Simple finite field nuclear relaxation method for calculating vibrational contribution to degenerate four-wave mixing

A simple extended finite field nuclear relaxation procedure for calculating vibrational contributions to degenerate four-wave mixing (also known as the intensity-dependent refractive index) is presented. As a by-product one also obtains the static vibrationally averaged linear polarizability, as well as the first and second hyperpolarizability. The methodology is validated by illustrative calculations on the water molecule. Further possible extensions are suggested

On the influence of stratospheric water vapor changes on the tropospheric circulation

Observations suggest that the mixing ratio of water vapour in the stratosphere has increased by 20–50% between the 1960s and mid-1990s. Here we show that inclusion of such a stratospheric water vapour (SWV) increase in a state-of-the-art climate model modifies the circulation of the extratropical troposphere: the modeled increase in the North Atlantic Oscillation (NAO) index is 40% of the observed increase in NAO index between 1965 and 1995, suggesting that if the SWV trend is real, it explains a significant fraction of the observed NAO trend. Our results imply that SWV changes provide a novel mechanism for communicating the effects of large tropical volcanic eruptions and ENSO events to the extratropical troposphere over timescales of a few years, which provides a mechanism for interannual climate predictability. Finally, we discuss our results in the context of regional climate change associated with changes in methane emissions.

Understanding mixing efficiency in the oceans. Do the nonlinearities of the equation of state matter?

There exist two central measures of turbulent mixing in turbulent stratified fluids that are both caused by molecular diffusion: 1) the dissipation rate D(APE) of available potential energy APE; 2) the turbulent rate of change Wr, turbulent of background gravitational potential energy GPEr. So far, these two quantities have often been regarded as the same energy conversion, namely the irreversible conversion of APE into GPEr, owing to the well known exact equality D(APE)=Wr, turbulent for a Boussinesq fluid with a linear equation of state. Recently, however, Tailleux (2009) pointed out that the above equality no longer holds for a thermally-stratified compressible, with the ratio ξ=Wr, turbulent/D(APE) being generally lower than unity and sometimes even negative for water or seawater, and argued that D(APE) and Wr, turbulent actually represent two distinct types of energy conversion, respectively the dissipation of APE into one particular subcomponent of internal energy called the "dead" internal energy IE0, and the conversion between GPEr and a different subcomponent of internal energy called "exergy" IEexergy. In this paper, the behaviour of the ratio ξ is examined for different stratifications having all the same buoyancy frequency N vertical profile, but different vertical profiles of the parameter Υ=α P/(ρCp), where α is the thermal expansion coefficient, P the hydrostatic pressure, ρ the density, and Cp the specific heat capacity at constant pressure, the equation of state being that for seawater for different particular constant values of salinity. It is found that ξ and Wr, turbulent depend critically on the sign and magnitude of dΥ/dz, in contrast with D(APE), which appears largely unaffected by the latter. These results have important consequences for how the mixing efficiency should be defined and measured in practice, which are discussed.

Evaluation of ozone and water vapor fields from the ECMWF reanalysis ERA-40 during 1991-1999 in comparison with UARS satellite and MOZAIC aircraft observations

[ 1] The European Centre for Medium-Range Weather Forecasts (ECMWF) 40-year Reanalysis (ERA-40) ozone and water vapor reanalysis fields during the 1990s have been compared with independent satellite data from the Halogen Occultation Experiment (HALOE) and Microwave Limb Sounder (MLS) instruments on board the Upper Atmosphere Research Satellite (UARS). In addition, ERA-40 has been compared with aircraft data from the Measurements of Ozone and Water Vapour by Airbus In-Service Aircraft (MOZAIC) program. Overall, in comparison with the values derived from the independent observations, the upper stratosphere in ERA-40 has about 5 - 10% more ozone and 15 - 20% less water vapor. This dry bias in the reanalysis appears to be global and extends into the middle stratosphere down to 40 hPa. Most of the discrepancies and seasonal variations between ERA-40 and the independent observations occur within the upper troposphere over the tropics and the lower stratosphere over the high latitudes. ERA-40 reproduces a weaker Antarctic ozone hole, and of less vertical extent, than the independent observations; values in the ozone maximum in the tropical stratosphere are lower for the reanalysis. ERA-40 mixing ratios of water vapor are considerably larger than those for MOZAIC, typically by 20% in the tropical upper troposphere, and they may exceed 60% in the lower stratosphere over high latitudes. The results imply that the Brewer-Dobson circulation in the ECMWF reanalysis system is too fast, as is also evidenced by deficiencies in the way ERA-40 reproduces the water vapor "tape recorder'' signal in the tropical stratosphere. Finally, the paper examines the biases and their temporal variation during the 1990s in the way ERA-40 compares to the independent observations. We also discuss how the evaluation results depend on the instrument used, as well as on the version of the data.

New magnetic nano-absorbent for the determination of n-octanol/water partition coefficients

A novel and generic miniaturization methodology for the determination of partition coefficient values of organic compounds in noctanol/water by using magnetic nanoparticles is, for the first time, described. We have successfully designed, synthesised and characterised new colloidal stable porous silica-encapsulated magnetic nanoparticles of controlled dimensions. These nanoparticles absorbing a tiny amount of n-octanol in their porous silica over-layer are homogeneously dispersed into a bulk aqueous phase (pH 7.40) containing an organic compound prior to magnetic separation. The small size of the particles and the efficient mixing allow a rapid establishment of the partition equilibrium of the organic compound between the solid supported n-octanol nano-droplets and the bulk aqueous phase. UV-vis spectrophotometry is then applied as a quantitative method to determine the concentration of the organic compound in the aqueous phase both before and after partitioning (after magnetic separation). log D values of organic compounds of pharmaceutical interest (0.65-3.50), determined by this novel methodology, were found to be in excellent agreement with the values measured by the shake-flask method in two independent laboratories, which are also consistent with the literature data. It was also found that this new technique gives a number of advantages such as providing an accurate measurement of log D value, a much shorter experimental time and a smaller sample size required. With this approach, the formation of a problematic emulsion, commonly encountered in shake-flask experiments, is eliminated. It is envisaged that this method could be applicable to the high throughput log D screening of drug candidates. (c) 2005 Elsevier B.V. All rights reserved.

Selective catalytic oxidation of alkylaromatic molecules by nanosize water droplets containing Co2+ species in supercritical carbon dioxide fluid

Stabilized nano-sized water droplet carrying water-soluble Co2+ species is employed as a new catalyst system for the oxidation of the alkyl aromatics in the presence of a fluorinated surfactant. This stable system contains no labile C-H structure and can facilitate excellent mixing of catalytic Co(II)/NaBr species, hydrocarbon substrates and oxygen in supercritical carbon dioxide fluid, which is demonstrated to be an excellent alternative solvent system to acetic acid or nitric acid for air oxidation of a number of alkyl aromatic hydrocarbons using Co(II) species at mild conditions. As a result, potential advantages of this 'greener' catalytic method including safer operation, easier separation and purification, higher catalytic activity with selectivity and without using corrosive or oxidation unstable solvent are therefore envisaged.

Moisture vertical structure, column water vapor, and tropical deep convection

The vertical structure of the relationship between water vapor and precipitation is analyzed in 5 yr of radiosonde and precipitation gauge data from the Nauru Atmospheric Radiation Measurement (ARM) site. The first vertical principal component of specific humidity is very highly correlated with column water vapor (CWV) and has a maximum of both total and fractional variance captured in the lower free troposphere (around 800 hPa). Moisture profiles conditionally averaged on precipitation show a strong association between rainfall and moisture variability in the free troposphere and little boundary layer variability. A sharp pickup in precipitation occurs near a critical value of CWV, confirming satellite-based studies. A lag–lead analysis suggests it is unlikely that the increase in water vapor is just a result of the falling precipitation. To investigate mechanisms for the CWV–precipitation relationship, entraining plume buoyancy is examined in sonde data and simplified cases. For several different mixing schemes, higher CWV results in progressively greater plume buoyancies, particularly in the upper troposphere, indicating conditions favorable for deep convection. All other things being equal, higher values of lower-tropospheric humidity, via entrainment, play a major role in this buoyancy increase. A small but significant increase in subcloud layer moisture with increasing CWV also contributes to buoyancy. Entrainment coefficients inversely proportional to distance from the surface, associated with mass flux increase through a deep lower-tropospheric layer, appear promising. These yield a relatively even weighting through the lower troposphere for the contribution of environmental water vapor to midtropospheric buoyancy, explaining the association of CWV and buoyancy available for deep convection.

Novel polyvinylpyrrolidones to improve delivery of poorly-water soluble drugs; from design to synthesis and evaluation

Polyvinylpyrrolidone is a widely used in tablet formulations with the linear form acting as a wetting agent and disintegrant whereas the cross-linked form is a super-disintegrant. We have previously reported that simply mixing the commercial cross-linked polymer with ibuprofen disrupted drug crystallinity with consequent improvements in drug dissolution behavior. In this study, we have designed and synthesized novel cross-linking agents containing a range of oligoether moieties which have then be polymerized with vinylpyrrolidone to generate a suite of novel excipients with enhanced hydrogen-bonding capabilities. The polymers have a porous surface and swell in most common solvents and in water; properties which suggest their value as disintegrants. The polymers were evaluated in simple physical mixtures with ibuprofen as a model poorly-water soluble drug. The results show that the novel PVPs induce the drug to become “X-ray amorphous”, which increased dissolution to a greater extent than that seen with commercial cross-linked PVP. The polymers stabilize the amorphous drug with no evidence for recrystallization seen after 20 weeks storage.

Towards effective water reuse: drivers, challenges and strategies shaping the organisational management of reclaimed water in Jordan

Treated wastewater or reclaimed water is gaining recognition as a valuable water resource around the world. To assess why, where and how water reuse takes place in Jordan, semi-structured interviews were conducted with representatives of 29 key organisations in 2008. The analysis reveals that water scarcity is a key driver for water reuse. However, despite such recognition, reuse was described positively by only a small proportion of the interviewees (n = 6). Negative and neutral perceptions regarding reuse dominated and the research found that this was related to two underlying challenges: (i) the requirement for more intensive management when using reclaimed water compared with freshwater and (ii) concern over societal acceptance of water reuse. These factors were found to be associated with the risks posed to humans and their environments, combined with negative emotional and cultural responses to human waste and its applications. Numerous strategies are identified that are employed by organisations to overcome these challenges. Wastewater treatment, regulation, monitoring, the mixing of treated effluent with freshwater and limited public discussion of water reuse are all employed to achieve maximum use of reclaimed water. Each strategy presents benefits of sort, but some may paradoxically also inhibit optimal use of reclaimed water. Careful modifications to the existing strategies of Jordanian agencies, such as more open discussion of reuse, could lead to greater social, economic and environmental gains.

Stirring and mixing in two-dimensional divergent flow

While stirring and mixing properties in the stratosphere are reasonably well understood in the context of balanced (slow) dynamics, as is evidenced in numerous studies of chaotic advection, the strongly enhanced presence of high-frequency gravity waves in the mesosphere gives rise to a significant unbalanced (fast) component to the flow. The present investigation analyses result from two idealized shallow-water numerical simulations representative of stratospheric and mesospheric dynamics on a quasi-horizontal isentropic surface. A generalization of the Hua–Klein Eulerian diagnostic to divergent flow reveals that velocity gradients are strongly influenced by the unbalanced component of the flow. The Lagrangian diagnostic of patchiness nevertheless demonstrates the persistence of coherent features in the zonal component of the flow, in contrast to the destruction of coherent features in the meridional component. Single-particle statistics demonstrate t2 scaling for both the stratospheric and mesospheric regimes in the case of zonal dispersion, and distinctive scaling laws for the two regimes in the case of meridional dispersion. This is in contrast to two-particle statistics, which in the mesospheric (unbalanced) regime demonstrate a more rapid approach to Richardson’s t3 law in the case of zonal dispersion and is evidence of enhanced meridional dispersion.

Managing a duopolistic water market with confirmed proposals. An experiment

We report results from experimental water markets in which owners of two different sources of water supply water to households and farmers. The final water quality consumed by each type of consumer is determined through mixing of qualities from two different resources. We compare the standard duopolistic market structure with an alternative market clearing mechanism inspired by games with confirmed strategies (which have been shown to yield collusive outcomes). As in the static case, complex dynamic markets operating under a confirmed proposals protocol yield less efficient outcomes because coordination among independent suppliers has the usual effects of restricting output and increasing prices to the users. Our results suggest that, when market mechanisms are used to allocate water to its users, the rule of thumb used by competition authorities can also serve as a guide towards water market regulation.

Investigations into the formation and characterization of phospholipid microemulsions. IV. Pseudo-ternary phase diagrams of systems containing water-lecithin-alcohol and oil; The influence of oil

Phase studies have been performed for quaternary systems composed of egg lecithin, cosurfactant, water and oil. The lecithin used was the commercially available egg lecithin Ovothin 200 (which comprises ≥ 92% phosphatidylcholine). The cosurfactants employed were propanol and butanol, and these were used at lecithin/cosurfactant mixing ratios (Km) of 1:1 and 1.94:1 (weight basis). Six polar oils were investigated, including the alkanoic acids, octanoic and oleic, their corresponding ethyl esters and the medium and long chain triglycerides, Miglyol 812 and soybean oil. All oils, irrespective of the alcohol and the Km used, gave rise to systems that produced a stable isotropic region along the surfactant/oil axis (designated as a reverse microemulsion system). In addition, the systems incorporating propanol at both Km and butanol at a Km of 1.94: 1, generally gave rise to a liquid crystalline region and, in some cases, a second isotropic non-birefingent area (designated as a normal microemulsion system). The phase behaviour observed was largely dependent upon the alcohol and Km used and the size and the polarity of the oil present.

Probing the mucoadhesive interactions between porcine gastric mucin and some water-soluble polymers

This study investigates the structural features of porcine gastric mucin (PGM) in aqueous dispersions and its interactions with water-soluble polymers (poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), poly(ethylene oxide), and poly(ethylene glycol)) using isothermal titration calorimetry, turbidimetric titration, dynamic light scattering, and transmission electron microscopy. It is established that PAA (450 kDa) and PMAA (100 kDa) exhibit strong specific interactions with PGM causing further aggregation of its particles, while PAA (2 kDa), poly(ethylene oxide) (1 000 kDa), and poly(ethylene glycol) (10 kDa) do not show any detectable effects on mucin. Sonication of mucin dispersions prior to their mixing with PAA (450 kDa) and PMAA (100 kDa) leads to more pronounced intensity of interactions.

Sea ice production and water mass modification in the eastern Laptev Sea

A simple polynya flux model driven by standard atmospheric forcing is used to investigate the ice formation that took place during an exceptionally strong and consistent western New Siberian (WNS) polynya event in 2004 in the Laptev Sea. Whether formation rates are high enough to erode the stratification of the water column beneath is examined by adding the brine released during the 2004 polynya event to the average winter density stratification of the water body, preconditioned by summers with a cyclonic atmospheric forcing (comparatively weakly stratified water column). Beforehand, the model performance is tested through a simulation of a well‐documented event in April 2008. Neglecting the replenishment of water masses by advection into the polynya area, we find the probability for the occurrence of density‐driven convection down to the bottom to be low. Our findings can be explained by the distinct vertical density gradient that characterizes the area of the WNS polynya and the apparent lack of extreme events in the eastern Laptev Sea. The simple approach is expected to be sufficiently rigorous, since the simulated event is exceptionally strong and consistent, the ice production and salt rejection rates are likely to be overestimated, and the amount of salt rejected is distrusted over a comparatively weakly stratified water column. We conclude that the observed erosion of the halocline and formation of vertically mixed water layers during a WNS polynya event is therefore predominantly related to wind‐ and tidally driven turbulent mixing processes.

Impact of the Arctic Ocean Atlantic water layer on Siberian shelf hydrography

This paper examines the role of the Arctic Ocean Atlantic water (AW) in modifying the Laptev Sea shelf bottom hydrography on the basis of historical records from 1932 to 2008, field observations carried out in April–May 2008, and 2002–2009 cross‐slope measurements. A climatology of bottom hydrography demonstrates warming that extends offshore from the 30–50 m depth contour. Bottom layer temperature‐time series constructed from historical records links the Laptev Sea outer shelf to the AW boundary current transporting warm and saline water from the North Atlantic. The AW warming of the mid‐1990s and the mid‐2000s is consistent with outer shelf bottom temperature variability. For April–May 2008 we observed on‐shelf near‐bottom warm and saline water intrusions up to the 20 m isobath. These intrusions are typically about 0.2°C warmer and 1–1.5 practical salinity units saltier than ambient water. The 2002–2009 cross‐slope observations are suggestive for the continental slope upward heat flux from the AW to the overlying low‐halocline water (LHW). The lateral on‐shelf wind‐driven transport of the LHW then results in the bottom layer thermohaline anomalies recorded over the Laptev Sea shelf. We also found that polynya‐induced vertical mixing may act as a drainage of the bottom layer, permitting a relatively small portion of the AW heat to be directly released to the atmosphere. Finally, we see no significant warming (up until now) over the Laptev Sea shelf deeper than 10–15 m in the historical record. Future climate change, however, may bring more intrusions of Atlantic‐modified waters with potentially warmer temperature onto the shelf, which could have a critical impact on the stability of offshore submarine permafrost.