that the end‐Permian Extinction occurs at the top of the uppermost coal bed, and the Permo‐Triassic boundary either within an immediately overlying mudrock succession or within a succeeding channel sandstone body, depending on locality due to lateral variation. Late Permian depositional environments were initially (during the Wuchiapingian) shallow marine and deltaic, but coastal plain fluvial environments with extensive coal‐forming mires became progressively established during the early late Permian, reflected in numerous preserved coal seams. The fluvial style of coastal plain channel deposits varies geographically. However, apart from the loss of peat‐forming mires, no significant long‐term change in depositional style (grain size, sediment‐body architecture, or sediment dispersal direction) was noted across the end‐Permian Extinction (pinpointed by turnover of the palaeoflora). There is no evidence for immediate aridification across the boundary despite a loss of coal from these successions. Rather, the end‐Permian Extinction marks the base of a long‐term, progressive trend towards better‐drained alluvial conditions into the Early Triassic. Indeed, the floral turnover was immediately followed by a flooding event in basinal depocentres, following which fluvial systems similar to those active prior to the end‐Permian Extinction were re‐established. The age of the floral extinction is constrained to 252.54 ± 0.08 to 252.10 ± 0.06 Ma by a suite of new Chemical Abrasion Isotope Dilution Thermal Ionization Mass Spectrometry U‐Pb ages on zircon grains. Another new age indicates that the return to fluvial sedimentation similar to that before the end‐Permian Extinction occurred in the basal Triassic (prior to 251.51 ± 0.14 Ma). The character of the surface separating coal‐bearing pre‐end‐Permian Extinction from coal‐barren post‐end‐Permian Extinction strata varies across the basins. In basin‐central locations, the contact varies from disconformable, where a fluvial channel body has cut down to the level of the top coal, to conformable where the top coal is overlain by mudrocks and interbedded sandstone–siltstone facies. In basin‐marginal locations, however, the contact is a pronounced erosional disconformity with coarse‐grained alluvial facies overlying older Permian rocks. There is no evidence that the contact is everywhere a disconformity or unconformity.  相似文献   
83.
利用GIS和遥感技术方法分析了2000—2014年那曲地区植被归一化指数(NDVI)的时空分布特征和变化趋势,探讨了NDVI与几种气象因子的关系。结果表明:空间上,研究区植被NDVI在空间上呈自西向东、自南向北逐步增大,高海拔地区小于低海拔地区的分布特点;时间上,近15a的NDVI总体上呈不显著性下降趋势,NDVI变化可以分为3个阶段,分别为2000—2005年较好,2006—2008年略差,2009—2014年好转。植被面积变化趋势表现为西北部植被处于稳定状态的面积居多,变化较明显的区域集中在中部和东南部地区的人口密集区,改善和退化区域呈现交错出现的特点。那曲地区植被变化的主要影响因素为降水量和热量因素引起的,人类活动在较短时间尺度上对植被也有较大影响。  相似文献   
84.
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   
85.
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   
86.
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   
87.
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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