Reaction of a phospholipid monolayer with gas-phase ozone at the air-water interface: measurement of surface excess and surface pressure in real time

The reaction between gas-phase ozone and monolayers of the unsaturated lipid 1-palmitoy1-2-oleoyl-sn-glycero-3-phosphocholine, POPC, on aqueous solutions has been studied in real time using neutron reflection and surface pressure measurements. The reaction between ozone and lung surfactant, which contains POPC, leads to decreased pulmonary function, but little is known shout the changes that occur to the interfacial material as a result of oxidation. The results reveal that the initial reaction of ozone with POPC leads to a rapid increase in surface pressure followed by a slow decrease to very low values. The neutron reflection measurements, performed on an isotopologue of POPC with a selectively deuterated palmitoyl strand, reveal that the reaction leads to loss of this strand from the air-water interface. suggesting either solubilization of the product lipid or degradation of the palmitoyl strand by a reactive species. Reactions of H-1-POPC on D2O reveal that the headgroup region of the lipids in aqueous solution is not dramatically perturbed by the reaction of POPC monolayers with ozone supporting degradation of the palmitoyl strand rather than solubilization. The results are consistent with the reaction of ozone with the oleoyl strand of POPC at the air water interface leading to the formation of OH radicals. the highly reactive OH radicals produced can then go on to react with the saturated palmitoyl strands leading to the formation or oxidized lipids with shorter alkyl tails.

The importance of surface pressure changes in the response of the atmosphere to zonally-symmetric thermal and mechanical forcing

he classical problem of the response of a balanced, axisymmetric vortex to thermal and mechanical forcing is re-examined, paying special attention to the lower boundary condition. The correct condition is DΦ/Dt = 0, where Φ is the geopotential and D/Dt the material derivative, which explicitly accounts for a mass redistribution as part of the mean-flow response. This redistribution is neglected when using the boundary condition Dp/Dt = 0, which has conventionally been applied in this problem. It is shown that applying the incorrect boundary condition, and thereby ignoring the surface pressure change, leads to a zonal wind acceleration δū/δt that is too strong, especially near the surface. The effect is significant for planetary-scale forcing even when applied at tropopause level. A comparison is made between the mean-flow evolution in a baroclinic life-cycle, as simulated in a fully nonlinear, primitive-equation model, and that predicted by using the simulated eddy fluxes in the zonally-symmetric response problem. Use of the correct lower boundary condition is shown to lead to improved agreement.

General relationships between pressure, weight, and mass of a hydrostatic fluid

In curved geometries the hydrostatic pressure in a fluid does not equal the weight per unit area of the fluid above it. General weight–pressure and mass–pressure relationships for hydrostatic fluids in any geometry are derived. As an example of the mass–pressure relationship, we find a geometric reduction in surface pressure as large as 5 mbar on Earth and 39 mbar on Titan. We also present a thermodynamic interpretation of the geometric correction which, as a corollary, provides an independent proof of the hydrostatic relationship for general geometries.

Ensemble prediction for nowcasting with a convection-permitting model—I: description of the system and the impact of radar-derived surface precipitation rates

A key strategy to improve the skill of quantitative predictions of precipitation, as well as hazardous weather such as severe thunderstorms and flash floods is to exploit the use of observations of convective activity (e.g. from radar). In this paper, a convection-permitting ensemble prediction system (EPS) aimed at addressing the problems of forecasting localized weather events with relatively short predictability time scale and based on a 1.5 km grid-length version of the Met Office Unified Model is presented. Particular attention is given to the impact of using predicted observations of radar-derived precipitation intensity in the ensemble transform Kalman filter (ETKF) used within the EPS. Our initial results based on the use of a 24-member ensemble of forecasts for two summer case studies show that the convective-scale EPS produces fairly reliable forecasts of temperature, horizontal winds and relative humidity at 1 h lead time, as evident from the inspection of rank histograms. On the other hand, the rank histograms seem also to show that the EPS generates too much spread for forecasts of (i) surface pressure and (ii) surface precipitation intensity. These may indicate that for (i) the value of surface pressure observation error standard deviation used to generate surface pressure rank histograms is too large and for (ii) may be the result of non-Gaussian precipitation observation errors. However, further investigations are needed to better understand these findings. Finally, the inclusion of predicted observations of precipitation from radar in the 24-member EPS considered in this paper does not seem to improve the 1-h lead time forecast skill.

Surface activity of surfactin recovered and purified from fermentation broth using a two-step ultrafiltration (UF) process

B. subtilis under certain types of media and fermentation conditions can produce surfactin, a biosurfactant which belongs to the lipopeptide class. Surfactin has exceptional surfactant activity, and exhibits some interesting biological characteristics such as antibacterial activity, antitumoral activity against ascites carcinoma cells, and a hypocholesterolemic activity that inhibits cAMP phosphodiesterase, as well as having anti-HIV properties. A cost effective recovery and purification of surfactin from fermentation broth using a two-step ultrafiltration (UF) process has been developed in order to reduce the cost of surfactin production. In this study, competitive adsorption of surfactin and proteins at the air-water interface was studied using surface pressure measurements. Small volumes of bovine serum albumin (BSA) and β-casein solutions were added to the air-water interface on a Langmuir trough and allowed to stabilise before the addition of surfactin to the subphase. Contrasting interfacial behaviour of proteins was observed with β-casein showing faster initial adsorption compared to BSA. On introduction of surfactin both proteins were displaced but a longer time were taken to displace β-casein. Overall the results showed surfactin were highly surface-active by forming a β-sheet structure at the air-water interface after reaching its critical micelle concentration (CMC) and were effective in removing both protein films, which can be explained following the orogenic mechanism. Results showed that the two-step UF process was effective to achieve high purity and fully functional surfactin.

On the use of a time sequence of surface pressures in four-dimensional data assimilation

The possibility of using a time sequence of surface pressure observations in four-dimensional data assimilation is being investigated. It is shown that a linear multilevel quasi-geostrophic model can be updated successfully with surface data alone, provided the number of time levels are at least as many as the number of vertical levels. It is further demonstrated that current statistical analysis procedures are very inefficient to assimilate surface observations, and it is shown by numerical experiments that the vertical interpolation must be carried out using the structure of the most dominating baroclinic mode in order to obtain a satisfactory updating. Different possible ways towards finding a practical solution are being discussed.

Global observations and forecast skill

The impact of selected observing systems on forecast skill is explored using the European Centre for Medium-Range Weather Forecasts (ECMWF) 40-yr reanalysis (ERA-40) system. Analyses have been produced for a surface-based observing system typical of the period prior to 1945/1950, a terrestrial-based observing system typical of the period 1950-1979 and a satellite-based observing system consisting of surface pressure and satellite observations. Global prediction experiments have been undertaken using these analyses as initial states, and which are available every 6 h, for the boreal winters of 1990/1991 and 2000/2001 and the summer of 2000, using a more recent version of the ECMWF model. The results show that for 500-hPa geopotential height, as a representative field, the terrestrial system in the Northern Hemisphere extratropics is only slightly inferior to the control system, which makes use of all observations for the analysis, and is also more accurate than the satellite system. There are indications that the skill of the terrestrial system worsens slightly and the satellite system improves somewhat between 1990/1991 and 2000/2001. The forecast skill in the Southern Hemisphere is dominated by the satellite information and this dominance is larger in the latter period. The overall skill is only slightly worse than that of the Northern Hemisphere. In the tropics (20 degrees S-20 degrees N), using the wind at 850 and 250 hPa as representative fields, the information content in the terrestrial and satellite systems is almost equal and complementary. The surface-based system has very limited skill restricted to the lower troposphere of the Northern Hemisphere. Predictability calculations show a potential for a further increase in predictive skill of 1-2 d in the extratropics of both hemispheres, but a potential for a major improvement of many days in the tropics. As well as the Eulerian perspective of predictability, the storm tracks have been calculated from all experiments and validated for the extratropics to provide a Lagrangian perspective.

Sensitivity of large-scale atmospheric analyses to humidity observations and its impact on the global water cycle and tropical and extratropical weather systems in ERA40

Reanalysis data obtained from data assimilation are increasingly used for diagnostic studies of the general circulation of the atmosphere, for the validation of modelling experiments and for estimating energy and water fluxes between the Earth surface and the atmosphere. Because fluxes are not specifically observed, but determined by the data assimilation system, they are not only influenced by the utilized observations but also by model physics and dynamics and by the assimilation method. In order to better understand the relative importance of humidity observations for the determination of the hydrological cycle, in this paper we describe an assimilation experiment using the ERA40 reanalysis system where all humidity data have been excluded from the observational data base. The surprising result is that the model, driven by the time evolution of wind, temperature and surface pressure, is able to almost completely reconstitute the large-scale hydrological cycle of the control assimilation without the use of any humidity data. In addition, analysis of the individual weather systems in the extratropics and tropics using an objective feature tracking analysis indicates that the humidity data have very little impact on these systems. We include a discussion of these results and possible consequences for the way moisture information is assimilated, as well as the potential consequences for the design of observing systems for climate monitoring. It is further suggested, with support from a simple assimilation study with another model, that model physics and dynamics play a decisive role for the hydrological cycle, stressing the need to better understand these aspects of model parametrization. .

Sensitivity of the ERA40 reanalysis to the observing system: determination of the global atmospheric circulation from reduced observations

The impact of selected observing systems on the European Centre for Medium-Range Weather Forecasts (ECMWF) 40-yr reanalysis (ERA40) is explored by mimicking observational networks of the past. This is accomplished by systematically removing observations from the present observational data base used by ERA40. The observing systems considered are a surface-based system typical of the period prior to 1945/50, obtained by only retaining the surface observations, a terrestrial-based system typical of the period 1950-1979, obtained by removing all space-based observations, and finally a space-based system, obtained by removing all terrestrial observations except those for surface pressure. Experiments using these different observing systems have been limited to seasonal periods selected from the last 10 yr of ERA40. The results show that the surface-based system has severe limitations in reconstructing the atmospheric state of the upper troposphere and stratosphere. The terrestrial system has major limitations in generating the circulation of the Southern Hemisphere with considerable errors in the position and intensity of individual weather systems. The space-based system is able to analyse the larger-scale aspects of the global atmosphere almost as well as the present observing system but performs less well in analysing the smaller-scale aspects as represented by the vorticity field. Here, terrestrial data such as radiosondes and aircraft observations are of paramount importance. The terrestrial system in the form of a limited number of radiosondes in the tropics is also required to analyse the quasi-biennial oscillation phenomenon in a proper way. The results also show the dominance of the satellite observing system in the Southern Hemisphere. These results all indicate that care is required in using current reanalyses in climate studies due to the large inhomogeneity of the available observations, in particular in time.

Preferred structures in large-scale circulation and the effect of doubling greenhouse gas concentration in HadCM3

Preferred structures in the surface pressure variability are investigated in and compared between two 100-year simulations of the Hadley Centre climate model HadCM3. In the first (control) simulation, the model is forced with pre-industrial carbon dioxide concentration (1×CO2) and in the second simulation the model is forced with doubled CO2 concentration (2×CO2). Daily winter (December-January-February) surface pressures over the Northern Hemisphere are analysed. The identification of preferred patterns is addressed using multivariate mixture models. For the control simulation, two significant flow regimes are obtained at 5% and 2.5% significance levels within the state space spanned by the leading two principal components. They show a high pressure centre over the North Pacific/Aleutian Islands associated with a low pressure centre over the North Atlantic, and its reverse. For the 2×CO2 simulation, no such behaviour is obtained. At higher-dimensional state space, flow patterns are obtained from both simulations. They are found to be significant at the 1% level for the control simulation and at the 2.5% level for the 2×CO2 simulation. Hence under CO2 doubling, regime behaviour in the large-scale wave dynamics weakens. Doubling greenhouse gas concentration affects both the frequency of occurrence of regimes and also the pattern structures. The less frequent regime becomes amplified and the more frequent regime weakens. The largest change is observed over the Pacific where a significant deepening of the Aleutian low is obtained under CO2 doubling.

Stratospheric Memory and Skill of Extended-Range Weather Forecasts

We use an empirical statistical model to demonstrate significant skill in making extended-range forecasts of the monthly-mean Arctic Oscillation (AO). Forecast skill derives from persistent circulation anomalies in the lowermost stratosphere and is greatest during boreal winter. A comparison to the Southern Hemisphere provides evidence that both the time scale and predictability of the AO depend on the presence of persistent circulation anomalies just above the tropopause. These circulation anomalies most likely affect the troposphere through changes to waves in the upper troposphere, which induce surface pressure changes that correspond to the AO.

Will Extratropical Storms Intensify in a Warmer Climate?

Extratropical cyclones and how they may change in a warmer climate have been investigated in detail with a high-resolution version of the ECHAM5 global climate model. A spectral resolution of T213 (63 km) is used for two 32-yr periods at the end of the twentieth and twenty-first centuries and integrated for the Intergovernmental Panel on Climate Change (IPCC) A1B scenario. Extremes of pressure, vorticity, wind, and precipitation associated with the cyclones are investigated and compared with a lower-resolution simulation. Comparison with observations of extreme wind speeds indicates that the model reproduces realistic values. This study also investigates the ability of the model to simulate extratropical cyclones by computing composites of intense storms and contrasting them with the same composites from the 40-yr ECMWF Re-Analysis (ERA-40). Composites of the time evolution of intense cyclones are reproduced with great fidelity; in particular the evolution of central surface pressure is almost exactly replicated, but vorticity, maximum wind speed, and precipitation are higher in the model. Spatial composites also show that the distributions of pressure, winds, and precipitation at different stages of the cyclone life cycle compare well with those from ERA-40, as does the vertical structure. For the twenty-first century, changes in the distribution of storms are very similar to those of previous study. There is a small reduction in the number of cyclones but no significant changes in the extremes of wind and vorticity in both hemispheres. There are larger regional changes in agreement with previous studies. The largest changes are in the total precipitation, where a significant increase is seen. Cumulative precipitation along the tracks of the cyclones increases by some 11% per track, or about twice the increase in global precipitation, while the extreme precipitation is close to the globally averaged increase in column water vapor (some 27%). Regionally, changes in extreme precipitation are even higher because of changes in the storm tracks.

Observed trends and teleconnections of the Siberian high: A recently declining center of action

This study investigates variability in the intensity of the wintertime Siberian high (SH) by defining a robust SH index (SHI) and correlating it with selected meteorological fields and teleconnection indices. A dramatic trend of -2.5 hPa decade(-1) has been found in the SHI between 1978 and 2001 with unprecedented (since 1871) low values of the SHI. The weakening of the SH has been confirmed by analyzing different historical gridded analyses and individual station observations of sea level pressure (SLP) and excluding possible effects from the conversion of surface pressure to SLP. SHI correlation maps with various meteorological fields show that SH impacts on circulation and temperature patterns extend far outside the SH source area extending from the Arctic to the tropical Pacific. Advection of warm air from eastern Europe has been identified as the main mechanism causing milder than normal conditions over the Kara and Laptev Seas in association with a strong SH. Despite the strong impacts of the variability in the SH on climatic variability across the Northern Hemisphere, correlations between the SHI and the main teleconnection indices of the Northern Hemisphere are weak. Regression analysis has shown that teleconnection indices are not able to reproduce the interannual variability and trends in the SH. The inclusion of regional surface temperature in the regression model provides closer agreement between the original and reconstructed SHI.

The diurnal cycle of convection and atmospheric tides in an aquaplanet

The diurnal cycle of tropical convection and its relationship to the atmospheric tides is investigated using an aquaplanet GCM. The diurnal and semidiurnal harmonics of precipitation are both found to contribute significantly to the total diurnal variability of precipitation in the model, which is broadly consistent with observations of the diurnal cycle of convection over the open ocean. The semidiurnal tide is found to be the dominant forcing for the semidiurnal harmonic of precipitation. In contrast the diurnal tide plays only a small role in forcing the diurnal harmonic of precipitation, which is dominated by the variations in shortwave and longwave heating. In both the diurnal and semidiurnal harmonics, the feedback onto the convection by the humidity tendencies due to the convection is found to be important in determining the phase of the harmonics. Further experiments show that the diurnal cycle of precipitation is sensitive to the choice of closure in the convection scheme. While the surface pressure signal of the simulated atmospheric tides in the model agree well with both theory and observations in their magnitude and phase, sensitivity experiments suggest that the role of the stratospheric ozone in forcing the semidiurnal tide is much reduced compared to theoretical predictions. Furthermore, the influence of the cloud radiative effects seems small. It is suggested that the radiative heating profile in the troposphere, associated primarily with the water vapor distribution, is more important than previously thought for driving the semidiurnal tide. However, this result may be sensitive to the vertical resolution and extent of the model.