Theory of Gas Hydrates: Effect of the Approximation of Rigid Water Lattice

One of the assumptions of the van der Waals and Platteeuw theory for gas hydrates is that the host water lattice is rigid and not distorted by the presence of guest molecules. In this work, we study the effect of this approximation on the triple-point lines of the gas hydrates. We calculate the triple-point lines of methane and ethane hydrates via Monte Carlo molecular simulations and compare the simulation results with the predictions of van der Waals and Platteeuw theory. Our study shows that even if the exact intermolecular potential between the guest molecules and water is known, the dissociation temperatures predicted by the theory are significantly higher. This has serious implications to the modeling of gas hydrate thermodynamics, and in spite of the several impressive efforts made toward obtaining an accurate description of intermolecular interactions in gas hydrates, the theory will suffer from the problem of robustness if the issue of movement of water molecules is not adequately addressed.

String-like propagation of the 5-coordinated defect state in supercooled water: molecular origin of dynamic and thermodynamic anomalies

We find that at low temperature water, large amplitude (similar to 60 degrees) rotational jumps propagate like a string, with the length of propagation increasing with lowering temperature. The strings are formed by mobile 5-coordinated water molecules which move like a Glarum defect (J. Chem. Phys., 1960, 33, 1371), causing water molecules on the path to change from 4-coordinated to 5-coordinated and again back to 4-coordinated water, and in the process cause the tagged water molecule to jump, by following essentially the Laage-Hynes mechanism (Science, 2006, 311, 832-835). The effects on relaxation of the propagating defect causing large amplitude jumps are manifested most dramatically in the mean square displacement (MSD) and also in the rotational time correlation function of the O-H bond of the molecule that is visited by the defect (transient transition to the 5-coordinated state). The MSD and the decay of rotational time correlation function, both remain quenched in the absence of any visit by the defect, as postulated by Glarum long time ago. We establish a direct connection between these propagating events and the known thermodynamic and dynamic anomalies in supercooled water. These strings are found largely in the regions that surround the relatively rigid domains of 4-coordinated water molecules. The propagating strings give rise to a noticeable dynamical heterogeneity, quantified here by a sharp rise in the peak of the four-point density response function, chi(4)(t). This dynamics heterogeneity is also responsible for the breakdown of the Stokes-Einstein relation.

Modeling Indian Ocean circulation: Bay of Bengal fresh water plume and the Arabian Sea Mini Warm Pool

The Indian subcontinent divides the north Indian Ocean into two tropical basins, namely the Arabian Sea and the Bay of Bengal. The Arabian Sea has high salinity whereas the salinity of the Bay of Bengal is much lower due to the contrast in freshwater forcing of the two basins. The freshwater received by the Bay in large amounts during the summer monsoon through river discharge is flushed out annually by ocean circulation. After the withdrawal of the summer monsoon, the Ganga – Brahmaputra river plume flows first along the Indian coast and then around Sri Lanka into the Arabian Sea creating a low salinity pool in the southeastern Arabian Sea (SEAS). In the same region, during the pre-monsoon months of February – April, a warm pool, known as the Arabian Sea Mini Warm Pool (ASMWP), which is distinctly warmer than the rest of the Indian Ocean, takes shape. In fact, this is the warmest region in the world oceans during this period. Simulation of the river plume and its movement as well as its implications to thermodynamics has been a challenging problem for models of Indian Ocean. Here we address these issues using an ocean general circulation model – first we show that the model is capable of reproducing fresh plumes in the Bay of Bengal as well as its movement and then we use the model to determine the processes that lead to formation of the ASMWP. Hydrographic observations from the western Bay of Bengal have shown the presence of a fresh plume along the northern part of the Indian coast during summer monsoon. The Indian Ocean model when forced by realistic winds and climatological river discharge reproduces the fresh plume with reasonable accuracy. The fresh plume does not advect along the Indian coast until the end of summer monsoon. The North Bay Monsoon Current, which flows eastward in the northern Bay, separates the low salinity water from the more saline southern parts of the bay and thus plays an important role in the fresh water budget of the Bay of Bengal. The model also reproduces the surge of the fresh-plume along the Indian coast, into the Arabian Sea during northeast monsoon. Mechanisms that lead to the formation of the Arabian Sea Mini Warm Pool are investigated using several numerical experiments. Contrary to the existing theories, we find that salinity effects are not necessary for the formation of the ASMWP. The orographic effects of the Sahyadris (Western Ghats) and resulting reduction in wind speed leads to the formation of the ASMWP. During November – April, the SEAS behave as a low-wind heatdominated regime where the evolution of sea surface temperature is solely determined by atmospheric forcing. In such regions the evolution of surface layer temperature is not dependent on the characteristics of the subsurface ocean such as the barrier layer and temperature inversion.

The Behaviour of Two-Phase Flow of DNAPL and Water through a Fractured Rock under Confining Pressure

This study presents the characterization of DNAPL and water flow in a fracture under confining pressure. A comprehensive mathematical model and the conditions under which DNAPL will enter an initially water-saturated deforming rock fracture are discussed. A numerical model with which to predict the quantity of each phase in terms of their saturations in deforming rock joint is developed. The effect of varying confining stresses on the traverse time of DNAPL across a fractured aquitard is studied. The sensitivity analysis for physical and hydraulic properties like initial fracture apertures, fracture dips, equivalent fracture aperture and confining pressures are performed and discussed.

Exploring use of climate information for optimal design of water resources infrastructure

We conducted surveys of fire and fuels managers at local, regional, and national levels to gain insights into decision processes and information flows in wildfire management. Survey results in the form of fire managers’ decision calendars show how climate information needs vary seasonally, over space, and through the organizational network, and help determine optimal points for introducing climate information and forecasts into decision processes. We identified opportunities to use climate information in fire management, including seasonal to interannual climate forecasts at all organizational levels, to improve the targeting of fuels treatments and prescribed burns, the positioning and movement of initial attack resources, and staffing and budgeting decisions. Longer-term (5–10 years) outlooks also could be useful at the national level in setting budget and research priorities. We discuss these opportunities and examine the kinds of organizational changes that could facilitate effective use of existing climate information and climate forecast capabilities.

Spin Probe Signature of Freezing in Water Slow Cooling Experiment: Our Observation is Global or Local?

First systematic spin probe ESR study of water freezing has been conducted using TEMPOL and TEMPO as the probes. The spin probe signature of the water freezing has been described in terms of the collapse of narrow triplet spectrum into a single broad line. This spin probe signature of freezing has been observed at an anomalously low temperature when a milimoler solution of TEMPOL is slowly cooled from room temperature. A systematic observation has revealed a spin probe concentration dependence of these freezing and respective melting points. These results can be explained in terms of localization of spin probe and liquid water,most probably in the interstices of ice grains, in an ice matrix. The lowering of spin probe freezing point, along with the secondary evidences, like spin probe concentration dependence of peak-to-peak width in frozen limit signal, indicates a possible size dependence of these localizations/entrapments with spin probe concentration. A weak concentration dependence of spin probe assisted freezing and melting points, which has been observed for TEMPO in comparison to TEMPOL, indicates different natures of interactions with water of these two probes. This view is also supported by the relaxation behavior of the two probes.

Protocols for Collection, Preservation and Enumeration of Diatoms from Aquatic Habitats fro Water Quality Monitoring in India

Diatoms have become important organisms for monitoring freshwaters and their value has been recognised in Europe, American and African continents. If India is to include diatoms in the current suite of bioindicators, then thorough testing of diatom-based techniques is required. This paper provides guidance on methods through all stages of diatom collection from different habitats from streams and lakes, preparation and examination for the purposes of water quality assessment that can be adapted to most aquatic ecosystems in India.

The advection-condensation model and water-vapour probability density functions

The statistically steady humidity distribution resulting from an interaction of advection, modelled as an uncorrelated random walk of moist parcels on an isentropic surface, and a vapour sink, modelled as immediate condensation whenever the specific humidity exceeds a specified saturation humidity, is explored with theory and simulation. A source supplies moisture at the deep-tropical southern boundary of the domain and the saturation humidity is specified as a monotonically decreasing function of distance from the boundary. The boundary source balances the interior condensation sink, so that a stationary spatially inhomogeneous humidity distribution emerges. An exact solution of the Fokker-Planck equation delivers a simple expression for the resulting probability density function (PDF) of the wate-rvapour field and also the relative humidity. This solution agrees completely with a numerical simulation of the process, and the humidity PDF exhibits several features of interest, such as bimodality close to the source and unimodality further from the source. The PDFs of specific and relative humidity are broad and non-Gaussian. The domain-averaged relative humidity PDF is bimodal with distinct moist and dry peaks, a feature which we show agrees with middleworld isentropic PDFs derived from the ERA interim dataset. Copyright (C) 2011 Royal Meteorological Society