Dissociation constants of protonated cysteine species in seawater media

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.     

Helium and neon in comet 81P/Wild 2 samples from the NASA Stardust mission

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.     

Uncertainty and asymmetric information: An overview

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.     

The international legal framework for marine spatial planning

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.     

Designation of marine protected areas in Belgium: A legal and ecological success?

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.     

Multivariate analysis of fluorescence and source identification of dissolved organic matter in Jiaozhou Bay, China

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.     

Experimental impact cratering: A summary of the major results of the MEMIN research unit

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.     

Better air for better health: Forging synergies in policies for energy access,climate change and air pollution

Air pollution and its related health impacts are a global concern. This paper addresses how current policies on air pollution, climate change and access to clean cooking fuels can effectively reduce both outdoor and household air pollution and improve human health. A state of the art modeling framework is used that combines an integrated assessment model and an atmospheric model to estimate the spatial extent and distribution of outdoor air pollution exposures. Estimates of household energy access and use are modeled by accounting for heterogeneous household energy choices and affordability constraints for rural and urban populations spanning the entire income distribution. Results are presented for 2030 for a set of policy scenarios on air pollution, climate change and energy access and include spatially explicit emissions of air pollutants; ambient concentrations of PM2.5; and health impacts in terms of disability adjusted life years (DALYs) from both ambient and household air pollution. The results stress the importance of enforcing current worldwide air quality legislation in addressing the impacts of outdoor air pollution. A combination of stringent policies on outdoor air pollution, climate change and access to clean cooking fuels is found to be effective in achieving reductions in average ambient PM2.5 exposures to below World Health Organization recommended levels for a majority of the world's population and results in a significant decline in the global burden of disease from both outdoor and household air pollution.     

The Gibbs method and Duhem's theorem: The quantitative relationships among P,T, chemical potential,phase composition and reaction progress in igneous and metamorphic systems

The Gibbs method permits simultaneous evaluation of the relationships among all intensive thermodynamic variables of a heterogeneous system in equilibrium. Addition of mass balance constraints permits simultaneous evaluation of both intensive and extensive variables so that changes in phase chemistry and modes may be monitored. Assumption of closed system behavior results in a system of equations with two degrees of freedom, regardless of the thermodynamic variance, as specified by Duhem's theorem. Open system behavior increases the number of degrees of freedom by the number of components to which the system is open. The methodology presented is therefore a formal statement of the constraints among the differential of all of the intensive and extensive variables of a heterogeneous system.Examples of the application of this formalism include contouring pressure-temperature space for mineral composition, modal changes and reaction progress; contouring reaction space with pressure, temperature and mineral composition; and calculation of compositional and modal changes of phases for prescribed changes in pressure and temperature, as, for example, in the calculation of synthetic garnet zoning profiles or liquid lines of descent in crystallizing magmas.     

Chromium(VI) reduction by sulphur(IV) in aqueous solutions

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 ΔH_app 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