Dynamic treatment of vibrational energy relaxation in a heterogeneous and fluctuating environment

A computational approach to describe the energy relaxation of a high-frequency vibrational mode in a fluctuating heterogeneous environment is outlined. Extending previous work [H. Fujisaki, Y. Zhang, and J.E. Straub, J. Chem. Phys. {\bf 124}, 144910 (2006)], second-order time-dependent perturbation theory is employed which includes the fluctuations of the parameters in the Hamiltonian within the vibrational adiabatic approximation. This means that the time-dependent vibrational frequencies along an MD trajectory are obtained via a partial geometry optimization of the solute with fixed solvent and a subsequent normal mode calculation. Adopting the amide I mode of N-methylacetamide in heavy water as a test problem, it is shown that the inclusion of dynamic fluctuations may significantly change the vibrational energy relaxation. In particular, it is found that relaxation occurs in two phases, because for short times ($\lesssim$ 200 fs) the spectral density appears continuous due to the frequency-time uncertainty relation, while at longer times the discrete nature of the bath becomes apparent. Considering the excellent agreement between theory and experiment, it is speculated if this behavior can explain the experimentally obtained biphasic relaxation the amide I mode of N-methylacetamide.Comment: 24 pages, 7 figures, submitted to J. Chem. Phy

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

Fixed nitrogen is an essential chemical building block for plant and animal protein, which makes ammonia (NH3) a central component of synthetic fertilizer for the global production of food and biofuels. A global project on artificial photosynthesis may foster the development of production technologies for renewable NH3 fertilizer, hydrogen carrier and combustion fuel. This article presents an alternative path for the production of NH3 from nitrogen, water, and solar energy. The process is based on a thermochemical redox cycle driven by concentrated solar process heat at 700-1200°C that yields NH3 via the oxidation of a metal nitride with water. The metal nitride is recycled via solar-driven reduction of the oxidized redox material with nitrogen at atmospheric pressure. We employ electronic structure theory for the rational high-throughput design of novel metal nitride redox materials and to show how transition-metal doping controls the formation and consumption of nitrogen vacancies in metal nitrides. We confirm experimentally that iron doping of manganese nitride increases the concentration of nitrogen vacancies compared to no doping. The experiments are rationalized through the average energy of the dopant d-states, a descriptor for the theory-based design of advanced metal nitride redox materials to produce sustainable solar thermochemical ammonia

Anti-microbial Use in Animals: How to Assess the Trade-offs

Antimicrobials are widely used in preventive and curative medicine in animals. Benefits from curative use are clear – it allows sick animals to be healthy with a gain in human welfare. The case for preventive use of antimicrobials is less clear cut with debates on the value of antimicrobials as growth promoters in the intensive livestock industries. The possible benefits from the use of antimicrobials need to be balanced against their cost and the increased risk of emergence of resistance due to their use in animals. The study examines the importance of animals in society and how the role and management of animals is changing including the use of antimicrobials. It proposes an economic framework to assess the trade-offs of anti-microbial use and examines the current level of data collection and analysis of these trade-offs. An exploratory review identifies a number of weaknesses. Rarely are we consistent in the frameworks applied to the economic assessment anti-microbial use in animals, which may well be due to gaps in data or the prejudices of the analysts. There is a need for more careful data collection that would allow information on (i) which species and production systems antimicrobials are used in, (ii) what active substance of antimicrobials and the application method and (iii) what dosage rates. The species need to include companion animals as well as the farmed animals as it is still not known how important direct versus indirect spread of resistance to humans is. In addition, research is needed on pricing antimicrobials used in animals to ensure that prices reflect production and marketing costs, the fixed costs of anti-microbial development and the externalities of resistance emergence. Overall, much work is needed to provide greater guidance to policy, and such work should be informed by rigorous data collection and analysis systems

Livestock to 2020: The next food revolution

A team of researchers from the International Food Policy Research Institute (IFPRI), the Food and Agricultural Organization of the United Nations (FAO), and the International Livestock Research Institute (ILRI) collaborated to produce this comprehensive and even-handed attempt at defining the nature, extent scope, and implications of what they term the "Livestock Revolution" in developing countries. Looking forward to 2020, they argue convincingly that the structural shifts in world agriculture being brought about by shifts in developing country demand for foods of animal origin will continue and that increasingly global markets have the ability to supply both cereal and animal products in desired quantities without undue price rises. Topics of discussion include livestock revolution, recent transformation of livestock food demand; accompanying transformation of livestock supply; projections of future demand and supply to 2020; implications of the livestock revolution for world trade and food prices; nutrition, food security, and poverty alleviation; environmental sustainability; public health, technology needs and prospects; and taking stock and moving forward

Seasonality constraints to livestock grazing intensity

Increasing food production is essential to meet the future food demand of a growing world population. In the light of pressing sustainability challenges like climate change and the importance of the global livestock system for food security as well as GHG emissions, finding ways to increasing food production sustainably and without increasing competition for food crops is essential. Yet, many unknowns relate to livestock grazing, in particular grazing intensity, an essential variable to assess the sustainability of livestock systems. Here we explore ecological limits to grazing intensity (GI; i.e., the fraction of Net Primary Production consumed by grazing animals) by analysing the role of seasonality in natural grasslands. We estimate seasonal limitations to GI by combining monthly Net Primary Production data and a map of global livestock distribution with assumptions on the length of non-favourable periods that can be bridged by livestock (e.g., by browsing dead standing biomass, storage systems or biomass conservation). This allows us to derive a seasonality-limited potential GI, which we compare with the GI prevailing in 2000. We find that GI in 2000 lies below its potential on 39% of the total global natural grasslands, which has a potential for increasing biomass extraction of up to 181 MtC/yr. In contrast, on 61% of the area GI exceeds the potential, made possible by management. Mobilizing this potential could increase milk production by 5%, meat production by 4%, or contribute to free up to 2.8 Mio km² of grassland area at the global scale if the numerous socio-ecological constraints can be overcome. We discuss socio-ecological trade-offs, which may reduce the estimated potential considerably and require the establishment of sound monitoring systems and an improved understanding of livestock system’s role in the Earth system

Cloud microphysical effects of turbulent mixing and entrainment

Turbulent mixing and entrainment at the boundary of a cloud is studied by means of direct numerical simulations that couple the Eulerian description of the turbulent velocity and water vapor fields with a Lagrangian ensemble of cloud water droplets that can grow and shrink by condensation and evaporation, respectively. The focus is on detailed analysis of the relaxation process of the droplet ensemble during the entrainment of subsaturated air, in particular the dependence on turbulence time scales, droplet number density, initial droplet radius and particle inertia. We find that the droplet evolution during the entrainment process is captured best by a phase relaxation time that is based on the droplet number density with respect to the entire simulation domain and the initial droplet radius. Even under conditions favoring homogeneous mixing, the probability density function of supersaturation at droplet locations exhibits initially strong negative skewness, consistent with droplets near the cloud boundary being suddenly mixed into clear air, but rapidly approaches a narrower, symmetric shape. The droplet size distribution, which is initialized as perfectly monodisperse, broadens and also becomes somewhat negatively skewed. Particle inertia and gravitational settling lead to a more rapid initial evaporation, but ultimately only to slight depletion of both tails of the droplet size distribution. The Reynolds number dependence of the mixing process remained weak over the parameter range studied, most probably due to the fact that the inhomogeneous mixing regime could not be fully accessed when phase relaxation times based on global number density are considered.Comment: 17 pages, 10 Postscript figures (figures 3,4,6,7,8 and 10 are in reduced quality), to appear in Theoretical Computational Fluid Dynamic

Photodissociation dynamics of the iodide-uracil (I-U) complex

Photofragment action spectroscopy and femtosecond time-resolved photoelectron imaging are utilized to probe the dissociation channels in iodide-uracil (I− ⋅ U) binary clusters upon photoexcitation. The photofragment action spectra show strong I− and weak [U- H]− ion signal upon photoexcitation. The action spectra show two bands for I− and [U- H]− production peaking around 4.0 and 4.8 eV. Time-resolved experiments measured the rate of I− production resulting from excitation of the two bands. At 4.03 eV and 4.72 eV, the photoelectron signal from I− exhibits rise times of 86 ± 7 ps and 36 ± 3 ps, respectively. Electronic structure calculations indicate that the lower energy band, which encompasses the vertical detachment energy (4.11 eV) of I−U, corresponds to excitation of a dipole-bound state of the complex, while the higher energy band is primarily a π-π∗ excitation on the uracil moiety. Although the nature of the two excited states is very different, the long lifetimes for I− production suggest that this channel results from internal conversion to the I− ⋅ U ground state followed by evaporation of I−. This hypothesis was tested by comparing the dissociation rates to Rice-Ramsperger-Kassel-Marcus calculations

Feeding the Worlth Healthily: the Challenge of Measuring the effects of Agriculture on Health

Agricultural production, food systems and population health are intimately linked. While there is a strong evidence base to inform our knowledge of what constitutes a healthy human diet, we know little about actual food production or consumption in many populations and how developments in the food and agricultural system will affect dietary intake patterns and health. The paucity of information on food production and consumption is arguably most acute in low- and middle-income countries, where it is most urgently needed to monitor levels of under-nutrition, the health impacts of rapid dietary transition and the increasing ‘double burden’ of nutrition-related disease. Food availability statistics based on food commodity production data are currently widely used as a proxy measure of national-level food consumption, but using data from the UK and Mexico we highlight the potential pitfalls of this approach. Despite limited resources for data collection, better systems of measurement are possible. Important drivers to improve collection systems may include efforts to meet international development goals and partnership with the private sector. A clearer understanding of the links between the agriculture and food system and population health will ensure that health becomes a critical driver of agricultural change

Scarring Effects on Tunneling in Chaotic Double-Well Potentials

The connection between scarring and tunneling in chaotic double-well potentials is studied in detail through the distribution of level splittings. The mean level splitting is found to have oscillations as a function of energy, as expected if scarring plays a role in determining the size of the splittings, and the spacing between peaks is observed to be periodic of period {$2\pi\hbar$} in action. Moreover, the size of the oscillations is directly correlated with the strength of scarring. These results are interpreted within the theoretical framework of Creagh and Whelan. The semiclassical limit and finite-{$\hbar$} effects are discussed, and connections are made with reaction rates and resonance widths in metastable wells.Comment: 22 pages, including 11 figure

Re-framing the climate change debate in the livestock sector: mitigation and adaptation options

Livestock play a key role in the climate change debate. As with crop-based agriculture, the sector is both a net greenhouse gas emitter and vulnerable to climate change. At the same time, it is an essential food source for millions of people worldwide, with other functions apart from food security such as savings and insurance. By comparison with crop-based agriculture, the interactions of livestock and climate change have been much less studied. The debate around livestock is confusing due to the coexistence of multiple livestock farming systems with differing functions for humans, greenhouse gas (GHG) emission profiles and different characteristics and boundary issues in their measurement, which are often pooled together. Consequently, the diversity of livestock farming systems and their functions to human systems are poorly represented and the role of the livestock sector in the climate change debate has not been adequately addressed. In this article, building upon the Intergovernmental Panel on Climate Change Fifth Assessment Report (IPCC 5AR) findings, we review recent literature on livestock and climate change so as better to include this diversity in the adaptation and mitigation debate around livestock systems. For comparative purposes we use the same categories of managerial, technical, behavioral and policy-related action to organize both mitigation and adaptation options. We conclude that different livestock systems provide different functions to different human systems and require different strategies, so they cannot readily be pooled together. We also observe that, for the different livestock systems, several win-win strategies exist that effectively tackle both mitigation and adaptation options as well as food security