Influence of Hydrophilic Surface Specificity on the Structural Properties of Confined Water

The influence of chemical specificity of hydrophilic surfaces on the structure of confined water in the subnanometer regime is investigated using grand canonical Monte Carlo Simulations. The structural variations for water confined between hydroxylated silica surfaces are contrasted with water confined between mica surfaces. Although both surfaces are hydrophilic, our Study shows that hydration of potassium ions on the mica surface has a strong influence on the water Structure and solvation force response of confined water. In contrast to the disrupted hydrogen bond network observed for water confined between Mica Surfaces, water between silica surfaces retains its hydrogen bond network displaying bulklike structural features down to surface separations as small as 0.45 nm. Hydrogen bonding of all invariant contact water layer with the surface silanol groups aids in maintaining a constant number of hydrogen bonds per water molecule for the silica surfaces. As a consequence water depletion and rearrangement upon decreasing confinement is a strong function of the hydrophilic surface specificity, particularly at smaller separations. An oscillatory solvation force response is only observed for water confined between Silica surfaces, and bulklike features are observed for both Surfaces above a surface separation of about 1.2 nm. We evaluate and contrast the water density, dipole moment distributions, pi pair correlation functions, and solvation forces as a function of the surface separation.

Phylogeography and hybrid swarms: history of brackish water bivalve diversity in North European marginal seas

This study addressed the large-scale molecular zoogeography in two brackish water bivalve molluscs, Macoma balthica and Cerastoderma glaucum, and genetic signatures of the postglacial colonization of Northern Europe by them. The traditional view poses that M. balthica in the Baltic, White and Barents seas (i.e. marginal seas) represent direct postglacial descendants of the adjacent Northeast Atlantic populations, but this has recently been challenged by observations of close genetic affinities between these marginal populations and those of the Northeast Pacific. The primary aim of the thesis was to verify, quantify and characterize the Pacific genetic contribution across North European populations of M. balthica and to resolve the phylogeographic histories of the two bivalve taxa in range-wide studies using information from mitochondrial DNA (mtDNA) and nuclear allozyme polymorphisms. The presence of recent Pacific genetic influence in M. balthica of the Baltic, White and Barents seas, along with an Atlantic element, was confirmed by mtDNA sequence data. On a broader temporal and geographical scale, altogether four independent trans-Arctic invasions of Macoma from the Pacific since the Miocene seem to have been involved in generating the current North Atlantic lineage diversity. The latest trans-Arctic invasion that affected the current Baltic, White and Barents Sea populations probably took place in the early post-glacial. The nuclear genetic compositions of these marginal sea populations are intermediate between those of pure Pacific and Atlantic subspecies. In the marginal sea populations of mixed ancestry (Barents, White and Northern Baltic seas), the Pacific and Atlantic components are now randomly associated in the genomes of individual clams, which indicates both pervasive historical interbreeding between the previously long-isolated lineages (subspecies), and current isolation of these populations from the adjacent pure Atlantic populations. These mixed populations can be characterized as self-supporting hybrid swarms, and they arguably represent the most extensive marine animal hybrid swarms so far documented. Each of the three swarms still has a distinct genetic composition, and the relative Pacific contributions vary from 30 to 90 % in local populations. This diversity highlights the potential of introgressive hybridization to rapidly give rise to new evolutionarily and ecologically significant units in the marine realm. In the south of the Danish straits and in the Southern Baltic Sea, a broad genetic transition zone links the pure North Sea subspecies M. balthica rubra to the inner Baltic hybrid swarm, which has about 60 % of Pacific contribution in its genome. This transition zone has no regular smooth clinal structure, but its populations show strong genotypic disequilibria typical of a hybrid zone maintained by the interplay of selection and gene flow by dispersing pelagic larvae. The structure of the genetic transition is partly in line with features of Baltic water circulation and salinity stratification, with greater penetration of Atlantic genes on the Baltic south coast and in deeper water populations. In all, the scenarios of historical isolation and secondary contact that arise from the phylogeographic studies of both Macoma and Cerastoderma shed light to the more general but enigmatic patterns seen in marine phylogeography, where deep genetic breaks are often seen in species with high dispersal potential.

Sediment resuspension as a water quality regulator in lakes

Sediment resuspension, the return of the bottom material into the water column, is an important process that can have various effects on a lake ecosystem. Resuspension caused by wind-induced wave disturbance, currents, turbulent fluctuations and bioturbation affects water quality characteristics such as turbidity, light conditions, and concentrations of suspended solids (SS) and nutrients. Resuspension-mediated increase in turbidity may favour the dominance of phytoplankton over macrophytes. The predator-prey interactions contributing to the trophic state of a lake may also be influenced by increasing turbidity. Directly, the trophic state of a lake can be influenced by the effect of sediment resuspension on nutrient cycling. Resuspension enhances especially the cycling of phosphorus by bringing the sedimentary nutrients back into the water column and may thereby induce switches between phosphorus and nitrogen limitation. The contribution of sediment resuspension to gross sedimentation, turbidity, and concentration of SS and nutrients was studied in a small, deep lake as well as in a multibasin lake with deep and shallow areas. The effect of ice cover on sediment resuspension and thereby on phosphorus concentrations was also studied. The rates of gross sedimentation and resuspen¬sion were estimated with sediment traps and the associations between SS and nutrients were considered. Sediment resuspension, caused by wind activity, comprised most of the gross sedimenta¬tion and strongly contributed to the concentration of SS and turbidity in the lakes studied. Additionally, via the influence on SS, resuspension affected the concentration of total phosphorus (TP) and soluble reactive phosphorus (SRP), as well as the total nitrogen to total phosphorus (TN:TP) ratio. Although contrasting results concerning the dependence between the SS and SRP concentrations were observed, it could be concluded that sediment resuspension during strong algal blooms (pH > 9) led to aerobic release of P. The main findings of this thesis were that in the course of the growing season, sediment resuspension coupled with phytoplankton succession led to liberation of P from resuspended particles, which in turn resulted in high TP concentrations and low TN:TP ratios. This development was likely a cause of strong cyanobacterial blooms in midsummer.

Behaviour of natural zeolites used for the treatment of simulated and actual coal seam gas water

Coal seam gas operations produce significant quantities of associated water which often require demineralization. Ion exchange with natural zeolites has been proposed as a possible approach. The interaction of natural zeolites with solutions of sodium chloride and sodium bicarbonate in addition to coal seam gas water is not clear. Hence, we investigated ion exchange kinetics, equilibrium, and column behaviour of an Australian natural zeolite. Kinetic tests suggested that the pseudo first order equation best simulated the data. Intraparticle diffusion was part of the rate limiting step and more than one diffusion process controlled the overall rate of sodium ion uptake. Using a constant mass of zeolite and variable concentration of either sodium chloride or sodium bicarbonate resulted in a convex isotherm which was fitted by a Langmuir model. However, using a variable mass of zeolite and constant concentration of sodium ions revealed that the exchange of sodium ions with the zeolite surface sites was in fact unfavourable. Sodium ion exchange from bicarbonate solutions (10.3 g Na/kg zeolite) was preferred relative to exchange from sodium chloride solutions (6.4 g Na/kg zeolite). The formation of calcium carbonate species was proposed to explain the observed behaviour. Column studies of coal seam gas water showed that natural zeolite had limited ability to reduce the concentration of sodium ions (loading 2.1 g Na/kg zeolite) with rapid breakthrough observed. It was concluded that natural zeolites may not be suitable for the removal of cations from coal seam gas water without improvement of their physical properties.

Vitrification, relaxation and free volume in glycerol-water binary liquid mixture:Spin probe ESR studies

Glass transition and relaxation of the glycerol-water (G-W) binary mixture system have been studied over the glycerol concentration range of 5-85 mol% by using the highly sensitive technique of electron spin resonance (ESR). For the water rich mixture the glass transition,sensed by the dissolved spin probe, arises from the vitrified mesoscopic portion of the binary system. The concentration dependence of the glass transition temperature manifests a closely related molecular level cooperativity in the system. A drastic change in the mesoscopic structure of the system at the critical concentration of 40 mol is confirmed by an estimation of the spin probe effective volume in a temperature range where the tracer reorientation is strongly coupled to the system dynamics.

A shallow water AUV for benthic and water column observations

Autonomous underwater vehicles (AUVs) are becoming commonplace in the study of inshore coastal marine habitats. Combined with shipboard systems, scientists are able to make in-situ measurements of water column and benthic properties. In CSIRO, autonomous gliders are used to collect water column data, while surface vessels are used to collect bathymetry information through the use of swath mapping, bottom grabs, and towed video systems. Although these methods have provided good data coverage for coastal and deep waters beyond 50m, there has been an increasing need for autonomous in-situ sampling in waters less than 50m deep. In addition, the collection of benthic and water column data has been conducted separately, requiring extensive post-processing to combine data streams. As such, a new AUV was developed for in-situ observations of both benthic habitat and water column properties in shallow waters. This paper provides an overview of the Starbug X AUV system, its operational characteristics including vision-based navigation and oceanographic sensor integration.

Ce0.67Cr0.33O2.11: A New Low-Temperature O-2 Evolution Material and H-2 Generation Catalyst by Thermochemical Splitting of Water

Ce0.67Cr0.33O2.11 was synthesized by hydrothermal method using diethylenetriamine as complexing agent (Chem. Mater. 2008, 20, 7268). Ce0.67Cr0.33O2.11 being the only compound likes UO2+delta to have excess oxygen, it releases a large proportion of its lattice oxygen (0.167 M [O]/mole of compound) at relatively low temperature (465 degrees C) directly and it has been utilized for generation of H-2 by thermo-splitting of water. An almost stoichiometric amount of H-2 (0.152 M/Mole of compound) is generated at much lower temperature (65 degrees C). There is an almost comparable amount of oxygen release and hydrogen generation over this material at very low temperature comparedto other CeO2-MOx (Mn, Fe, Cu, and Ni) mixed-oxide solid solutions (O-2 evolution >= 1300 degrees C and H-2 generation at 1000 degrees C). The reversible nature of oxygen release and intake of this material is attributed to its fluorite Structure and coupling between the Ce4+/Ce3+ and Cr4+/6+/Cr3+ redox couples. Compound shows reversible oxygen release and intake by H2O absorption and subsequent hydrogen release to gain parent structure and hence this material can be utilized for generation of H-2 at very low temperature by thermo-chemical splitting of water.

Effect of Bottom Bubbling Conditions on Surface Reaction Rate in Oxygen-Water System

In secondary steelmaking, the enhancement of the reaction rate in the low carbon period during the decarburization of steel is considered the most effective method to produce ultralow carbon steel. In a previous study, it was revealed that the surface reaction is dominant during the final stage of the actual refining process. In order to improve the surface reaction rate, it is necessary to enlarge the reaction region, which is usually achieved by increasing the plume eye area. In this study, water model experiments were carried out to estimate the influence of bottom stirring conditions on the gas-liquid reaction rate; for this purpose, the deoxidation rate during the bottom bubbling process was measured. Five types of nozzle configurations were used to study the effect of the plume eye area on the reaction rate at various gas flow rates. The results reveal that the surface reaction rate is influenced by the gas flow rate and the plume eye area. An empirical correlation was developed for the reaction rate and the plume eye area. This correlation was applied to estimate the gas-liquid reaction rate mat the bath surface.

Channelled porous TiO2 synthesized with a water-in-oil microemulsion

Porous titanium dioxide synthesized with a bicontinuous surfactant template is a promising method that leads to a high active surface area electrode. The template used is based on a water/isooctane/dioctyl sodium sulfosuccinate salt together with lecithin. Several parameters were varied during the synthesis to understand and optimize channel formation mechanisms. The material is patterned in stacked conical channels, widening towards the centre of the grains. The active surface area increased by 116% when the concentration of alkoxide precursors was decreased and increased by 241% when the template formation temperature was decreased to 10C. Increasing the oil phase viscosity tends to widen the pore aperture, thus decreasing the overall active surface area. Changing the phase proportions alters the microemulsion integrity and disrupts channel formation.

Abatement of fluoride from water using manganese dioxide-coated activated alumina

Batch adsorption of fluoride onto manganese dioxide-coated activated alumina (MCAA) has been studied. Adsorption experiments were carried out at various pH (3–9), time interval (0–6 h), adsorbent dose (1–16 g/l), initial fluoride concentration (1–25 mg/l) and in the presence of different anions. Adsorption isotherms have been modeled using Freundlich, Langmuir and Dubinin–Raduskevich isotherms and adsorption followed Langmuir isotherm model. Kinetic studies revealed that the adsorption followed second-order rate kinetics. MCAA could remove fluoride effectively (up to 0.2 mg/l) at pH 7 in 3 h with 8 g/l adsorbent dose when 10 mg/l of fluoride was present in 50 ml of water. In the presence of other anions, the adsorption of fluoride was retared. The mechanism of fluoride uptake by MCAA is due to physical adsorption as well as through intraparticle diffusion which was confirmed by kinetics, Dubinin–Raduskevich isotherm, zeta-potential measurements and mapping studies of energy-dispersive analysis of X-ray.

An Insight to the Dynamics of Conserved Water Molecular Triad in IMPDH II (Human): Recognition of Cofactor and Substrate to Catalytic Arg 322

Inosine 5' monophosphate dehydrogenase (IMPDH II) is a key enzyme involved in the de novo biosynthesis pathway of purine nucleotides and is also considered to be an excellent target for cancer inhibitor design. The conserve R 322 residue (in human) is thought to play some role in the recognition of inhibitor and cofactor through the catalytic D 364 and N 303. The 15 ns simulation and the water dynamics of the three different PDB structures (1B3O, 1NF7, and 1NFB) of human IMPDH by CHARMM force field have clearly indicated the involvement of three conserved water molecules (W-L, W-M, and W-C) in the recognition of catalytic residues (R 322, D 364, and N 303) to inhibitor and cofactor. Both the guanidine nitrogen atoms (NH1 and NH 2) of the R 322 have anchored the di- and mono-nucleotide (cofactor and inhibitor) binding domains via the conserved W-C and W-L water molecules. Another conserved water molecule W-M seems to bridge the two domains including the R 322 and also the W-C and W-L through seven centers H-bonding coordination. The conserved water molecular triad (W-C - W-M - W-L) in the protein complex may thought to play some important role in the recognition of inhibitor and cofactor to the protein through R 322 residue.

Water balance modelling in a tropical watershed under deciduous forest (Mule Hole, India): Regolith matric storage buffers the groundwater recharge process

Accurate estimations of water balance are needed in semi-arid and sub-humid tropical regions, where water resources are scarce compared to water demand. Evapotranspiration plays a major role in this context, and the difficulty to quantify it precisely leads to major uncertainties in the groundwater recharge assessment, especially in forested catchments. In this paper, we propose to assess the importance of deep unsaturated regolith and water uptake by deep tree roots on the groundwater recharge process by using a lumped conceptual model (COMFORT). The model is calibrated using a 5 year hydrological monitoring of an experimental watershed under dry deciduous forest in South India (Mule Hole watershed). The model was able to simulate the stream discharge as well as the contrasted behaviour of groundwater table along the hillslope. Water balance simulated for a 32 year climatic time series displayed a large year-to-year variability, with alternance of dry and wet phases with a time period of approximately 14 years. On an average, input by the rainfall was 1090 mm year(-1) and the evapotranspiration was about 900 mm year(-1) out of which 100 mm year(-1) was uptake from the deep saprolite horizons. The stream flow was 100 mm year(-1) while the groundwater underflow was 80 mm year(-1). The simulation results suggest that (i) deciduous trees can uptake a significant amount of water from the deep regolith, (ii) this uptake, combined with the spatial variability of regolith depth, can account for the variable lag time between drainage events and groundwater rise observed for the different piezometers and (iii) water table response to recharge is buffered due to the long vertical travel time through the deep vadose zone, which constitutes a major water reservoir. This study stresses the importance of long term observations for the understanding of hydrological processes in tropical forested ecosystems. (C) 2009 Elsevier B.V. All rights reserved.

BDST modelling of sodium ion exchange column behaviour with strong acid cation resin in relation to coal seam water treatment

Reverse osmosis is the dominant technology utilized for desalination of saline water produced during the extraction of coal seam gas. Alternatively, ion exchange is of interest due to potential cost advantages. However, there is limited information regarding the column performance of strong acid cation resin for removal of sodium ions from both model and actual coal seam water samples. In particular, the impact of bed depth, flow rate, and regeneration was not clear. Consequently, this study applied Bed Depth Service Time (BDST) models to reveal that increasing sodium ion concentration and flow rates diminished the time required for breakthrough to occur. The loading of sodium ions on fresh resin was calculated to be ca. 71.1 g Na/kg resin. Difficulties in regeneration of the resin using hydrochloric acid solutions were discovered, with 86% recovery of exchange sites observed. The maximum concentration of sodium ions in the regenerant brine was found to be 47,400 mg/L under the conditions employed. The volume of regenerant waste formed was 6.2% of the total volume of water treated. A coal seam water sample was found to load the resin with only 53.5 g Na/kg resin, which was consistent with not only the co-presence of more favoured ions such as calcium, magnesium, barium and strontium, but also inefficient regeneration of the resin prior to the coal seam water test.