Dynamically Slow Processes in Supercooled Water Confined Between Hydrophobic Plates

We study the dynamics of water confined between hydrophobic flat surfaces at low temperature. At different pressures, we observe different behaviors that we understand in terms of the hydrogen bonds dynamics. At high pressure, the formation of the open structure of the hydrogen bond network is inhibited and the surfaces can be rapidly dehydrated by decreasing the temperature. At lower pressure the rapid ordering of the hydrogen bonds generates heterogeneities that are responsible for strong non-exponential behavior of the correlation function, but with no strong increase of the correlation time. At very low pressures, the gradual formation of the hydrogen bond network is responsible for the large increase of the correlation time and, eventually, the dynamical arrest of the system and of the dehydration process.Comment: 14 pages, 3 figure

Hydrogen-Bonded Liquids: Effects of Correlations of Orientational Degrees of Freedom

We improve a lattice model of water introduced by Sastry, Debenedetti, Sciortino, and Stanley to give insight on experimental thermodynamic anomalies in supercooled phase, taking into account the correlations between intra-molecular orientational degrees of freedom. The original Sastry et al. model including energetic, entropic and volumic effect of the orientation-dependent hydrogen bonds (HBs), captures qualitatively the experimental water behavior, but it ignores the geometrical correlation between HBs. Our mean-field calculation shows that adding these correlations gives a more water-like phase diagram than previously shown, with the appearance of a solid phase and first-order liquid-solid and gas-solid phase transitions. Further investigation is necessary to be able to use this model to characterize the thermodynamic properties of the supercooled region.Comment: 7 pages latex, 3 figures EP

Effect of hydrogen bond cooperativity on the behavior of water

Four scenarios have been proposed for the low--temperature phase behavior of liquid water, each predicting different thermodynamics. The physical mechanism which leads to each is debated. Moreover, it is still unclear which of the scenarios best describes water, as there is no definitive experimental test. Here we address both open issues within the framework of a microscopic cell model by performing a study combining mean field calculations and Monte Carlo simulations. We show that a common physical mechanism underlies each of the four scenarios, and that two key physical quantities determine which of the four scenarios describes water: (i) the strength of the directional component of the hydrogen bond and (ii) the strength of the cooperative component of the hydrogen bond. The four scenarios may be mapped in the space of these two quantities. We argue that our conclusions are model-independent. Using estimates from experimental data for H bond properties the model predicts that the low-temperature phase diagram of water exhibits a liquid--liquid critical point at positive pressure.Comment: 18 pages, 3 figure

Exploring the global scientific literature on urban metabolism

Urban ecosystems can be conceptualized like living organisms supported by material and energy flows that allow the generation of ecosystem structures and functions and the production of goods and services. Urban metabolism accounts for the flows of materials, energy, resources, food, and people in cities, providing a framework for the study of the interactions between natural and socio-economic systems. In this paper, the global scientific literature on urban metabolism was explored to identify knowledge gaps and emerging research areas over the last decades. A bibliometric network analysis was implemented to generate maps based on network data of scientific publications displaying relationships among scientific journals, researchers, countries, and keywords. The total number of publications on urban metabolism from 1990 to 2019 resulted in 498 documents. USA and China resulted the first countries publishing on urban metabolism while among the journals, the Journal of Industrial Ecology and Journal of Cleaner Production resulted the first in the ranking. The co-occurrence network map of keywords showed that, over the last decade, the main focus of research on urban metabolism has shifted from environmental issues to environmental accounting and socio-economic aspects. Considering the importance of urban systems for the achievement of local and global sustainability goals, it is likely that the scientific literature on urban metabolism will continue growing over the next years. Being cities characterized by complex relationships between natural and socio-economic systems, it is desirable that future studies will explore the multidimensional features of urban metabolism through multi-criteria assessment frameworks

Integranular corrosion susceptibility analysis in austeno-ferritic (duplex) stainless steels

Abstract: Austenitic-ferritic stainless steels combine the favorable properties of ferrite and austenite, showing both high mechanical properties and very good corrosion resistance. These steels are characterized by the precipitation of many secondary phases, carbides and nitrides for tempering temperatures between 200 and 1050°C. This phenomenon implies a high susceptibility to localized corrosion, however better than austenitic and ferritic grades. In this work, the susceptibility to intergranular corrosion in of two duplex stainless steel characterized by analogous ferrite/austenite volume fraction was investigated. A "standard" duplex stainless steel SAF 2205 and a "super" duplex stainless steel SAF 2507 were investigated by means of potentiostatic reactivations tests. In addition, chronoamperometric tests and light optical microscope observations of the specimens surfaces were performed in order to analyze the evolution of the corrosion morphologies

More than one dynamic crossover in protein hydration water

Studies of liquid water in its supercooled region have led to many insights into the structure and behavior of water. While bulk water freezes at its homogeneous nucleation temperature of approximately 235 K, for protein hydration water, the binding of water molecules to the protein avoids crystallization. Here we study the dynamics of the hydrogen bond (HB) network of a percolating layer of water molecules, comparing measurements of a hydrated globular protein with the results of a coarse-grained model that has been shown to successfully reproduce the properties of hydration water. With dielectric spectroscopy we measure the temperature dependence of the relaxation time of protons charge fluctuations. These fluctuations are associated to the dynamics of the HB network of water molecules adsorbed on the protein surface. With Monte Carlo (MC) simulations and mean--field (MF) calculations we study the dynamics and thermodynamics of the model. In both experimental and model analyses we find two dynamic crossovers: (i) one at about 252 K, and (ii) one at about 181 K. The agreement of the experiments with the model allows us to relate the two crossovers to the presence of two specific heat maxima at ambient pressure. The first is due to fluctuations in the HB formation, and the second, at lower temperature, is due to the cooperative reordering of the HB network

Assessing natural capital value in the network of Italian marine protected areas: A comparative approach

Marine and coastal natural capital stocks provide a bundle of ecosystem services vital for human well-being. The biophysical and economic assessment of the value of natural capital stocks is much needed for achieving nature conservation goals, while ensuring the sustainable exploitation of marine resources. Marine Protected Areas (MPAs) are increasingly being established worldwide to protect and conserve natural capital stocks from anthropogenic threats. In this study, a biophysical and trophodynamic model based on the emergy accounting method was used to assess the value of natural capital for a set of Italian MPAs. In particular, the assessment focused on four main macro-habitats: 1) sciaphilic hard bottom (SHB), 2) photophilic hard bottom (PHB), 3) soft bottom (SB), and 4) Posidonia oceanica seagrass beds (PSB). The emergy method allowed the assessment of natural capital stocks in terms of direct and indirect solar energy flows invested by nature for their generation. The SHB habitat showed the highest emergy density value in most of the investigated MPAs, confirming the high convergence of input resource flows in the formation of this habitat. When considering extensive indicators, the contribution of the PSB habitat to the total value of natural capital was higher than other habitats in most MPAs. In addition, to facilitate the understanding of the results in socio-economic contexts, the biophysical values of natural capital stocks were converted into monetary units. The total value of natural capital in the investigated MPAs ranged from about 8 to 1163 M€. In conclusion, assessing the value of natural capital can support local managers and policy makers in charge for achieving nature conservation targets while ensuring the sustainable exploitation of natural resources

Trends and evolution in the concept of marine ecosystem services: An overview

The biotic and abiotic assets of the marine environment form the “marine natural capital” embedded in the global ocean. Marine natural capital provides the flow of “marine ecosystem services” that are directly used or enjoyed by people providing benefits to human well-being. They include provisioning services (e.g., food), regulation and maintenance services (e.g., carbon sequestration and storage, and coastal protection), and cultural services (e.g., tourism and recreational benefits). In recent decades, human activities have increased the pressures on marine ecosystems, often leading to ecosystem degradation and biodiversity loss and, in turn, affecting their ability to provide benefits to humans. Therefore, effective management strategies are crucial to the conservation of healthy and diverse marine ecosystems and to ensuring their long-term generation of goods and services. Biophysical, economic, and sociocultural assessments of marine ecosystem services are much needed to convey the importance of natural resources to managers and policy makers supporting the development and implementation of policies oriented for the sustainable management of marine resources. In addition, the accounting of marine ecosystem service values can be usefully complemented by their mapping to enable the identification of priority areas and management strategies and to facilitate science–policy dialogue. Given this premise, this study aims to review trends and evolution in the concept of marine ecosystem services. In particular, the global scientific literature on marine ecosystem services is explored by focusing on the following main aspects: the definition and classification of marine ecosystem services; their loss due to anthropogenic pressures, alternative assessment, and mapping approaches; and the inclusion of marine ecosystem services into policy and decision-making processes