Accurate analysis of noble gas concentrations in small water samples and its application to fluid inclusions in stalagmites

The concentrations of dissolved noble gases in water are widely used as a climate proxy to determine noble gas temperatures (NGTs); i.e., the temperature of the water when gas exchange last occurred. In this paper we make a step forward to apply this principle to fluid inclusions in stalagmites in order to reconstruct the cave temperature prevailing at the time when the inclusion was formed. We present an analytical protocol that allows us accurately to determine noble gas concentrations and isotope ratios in stalagmites, and which includes a precise manometrical determination of the mass of water liberated from fluid inclusions. Most important for NGT determination is to reduce the amount of noble gases liberated from air inclusions, as they mask the temperature-dependent noble gas signal from the water inclusions. We demonstrate that offline pre-crushing in air to subsequently extract noble gases and water from the samples by heating is appropriate to separate gases released from air and water inclusions. Although a large fraction of recent samples analysed by this technique yields NGTs close to present-day cave temperatures, the interpretation of measured noble gas concentrations in terms of NGTs is not yet feasible using the available least squares fitting models. This is because the noble gas concentrations in stalagmites are not only composed of the two components air and air saturated water (ASW), which these models are able to account for. The observed enrichments in heavy noble gases are interpreted as being due to adsorption during sample preparation in air, whereas the excess in He and Ne is interpreted as an additional noble gas component that is bound in voids in the crystallographic structure of the calcite crystals. As a consequence of our study's findings, NGTs will have to be determined in the future using the concentrations of Ar, Kr and Xe only. This needs to be achieved by further optimizing the sample preparation to minimize atmospheric contamination and to further reduce the amount of noble gases released from air inclusions.

CLSM method for the dynamic observation of pH change within polymer matrices for oral delivery

If acid-sensitive drugs or cells are administered orally, there is often a reduction in efficacy associated with gastric passage. Formulation into a polymer matrix is a potential method to improve their stability. The visualization of pH within these materials may help better understand the action of these polymer systems and allow comparison of different formulations. We herein describe the development of a novel confocal laser-scanning microscopy (CLSM) method for visualizing pH changes within polymer matrices and demonstrate its applicability to an enteric formulation based on chitosan-coated alginate gels. The system in question is first shown to protect an acid-sensitive bacterial strain to low pH, before being studied by our technique. Prior to this study, it has been claimed that protection by these materials is a result of buffering, but this has not been demonstrated. The visualization of pH within these matrices during exposure to a pH 2.0 simulated gastric solution showed an encroachment of acid from the periphery of the capsule, and a persistence of pHs above 2.0 within the matrix. This implies that the protective effect of the alginate-chitosan matrices is most likely due to a combination of buffering of acid as it enters the polymer matrix and the slowing of acid penetration.

A two-tiered approach to long-range climate forecasting

Long-range global climate forecasts were made by use of a model for predicting a tropical Pacific sea-surface temperature (SST) in tandem with an atmospheric general circulation model. The SST is predicted first at long lead times into the future. These ocean forecasts are then used to force the atmospheric model and so produce climate forecasts at lead times of the SST forecasts. Prediction of seven large climatic events of the 1970s to 1990s by this technique are in good agreement with observations over many regions of the globe.

Optimizing layer-by-layer deposition of interpolymer complexes on solid substrates using Biacore

The layer-by-layer deposition of polymers onto surfaces allows the fabrication of multilayered materials for a wide range of applications, from drug delivery to biosensors. This work describes the analysis of complex formation between poly(acrylic acid) and methylcellulose in aqueous solutions using Biacore, a surface plasmon resonance analytical technique, traditionally used to examine biological interactions. This technique characterized the layer-by-layer deposition of these polymers on the surface of a Biacore sensor chip. The results were subsequently used to optimize the experimental conditions for sequential layer deposition on glass slides. The role of the solution pH and poly(acrylic acid) molecular weight on the formation of interpolymer multilayered coatings was researched, and showed that the optimal deposition of the polymer complexes was achieved at pHs ≤2.5 with a poly(acrylic acid) molecular weight of 450 kDa.

A case study of boundary layer ventilation by convection and coastal processes

It is often assumed that ventilation of the atmospheric boundary layer is weak in the absence of fronts, but is this always true? In this paper we investigate the processes responsible for ventilation of the atmospheric boundary layer during a nonfrontal day that occurred on 9 May 2005 using the UK Met Office Unified Model. Pollution sources are represented by the constant emission of a passive tracer everywhere over land. The ventilation processes observed include shallow convection, turbulent mixing followed by large-scale ascent, a sea breeze circulation and coastal outflow. Vertical distributions of tracer are validated qualitatively with AMPEP (Aircraft Measurement of chemical Processing Export fluxes of Pollutants over the UK) CO aircraft measurements and are shown to agree impressively well. Budget calculations of tracers are performed in order to determine the relative importance of these ventilation processes. Coastal outflow and the sea breeze circulation were found to ventilate 26% of the boundary layer tracer by sunset of which 2% was above 2 km. A combination of coastal outflow, the sea breeze circulation, turbulent mixing and large-scale ascent ventilated 46% of the boundary layer tracer, of which 10% was above 2 km. Finally, coastal outflow, the sea breeze circulation, turbulent mixing, large-scale ascent and shallow convection together ventilated 52% of the tracer into the free troposphere, of which 26% was above 2 km. Hence this study shows that significant ventilation of the boundary layer can occur in the absence of fronts (and thus during high-pressure events). Turbulent mixing and convection processes can double the amount of pollution ventilated from the boundary layer.

Boundary-layer ventilation by baroclinic lifecycles

Ventilation of the boundary layer has an important effect on local and regional air quality and is a prerequisite for long-range pollution transport. Once in the free troposphere, pollutants can alter the chemical composition of the troposphere and impact on the Earth's radiative forcing. Idealised baroclinic life cycles, LC1 and LC2, have been simulated in a three-dimensional dry hemispheric model in the presence of boundary-layer turbulent fluxes. A passive tracer is added to the simulations to represent pollution emitted at, or near, the surface. A simple conveyor-belt diagnostic is developed to objectively identify regions of the boundary layer that can be ventilated by either warm or cold conveyor belts. Transport of pollutants within and above the boundary layer is examined on synoptic scales. Three different physical mechanisms are found to interact with each other to ventilate pollutants out of the boundary layer. These mechanisms are turbulent mixing within the boundary layer, horizontal advection due to Ekman convergence and divergence within the boundary layer, and advection by the warm conveyor belt. The mass of tracer ventilated by the two life cycles is remarkably similar given the differences in frontal structure, suggesting that the large-scale baroclinicity is an effective constraint on ventilation.

Layer-by-layer electrostatic entrapment of protein molecules on superparamagnetic nanoparticle: new strategy to enhance adsorption capacity and maintain biological activity

There is a recent interest to use inorganic-based magnetic nanoparticles as a vehicle to carry biomolecules for various biophysical applications, but direct attachment of the molecules is known to alter their conformation leading to attenuation in activity. In addition, surface immobilization has been limited to monolayer coverage. It is shown that alternate depositions of negatively charged protein molecules, typically bovine serum albumin (BSA) with a positively charged aminocarbohydrate template such as glycol chitosan (GC) on magnetic iron oxide nanoparticle surface as a colloid, are carried out under pH 7.4. Circular dichroism (CD) clearly reveals that the secondary structure of the entrapped BSA sequential depositions in this manner remains totally unaltered which is in sharp contrast to previous attempts. Probing the binding properties of the entrapped BSA using small molecules (Site I and Site II drug compounds) confirms for the first time the full retention of its biological activity as compared with native BSA, which also implies the ready accessibility of the entrapped protein molecules through the porous overlayers. This work clearly suggests a new method to immobilize and store protein molecules beyond monolayer adsorption on a magnetic nanoparticle surface without much structural alteration. This may find applications in magnetic recoverable enzymes or protein delivery.

A calibrated, non-invasive method for measuring the internal interface height field at high resolution in the rotating, two-layer annulus

We describe a remote sensing method for measuring the internal interface height field in a rotating, two-layer annulus laboratory experiment. The method is non-invasive, avoiding the possibility of an interaction between the flow and the measurement device. The height fields retrieved are accurate and highly resolved in both space and time. The technique is based on a flow visualization method developed by previous workers, and relies upon the optical rotation properties of the working liquids. The previous methods returned only qualitative interface maps, however. In the present study, a technique is developed for deriving quantitative maps by calibrating height against the colour fields registered by a camera which views the flow from above. We use a layer-wise torque balance analysis to determine the equilibrium interface height field analytically, in order to derive the calibration curves. With the current system, viewing an annulus of outer radius 125 mm and depth 250 mm from a distance of 2 m, the inferred height fields have horizontal, vertical and temporal resolutions of up to 0.2 mm, 1 mm and 0.04 s, respectively.

Function of the hydration layer around an antifreeze protein revealed by atomistic molecular dynamics simulations

Atomistic molecular dynamics simulations are used to investigate the mechanism by which the antifreeze protein from the spruce budworm, Choristoneura fumiferana, binds to ice. Comparison of structural and dynamic properties of the water around the three faces of the triangular prism-shaped protein in aqueous solution reveals that at low temperature the water structure is ordered and the dynamics slowed down around the ice-binding face of the protein, with a disordering effect observed around the other two faces. These results suggest a dual role for the solvation water around the protein. The preconfigured solvation shell around the ice-binding face is involved in the initial recognition and binding of the antifreeze protein to ice by lowering the barrier for binding and consolidation of the protein:ice interaction surface. Thus, the antifreeze protein can bind to the molecularly rough ice surface by becoming actively involved in the formation of its own binding site. Also, the disruption of water structure around the rest of the protein helps prevent the adsorbed protein becoming covered by further ice growth.

Layer-by-layer deposition of praseodymium oxide on tin-doped indium oxide (ITO) surface

Praseodymium oxide as a thin film of controllable layer is known to display many unique physiochemical properties, which can be useful to ceramic, semiconductive and sensor industries. Here in this short paper, we describe a new chemical method of depositing praseodymium oxide on tin-doped indium oxide (ITO) surface using a layer-by-layer approach. The process is carried out by dipping the ITO in solutions of adsorbable polycationic chitosan and alkaline praseodymium hydroxide Pr(OH)(3) alternatively in order to build up the well-defined multi-layers. XRD suggests that the predominant form of the oxide is Pr6O11, obtained after heat treatment of the deposited ITO in static air at 500 degrees C. Microscopic studies including AFM, TEM and SEM indicate that the deposited oxide particles are uniform in size and shape (cylindrical), mesoporous and the thickness of the film can be controlled. AC impedance measurements of the deposited materials also reveal that the oxide layers display a high electrical conductivity hence suitable for sensor uses. (c) 2006 Elsevier B.V. All rights reserved.

Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB): oxidation of oleic acid by ozone

We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB) based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007). K2-SUB is applied to a popular model system of atmospheric heterogeneous chemistry: the interaction of ozone with oleic acid. We show that our modelling approach allows de-convoluting surface and bulk processes, which has been a controversial topic and remains an important challenge for the understanding and description of atmospheric aerosol transformation. In particular, we demonstrate how a detailed treatment of adsorption and reaction at the surface can be coupled to a description of bulk reaction and transport that is consistent with traditional resistor model formulations. From literature data we have derived a consistent set of kinetic parameters that characterise mass transport and chemical reaction of ozone at the surface and in the bulk of oleic acid droplets. Due to the wide range of rate coefficients reported from different experimental studies, the exact proportions between surface and bulk reaction rates remain uncertain. Nevertheless, the model results suggest an important role of chemical reaction in the bulk and an approximate upper limit of similar to 10(-11) cm(2) s(-1) for the surface reaction rate coefficient. Sensitivity studies show that the surface accommodation coefficient of the gas-phase reactant has a strong non-linear influence on both surface and bulk chemical reactions. We suggest that K2-SUB may be used to design, interpret and analyse future experiments for better discrimination between surface and bulk processes in the oleic acid-ozone system as well as in other heterogeneous reaction systems of atmospheric relevance.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (carbon-carbon double bonds) can reach chemical lifetimes of many hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (< 10(-10) cm(2) s(-1)). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas–particle interactions (P¨oschl et al., 5 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface 10 concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory stud15 ies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical lifetimes of 20 multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (10−10 cm2 s−1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB 25 as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Generation of inertia-gravity waves in the rotating thermal annulus by a localised boundary layer instability

Waves with periods shorter than the inertial period exist in the atmosphere (as inertia-gravity waves) and in the oceans (as Poincaré and internal gravity waves). Such waves owe their origin to various mechanisms, but of particular interest are those arising either from local secondary instabilities or spontaneous emission due to loss of balance. These phenomena have been studied in the laboratory, both in the mechanically-forced and the thermally-forced rotating annulus. Their generation mechanisms, especially in the latter system, have not yet been fully understood, however. Here we examine short period waves in a numerical model of the rotating thermal annulus, and show how the results are consistent with those from earlier laboratory experiments. We then show how these waves are consistent with being inertia-gravity waves generated by a localised instability within the thermal boundary layer, the location of which is determined by regions of strong shear and downwelling at certain points within a large-scale baroclinic wave flow. The resulting instability launches small-scale inertia-gravity waves into the geostrophic interior of the flow. Their behaviour is captured in fully nonlinear numerical simulations in a finite-difference, 3D Boussinesq Navier-Stokes model. Such a mechanism has many similarities with those responsible for launching small- and meso-scale inertia-gravity waves in the atmosphere from fronts and local convection.