Dynamical evolution of the 2003 southern hemisphere stratospheric winter using Envisat trace-gas observations

Data from the MIPAS instrument on Envisat, supplemented by meteorological analyses from ECMWF and the Met Office, are used to study the meteorological and trace-gas evolution of the stratosphere in the southern hemisphere during winter and spring 2003. A pole-centred approach is used to interpret the data in the physically meaningful context of the evolving stratospheric polar vortex. The following salient dynamical and transport features are documented and analysed: the merger of anticyclones in the stratosphere; the development of an intense, quasi-stationary anticyclone in spring; the associated top-down breakdown of the polar vortex; the systematic descent of air into the polar vortex; and the formation of a three-dimensional structure of a tracer filament on a planetary scale. The paper confirms and extends existing paradigms of the southern hemisphere vortex evolution. The quality of the MIPAS observations is seen to be generally good. though the water vapour retrievals are unrealistic above 10 hPa in the high-latitude winter.

North Atlantic Oscillation response to transient greenhouse gas forcing and the impact on European winter climate: a CMIP2 multi-model assessment

This study investigates the response of wintertime North Atlantic Oscillation (NAO) to increasing concentrations of atmospheric carbon dioxide (CO2) as simulated by 18 global coupled general circulation models that participated in phase 2 of the Coupled Model Intercomparison Project (CMIP2). NAO has been assessed in control and transient 80-year simulations produced by each model under constant forcing, and 1% per year increasing concentrations of CO2, respectively. Although generally able to simulate the main features of NAO, the majority of models overestimate the observed mean wintertime NAO index of 8 hPa by 5-10 hPa. Furthermore, none of the models, in either the control or perturbed simulations, are able to reproduce decadal trends as strong as that seen in the observed NAO index from 1970-1995. Of the 15 models able to simulate the NAO pressure dipole, 13 predict a positive increase in NAO with increasing CO2 concentrations. The magnitude of the response is generally small and highly model-dependent, which leads to large uncertainty in multi-model estimates such as the median estimate of 0.0061 +/- 0.0036 hPa per %CO2. Although an increase of 0.61 hPa in NAO for a doubling in CO2 represents only a relatively small shift of 0.18 standard deviations in the probability distribution of winter mean NAO, this can cause large relative increases in the probabilities of extreme values of NAO associated with damaging impacts. Despite the large differences in NAO responses, the models robustly predict similar statistically significant changes in winter mean temperature (warmer over most of Europe) and precipitation (an increase over Northern Europe). Although these changes present a pattern similar to that expected due to an increase in the NAO index, linear regression is used to show that the response is much greater than can be attributed to small increases in NAO. NAO trends are not the key contributor to model-predicted climate change in wintertime mean temperature and precipitation over Europe and the Mediterranean region. However, the models' inability to capture the observed decadal variability in NAO might also signify a major deficiency in their ability to simulate the NAO-related responses to climate change.

Chlorine tolerant, multilayer reverse-somosis membranes with high permeate flux and high salt rejection

A new class of high molecular weight polyethersulfone ionomers is described in which the ionic content can be varied, at will, over a very wide and fully-controllable range. A novel type of coating process enables these materials to be deposited from alcohol-type solvents as cohesive but very thin (50 – 250 nm) films on porous support-membranes, giving high-flux membranes (3.3 – 5.0 L m-2 h-1 bar-1) with very good, though not outstanding salt rejection (typically 92 - 96%). A secondary layer, of formaldehyde-cross-linked polyvinyl alcohol, can be deposited from aqueous solution on the surface of the ionomer membrane, and this layer increases salt rejection to greater than 99% without serious loss of water permeability. The final multi-layer membrane shows excellent chlorine tolerance in reverse-osmosis operation.

Profiling of phenols in human fecal water after raspberry supplementation.

The phenolic compositions of fecal water samples from ten free-living human subjects without marked dietary restrictions were monitored before and after intake of raspberry puree (200 g/day, 4 days) using gas chromatography-mass spectrometry. No single phenolic component was increased in all subjects after intake, but a majority of subjects had significant elevations in phenylacetic acid (7/10), 4-hydroxyphenylacetic acid (6/10), 3-hydroxyphenylacetic acid (5/10), 3-phenylpropionic acid and 3-(4-hydroxyphenyl)propionic acid. The levels of 3,4-dihydroxbenzoic acid were elevated in 8/10 subjects, significantly for 6 subjects (p < 0.05), and not significantly reduced in the other 2 subjects. In addition, unlike most other fecal metabolites, the increase was always >2-fold. This metabolite may be representative of the increased colonic dose of cyanidin anthocyanins. The colonic microbiota varied greatly between individuals, and supplementation with raspberries did not produce any statistically significant alterations in the profile of colonic bacteria, nor was a common pattern revealed to account for the interindividual variations observed in the fecal water phenolic profiles.

Sewage effluent clean-up reduces phosphorus but not phytoplankton in lowland chalk stream (River Kennet, UK) impacted by water mixing from adjacent canal

Information is provided on phosphorus in the River Kennet and the adjacent Kennet and Avon Canal in southern England to assess their interactions and the changes following phosphorus reductions in sewage treatment work (STW) effluent inputs. A step reduction in soluble reactive phosphorus (SRP) concentration within the effluent (5 to 13 fold) was observed from several STWs discharging to the river in the mid-2000s. This translated to over halving of SRP concentrations within the lower Kennet. Lower Kennet SRP concentrations change from being highest under base-flow to highest under storm-flow conditions. This represented a major shift from direct effluent inputs to a within-catchment source dominated system characteristic of the upper part to the catchment. Average SRP concentrations in the lower Kennet reduced over time towards the target for good water quality. Critically, there was no corresponding reduction in chlorophyll-a concentration, the waters remaining eutrophic when set against standards for lakes. Following the up gradient input of the main water and SRP source (Wilton Water), SRP concentrations in the canal reduced down gradient to below detection limits at times near its junction with the Kennet downstream. However, chlorophyll concentrations in the canal were in an order of magnitude higher than in the river. This probably resulted from long water residence times and higher temperatures promoting progressive algal and suspended sediment generations that consumed SRP. The canal acted as a point source for sediment, algae and total phosphorus to the river especially during the summer months when boat traffic disturbed the canal's bottom sediments and the locks were being regularly opened. The short-term dynamics of this transfer was complex. For the canal and the supply source at Wilton Water, conditions remained hypertrophic when set against standards for lakes even when SRP concentrations were extremely low.

Inter-laboratory variation of in vitro cumulative gas production profiles of feeds using manual and automated methods

A study was conducted to estimate variation among laboratories and between manual and automated techniques of measuring pressure on the resulting gas production profiles (GPP). Eight feeds (molassed sugarbeet feed, grass silage, maize silage, soyabean hulls, maize gluten feed, whole crop wheat silage, wheat, glucose) were milled to pass a I mm screen and sent to three laboratories (ADAS Nutritional Sciences Research Unit, UK; Institute of Grassland and Environmental Research (IGER), UK; Wageningen University, The Netherlands). Each laboratory measured GPP over 144 h using standardised procedures with manual pressure transducers (MPT) and automated pressure systems (APS). The APS at ADAS used a pressure transducer and bottles in a shaking water bath, while the APS at Wageningen and IGER used a pressure sensor and bottles held in a stationary rack. Apparent dry matter degradability (ADDM) was estimated at the end of the incubation. GPP were fitted to a modified Michaelis-Menten model assuming a single phase of gas production, and GPP were described in terms of the asymptotic volume of gas produced (A), the time to half A (B), the time of maximum gas production rate (t(RM) (gas)) and maximum gas production rate (R-M (gas)). There were effects (P<0.001) of substrate on all parameters. However, MPT produced more (P<0.001) gas, but with longer (P<0.001) B and t(RM gas) (P<0.05) and lower (P<0.001) R-M gas compared to APS. There was no difference between apparatus in ADDM estimates. Interactions occurred between substrate and apparatus, substrate and laboratory, and laboratory and apparatus. However, when mean values for MPT were regressed from the individual laboratories, relationships were good (i.e., adjusted R-2 = 0.827 or higher). Good relationships were also observed with APS, although they were weaker than for MPT (i.e., adjusted R-2 = 0.723 or higher). The relationships between mean MPT and mean APS data were also good (i.e., adjusted R 2 = 0. 844 or higher). Data suggest that, although laboratory and method of measuring pressure are sources of variation in GPP estimation, it should be possible using appropriate mathematical models to standardise data among laboratories so that data from one laboratory could be extrapolated to others. This would allow development of a database of GPP data from many diverse feeds. (c) 2005 Published by Elsevier B.V.

Time-resolved gas-phase kinetic and quantum chemical studies of reactions of silylene with chlorine-containing species. 1. HCl

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with HCL The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas, at five temperatures in the range of 296-611 K. The second-order rate constants fitted the Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-11.51 +/- 0.06) + (1.92 +/- 0.47 kJ mol(-1))/RTIn10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range of 10-100 Torr, but showed small decreases in value of no more than 20% ( +/- 10%) at I Toff, at both the highest and lowest temperatures. The data are consistent with formation of an initial weakly bound donor-acceptor complex, which reacts by two parallel pathways. The first is by chlorine-to-silicon H-shift to make vibrationally excited chlorosilane, SiH3Cl*, which yields HSiCl by H-2 elimination from silicon. In the second pathway, the complex proceeds via H-2 elimination (4-center process) to make chlorosilylene, HSiCl, directly. This interpretation is supported by ab initio quantum calculations carried out at the G3 level which reveal the direct H-2 elimination route for the first time. RRKM modeling predicts the approximate magnitude of the pressure effect but is unable to determine the proportions of each pathway. The experimental data agree with the only previous measurements at room temperature. Comparisons with other reactions of SiH2 are also drawn.

A pressure-jump time-resolved x-ray diffraction study of cubic-cubic transition kinetics in monoolein

In the past two decades, the geometric pathways involved in the transformations between inverse bicontinuous cubic phases in amphiphilic systems have been extensively theoretically modeled. However, little experimental data exists on the cubic-cubic transformation in pure lipid systems. We have used pressure-jump time-resolved X-ray diffraction to investigate the transition between the gyroid Q(II)(G) and double-diamond Q(II)(D) phases in mixtures of 1-monoolein in 30 wt% water. We find for this system that the cubic-cubic transition occurs without any detectable intermediate structures. In addition, we have determined the kinetics of the transition, in both the forward and reverse directions, as a function of pressure-jump amplitude, temperature, and water content. A recently developed model allows (at least in principle) the calculation of the activation energy for lipid phase transitions from such data. The analysis is applicable only if kinetic reproducibility is achieved, at least within one sample, and achievement of such kinetic reproducibility is shown here, by carrying out prolonged pressure-cycling. The rate of transformation shows clear and consistent trends with pressure-jump amplitude, temperature, and water content, all of which are shown to be in agreement with the effect of the shift in the position of the cubic-cubic phase boundary following a change in the thermodynamic parameters.

Influence of a halide ion on ribbons of water pentamer

Reactions of CuF2, CuCl2 center dot 2H(2)O and CuBr2 with 2,2'-dipyridylamine (HDPA) in water at room temperature using Cu: HDPA = 2: 1 mol yield [Cu(HDPA) (H2O)(2)F]F center dot 3H(2)O (1), Cu(HDPA) Cl-2 (2) and [Cu(HDPA) Br-2 (3) respectively. The structures of 2 and 3 are isostructural in spacegroup C-2 with cell dimensions; for 2, a = 14.702(8), b = 7.726(2), c = 4.829(6) angstrom, beta = 96.68(8)degrees and for 3, a = 14.2934(8), b = 7.9057(6), c = 5.1982(5) angstrom, beta = 94.049(7)degrees. In the X-ray crystal structure, the complex 1 is found to contain tapes of water pentamers. Our DFT calculations at the B3LYP/LanL2DZ level show that the reaction Cu(HDPA)X-2 + 2H(2)O = [Cu(HDPA)(H2O)(2)X]X is most exothermic in the gas phase when X- = F-, i.e., the tendency of water uptake is maximum for Cu(HDPA) F-2. It seems that the exothermicities of the aquations of Cu(HDPA) Cl-2 and Cu(HDPA) Br-2 are not sufficient to stabilise the type of ribbons of water observed in 1 and consequently water is eschewed when X- = Cl- or Br-.

Oxidation of oleic acid at the air-water interface and its potential effects on cloud critical supersaturations

The oxidation of organic films on cloud condensation nuclei has the potential to affect climate and precipitation events. In this work we present a study of the oxidation of a monolayer of deuterated oleic acid (cis-9-octadecenoic acid) at the air-water interface by ozone to determine if oxidation removes the organic film or replaces it with a product film. A range of different aqueous sub-phases were studied. The surface excess of deuterated material was followed by neutron reflection whilst the surface pressure was followed using a Wilhelmy plate. The neutron reflection data reveal that approximately half the organic material remains at the air-water interface following the oxidation of oleic acid by ozone, thus cleavage of the double bond by ozone creates one surface active species and one species that partitions to the bulk (or gas) phase. The most probable products, produced with a yield of similar to(87 +/- 14)%, are nonanoic acid, which remains at the interface, and azelaic acid (nonanedioic acid), which dissolves into the bulk solution. We also report a surface bimolecular rate constant for the reaction between ozone and oleic acid of (7.3 +/- 0.9) x 10(-11) cm(2) molecule s(-1). The rate constant and product yield are not affected by the solution sub-phase. An uptake coefficient of ozone on the oleic acid monolayer of similar to 4 x 10(-6) is estimated from our results. A simple Kohler analysis demonstrates that the oxidation of oleic acid by ozone on an atmospheric aerosol will lower the critical supersaturation needed for cloud droplet formation. We calculate an atmospheric chemical lifetime of oleic acid of 1.3 hours, significantly longer than laboratory studies on pure oleic acid particles suggest, but more consistent with field studies reporting oleic acid present in aged atmospheric aerosol.

Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coeffcients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic ( alkane) solvent. The droplet was exposed to gas- phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic- like substances, HULIS; a alpha- pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid- phase di. ffusion and reaction are the rate determining steps. Uptake coe. ffcients, g, were found to be ( 1.1 +/- 0.7) x 10(-5), ( 1.5 +/- 0.7) x 10 (-5) and ( 3.0 - 7.5) x 10 (-3) for the reactions of ozone with the fumarate, benzoate and a- pinene containing droplets, respectively. Liquid- phase bimolecular rate coe. cients for reactions of dissolved ozone molecules with fumarate, benzoate and a- pinene were also obtained: k(fumarate) = ( 2.7 +/- 2) x 10 (5), k(benzoate) = ( 3.5 +/- 3) x 10 (5) and k(alpha-pinene) = ( 1-3) x 10(7) dm(3) mol (-1) s (- 1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS- proxies and for the oxidation of a- pinene in pentadecane. The study of the alpha- pinene/ ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha- pinene suggest the formation of new species containing carbonyl groups.

Evaluation by volatile profile of the synergistic antioxidant effect between bovine serum albumin and virgin olive oil phenolic compounds in an oil-in-water emulsion

THE OXIDATIVE STABILITY OF OIL-IN-WATER EMULSIONS, CONTAINING BOVINE SERUM ALBUMIN (BSA) AND VIRGIN OLIVE OIL PHENOLIC COMPOUNDS, WAS STUDIED BY THE DETERMINATION OF THE FORMATION OF VOLATILE OXIDATION PRODUCTS. FOUR OIL-IN-WATER EMULSIONS WITH AND WITHOUT PHENOLS ISOLATED FROM VIRGIN OLIVE OIL AND BSA WERE PREPARED. THESE MODEL SYSTEMS WERE STORED AT 60 degrees C TO ACCELERATE LIPID OXIDATION. VOLATILE OXIDATION PRODUCTS WERE MONITORED EVERY THREE DAYS BY HEADSPACE SOLID-PHASE MICROEXTRACTION COUPLED WITH GAS CHROMATOGRAPHY. ALTHOUGH INDIVIDUALLY OLIVE OIL PHENOLIC COMPOUNDS AND BSA SHOWED A SIGNIFICANT ANTIOXIDANT ACTIVITY, THE COMBINATION OF THESE COMPONENTS SHOWED A VERY GOOD SYNERGY, QUANTIFIED AS 127%. IN FACT, THE EMULSION CONTAINING BOTH PHENOLIC COMPOUNDS AND BSA SHOWED A VERY LOW LEVEL OF OXIDATIVE DETERIORATION AFTER 45 DAYS STORAGE.

Bovine serum albumin produces a synergistic increase in the antioxidant activity of virgin olive oil phenolic compounds in oil-in-water emulsions

Virgin olive oil is valued for its flavor, but unacceptable off-flavors may develop on storage in food products containing this oil due to oxidation. The oxidative stability of oil-in-water emulsions containing bovine serum albumin (BSA) and virgin olive oil phenolic compounds was studied. Four oil-in-water emulsions with and without BSA and phenols isolated from virgin olive oil were prepared. These model systems were stored at 60 degrees C to speed up lipid oxidation. Primary and secondary oxidation products were monitored every three days. Peroxide values and conjugated diene contents were determined as measures of the primary oxidation products. p-Anisidine values and volatile compounds were determined as measures of the secondary oxidation products. This latter determination was carried out by headspace solid-phase microextraction coupled with gas chromatography. Although olive oil phenolic compounds and BSA contributed some antioxidant activity when present as individual additives, the combination of BSA with phenols in an emulsion showed 58-127% synergy, depending on which analytical method was used in the calculation. The emulsion containing phenolic compounds and BSA showed a low level of deterioration after 45 days of storage at 60 degrees C.

Recovery of norbixin from a raw extraction solution of annatto pigments using colloidal gas aphrons (CGAs)

Annatto dyes are widely used in food and are finding increasing interest also for their application in the pharmaceutical and cosmetics industry. Bixin is the main pigment extracted from annatto seeds and accounts for 80% of the carotenoids in the outer coat of the seeds; norbixin being the water-soluble form of the bixin. Typically annatto dyes are extracted from the seeds by mechanical means or solutions of alkali, edible oil or organic solvents, or a combination of the two depending on the desired final product. In this work CGAs are investigated as an alternative separation method for the recovery of norbixin from a raw extraction solution of annatto pigments in KOH. A volume of CGAs generated from a cationic surfactant (CTAB) solution is mixed with a volume of annatto solution and when the mixture is allowed to settle it separates into the top aphron phase and the bottom liquid phase. Potassium norbixinate presented in the annatto solution will interact with the surfactant in the aphron phase, which results in the effective separation of norbixin. Recovery= 94% was achieved at a CTAB to norbixin molar ratio of 3.3. In addition a mechanism of separation is proposed here based on the separation results with the cationic surfactant and an anionic surfactant (bis-2-ethyl hexyl sulfosuccinate, AOT) and measurements of surfactant to norbixin ratio in the aphron phase; electrostatic interactions between the surfactant and norbixin molecules result in the fort-nation of a coloured complex and effective separation of norbixin. (c) 2005 Elsevier B.V. All rights reserved.

An optimized reverse-phase high performance liquid chromatographic method for evaluating percutaneous absorption of glucosamine hydrochloride

A relatively simple, selective, precise and accurate high performance liquid chromatography (HPLC) method based on a reaction of phenylisothiocyanate (PITC) with glucosamine (GL) in alkaline media was developed and validated to determine glucosamine hydrochloride permeating through human skin in vitro. It is usually problematic to develop an accurate assay for chemicals traversing skin because the excellent barrier properties of the tissue ensure that only low amounts of the material pass through the membrane and skin components may leach out of the tissue to interfere with the analysis. In addition, in the case of glucosamine hydrochloride, chemical instability adds further complexity to assay development. The assay, utilising the PITC-GL reaction was refined by optimizing the reaction temperature, reaction time and PITC concentration. The reaction produces a phenylthiocarbarnyl-glucosamine (PTC-GL) adduct which was separated on a reverse-phase (RP) column packed with 5 mu m ODS (C-18) Hypersil particles using a diode array detector (DAD) at 245 nm. The mobile phase was methanol-water-glacial acetic acid (10:89.96:0.04 v/v/v, pH 3.5) delivered to the column at 1 ml min(-1) and the column temperature was maintained at 30 degrees C Using a saturated aqueous solution of glucosamine hydrochloride, in vitro permeation studies were performed at 32 +/- 1 degrees C over 48 h using human epidermal membranes prepared by a heat separation method and mounted in Franz-type diffusion cells with a diffusional area 2.15 +/- 0.1 cm(2). The optimum derivatisation reaction conditions for reaction temperature, reaction time and PITC concentration were found to be 80 degrees C, 30 min and 1 % v/v, respectively. PTC-Gal and GL adducts eluted at 8.9 and 9.7 min, respectively. The detector response was found to be linear in the concentration range 0-1000 mu g ml(-1). The assay was robust with intra- and inter-day precisions (described as a percentage of relative standard deviation, %R.S.D.) < 12. Intra- and inter-day accuracy (as a percentage of the relative error, %RE) was <=-5.60 and <=-8.00, respectively. Using this assay, it was found that GL-HCI permeates through human skin with a flux 1.497 +/- 0.42 mu g cm(-2) h(-1), a permeability coefficient of 5.66 +/- 1.6 x 10(-6) cm h(-1) and with a lag time of 10.9 +/- 4.6 h. (c) 2005 Elsevier B.V. All rights reserved.