O_3-N_2O correlations from the Atmospheric Chemistry Experiment: revisiting a diagnostic of transport and chemistry in the stratosphere

Our knowledge of stratospheric O3-N2O correlations is extended, and their potential for model-measurement comparison assessed, using data from the Atmospheric Chemistry Experiment (ACE) satellite and the Canadian Middle Atmosphere Model (CMAM). ACE provides the first comprehensive data set for the investigation of interhemispheric, interseasonal, and height-resolved differences of the O_3-N_2O correlation structure. By subsampling the CMAM data, the representativeness of the ACE data is evaluated. In the middle stratosphere, where the correlations are not compact and therefore mainly reflect the data sampling, joint probability density functions provide a detailed picture of key aspects of transport and mixing, but also trace polar ozone loss. CMAM captures these important features, but exhibits a displacement of the tropical pipe into the Southern Hemisphere (SH). Below about 21 km, the ACE data generally confirm the compactness of the correlations, although chemical ozone loss tends to destroy the compactness during late winter/spring, especially in the SH. This allows a quantitative comparison of the correlation slopes in the lower and lowermost stratosphere (LMS), which exhibit distinct seasonal cycles that reveal the different balances between diabatic descent and horizontal mixing in these two regions in the Northern Hemisphere (NH), reconciling differences found in aircraft measurements, and the strong role of chemical ozone loss in the SH. The seasonal cycles are qualitatively well reproduced by CMAM, although their amplitude is too weak in the NH LMS. The correlation slopes allow a "chemical" definition of the LMS, which is found to vary substantially in vertical extent with season.

Maximising umami taste in meat using natural ingredients: effects on chemistry, sensory perception and hedonic liking in young and old consumers

BACKGROUND: Umami taste in foods is elicited predominantly by the presence of glutamic acid and 5’-ribonucleotides, which act synergistically. This study aimed to use natural ingredients to maximise umami taste of a meat formulation and determine effects on liking of older consumers. METHODS: Cooked meat products with added natural ingredients (yeast extract, mycoscent, shiitake extract, tomato puree, soy sauce and soy bean paste) or monosodium glutamate (MSG) were prepared and compared to a control sample analytically (umami compounds), sensorially (sensory profile) and hedonically (liking by younger and older volunteers). Taste detection thresholds of sodium chloride and MSG of volunteers were collected. RESULTS: Four of the seven cooked meat products developed had a significantly higher content of umami-contributing compounds compared to the control. All products, except those containing MSG or tomato puree, were scored (by trained sensory panel) perceptually significantly higher in umami and / or salty taste compared to the control. Consumer tests showed a correlation of liking by the older cohort with perceived saltiness (ρ=0.76). CONCLUSION: The addition of natural umami-containing ingredients during the cooking of meat can provide enhanced umami and salty taste characteristics, this can lead to increased liking by some consumers, particularly those with raised taste detection thresholds.

Using transport diagnostics to understand chemistry climate model ozone simulations

We use observations of N2O and mean age to identify realistic transport in models in order to explain their ozone predictions. The results are applied to 15 chemistry climate models (CCMs) participating in the 2010 World Meteorological Organization ozone assessment. Comparison of the observed and simulated N2O, mean age and their compact correlation identifies models with fast or slow circulations and reveals details of model ascent and tropical isolation. This process‐oriented diagnostic is more useful than mean age alone because it identifies models with compensating transport deficiencies that produce fortuitous agreement with mean age. The diagnosed model transport behavior is related to a model’s ability to produce realistic lower stratosphere (LS) O3 profiles. Models with the greatest tropical transport problems compare poorly with O3 observations. Models with the most realistic LS transport agree more closely with LS observations and each other. We incorporate the results of the chemistry evaluations in the Stratospheric Processes and their Role in Climate (SPARC) CCMVal Report to explain the range of CCM predictions for the return‐to‐1980 dates for global (60°S–60°N) and Antarctic column ozone. Antarctic O3 return dates are generally correlated with vortex Cly levels, and vortex Cly is generally correlated with the model’s circulation, although model Cl chemistry and conservation problems also have a significant effect on return date. In both regions, models with good LS transport and chemistry produce a smaller range of predictions for the return‐to‐1980 ozone values. This study suggests that the current range of predicted return dates is unnecessarily broad due to identifiable model deficiencies.

Northern winter stratospheric temperature and ozone responses to ENSO inferred from an ensemble of Chemistry Climate Models

The connection between the El Ni˜no Southern Oscillation (ENSO) and the Northern polar stratosphere has been established from observations and atmospheric modeling. Here a systematic inter-comparison of the sensitivity of the modeled stratosphere to ENSO in Chemistry Climate Models (CCMs) is reported. This work uses results from a number of the CCMs included in the 2006 ozone assessment. In the lower stratosphere, the mean of all model simulations reports a warming of the polar vortex during strong ENSO events in February–March, consistent with but smaller than the estimate from satellite observations and ERA40 reanalysis. The anomalous warming is associated with an anomalous dynamical increase of column ozone north of 70� N that is accompanied by coherent column ozone decrease in the Tropics, in agreement with that deduced from the NIWA column ozone database, implying an increased residual circulation in the mean of all model simulations during ENSO. The spread in the model responses is partly due to the large internal stratospheric variability and it is shown that it crucially depends on the representation of the tropospheric ENSO teleconnection in the models.

Assessment of temperature, trace species, and ozone in chemistry-climate model simulations of the recent past

Simulations of the stratosphere from thirteen coupled chemistry-climate models (CCMs) are evaluated to provide guidance for the interpretation of ozone predictions made by the same CCMs. The focus of the evaluation is on how well the fields and processes that are important for determining the ozone distribution are represented in the simulations of the recent past. The core period of the evaluation is from 1980 to 1999 but long-term trends are compared for an extended period (1960–2004). Comparisons of polar high-latitude temperatures show that most CCMs have only small biases in the Northern Hemisphere in winter and spring, but still have cold biases in the Southern Hemisphere spring below 10 hPa. Most CCMs display the correct stratospheric response of polar temperatures to wave forcing in the Northern, but not in the Southern Hemisphere. Global long-term stratospheric temperature trends are in reasonable agreement with satellite and radiosonde observations. Comparisons of simulations of methane, mean age of air, and propagation of the annual cycle in water vapor show a wide spread in the results, indicating differences in transport. However, for around half the models there is reasonable agreement with observations. In these models the mean age of air and the water vapor tape recorder signal are generally better than reported in previous model intercomparisons. Comparisons of the water vapor and inorganic chlorine (Cly) fields also show a large intermodel spread. Differences in tropical water vapor mixing ratios in the lower stratosphere are primarily related to biases in the simulated tropical tropopause temperatures and not transport. The spread in Cly, which is largest in the polar lower stratosphere, appears to be primarily related to transport differences. In general the amplitude and phase of the annual cycle in total ozone is well simulated apart from the southern high latitudes. Most CCMs show reasonable agreement with observed total ozone trends and variability on a global scale, but a greater spread in the ozone trends in polar regions in spring, especially in the Arctic. In conclusion, despite the wide range of skills in representing different processes assessed here, there is sufficient agreement between the majority of the CCMs and the observations that some confidence can be placed in their predictions.

Uncertainties and assessments of chemistry-climate models of the stratosphere

In recent years a number of chemistry-climate models have been developed with an emphasis on the stratosphere. Such models cover a wide range of time scales of integration and vary considerably in complexity. The results of specific diagnostics are here analysed to examine the differences amongst individual models and observations, to assess the consistency of model predictions, with a particular focus on polar ozone. For example, many models indicate a significant cold bias in high latitudes, the “cold pole problem”, particularly in the southern hemisphere during winter and spring. This is related to wave propagation from the troposphere which can be improved by improving model horizontal resolution and with the use of non-orographic gravity wave drag. As a result of the widely differing modelled polar temperatures, different amounts of polar stratospheric clouds are simulated which in turn result in varying ozone values in the models. The results are also compared to determine the possible future behaviour of ozone, with an emphasis on the polar regions and mid-latitudes. All models predict eventual ozone recovery, but give a range of results concerning its timing and extent. Differences in the simulation of gravity waves and planetary waves as well as model resolution are likely major sources of uncertainty for this issue. In the Antarctic, the ozone hole has probably reached almost its deepest although the vertical and horizontal extent of depletion may increase slightly further over the next few years. According to the model results, Antarctic ozone recovery could begin any year within the range 2001 to 2008. The limited number of models which have been integrated sufficiently far indicate that full recovery of ozone to 1980 levels may not occur in the Antarctic until about the year 2050. For the Arctic, most models indicate that small ozone losses may continue for a few more years and that recovery could begin any year within the range 2004 to 2019. The start of ozone recovery in the Arctic is therefore expected to appear later than in the Antarctic.

Sensitivity of biogenic isoprene emissions to past, present and future environmental conditions and implications for atmospheric chemistry.

[1] We have implemented a process-based isoprene emission model in the HadGEM2 Earth-system model with coupled atmospheric chemistry in order to examine the feedback between isoprene emission and climate. Isoprene emissions and their impact on atmospheric chemistry and climate are estimated for preindustrial (1860–1869), present-day (2000–2009), and future (2100–2109) climate conditions. The estimate of 460 TgC/yr for present-day global total isoprene emission is consistent with previous estimates. Preindustrial isoprene emissions are estimated to be 26% higher than present-day. Future isoprene emissions using the RCP8.5 scenario are similar to present-day because increased emissions resulting from climate warming are countered by CO2 inhibition of isoprene emissions. The impact of biogenic isoprene emissions on the global O3 burden and CH4 lifetime is small but locally significant, and the impact of changes in isoprene emissions on atmospheric chemistry depends strongly on the state of climate and chemistry.

A Lagrangian model of air-mass photochemistry and mixing using a trajectory ensemble: the Cambridge Tropospheric Trajectory model of Chemistry And Transport (CiTTyCAT) version 4.2

A Lagrangian model of photochemistry and mixing is described (CiTTyCAT, stemming from the Cambridge Tropospheric Trajectory model of Chemistry And Transport), which is suitable for transport and chemistry studies throughout the troposphere. Over the last five years, the model has been developed in parallel at several different institutions and here those developments have been incorporated into one "community" model and documented for the first time. The key photochemical developments include a new scheme for biogenic volatile organic compounds and updated emissions schemes. The key physical development is to evolve composition following an ensemble of trajectories within neighbouring air-masses, including a simple scheme for mixing between them via an evolving "background profile", both within the boundary layer and free troposphere. The model runs along trajectories pre-calculated using winds and temperature from meteorological analyses. In addition, boundary layer height and precipitation rates, output from the analysis model, are interpolated to trajectory points and used as inputs to the mixing and wet deposition schemes. The model is most suitable in regimes when the effects of small-scale turbulent mixing are slow relative to advection by the resolved winds so that coherent air-masses form with distinct composition and strong gradients between them. Such air-masses can persist for many days while stretching, folding and thinning. Lagrangian models offer a useful framework for picking apart the processes of air-mass evolution over inter-continental distances, without being hindered by the numerical diffusion inherent to global Eulerian models. The model, including different box and trajectory modes, is described and some output for each of the modes is presented for evaluation. The model is available for download from a Subversion-controlled repository by contacting the corresponding authors.

Ozone climatology using interactive chemistry: results from the Canadian Middle Atmosphere Model

The climatology of ozone produced by the Canadian Middle Atmosphere Model (CMAM) is presented. This three-dimensional global model incorporates the radiative feedbacks of ozone and water vapor calculated on-line with a photochemical module. This module includes a comprehensive gas-phase reaction set and a limited set of heterogeneous reactions to account for processes occurring on background sulphate aerosols. While transport is global, photochemistry is solved from about 400 hPa to the top of the model at ∼95 km. This approach provides a complete and comprehensive representation of transport, emission, and photochemistry of various constituents from the surface to the mesopause region. A comparison of model results with observations indicates that the ozone distribution and variability are in agreement with observations throughout most of the model domain. Column ozone annual variation is represented to within 5–10% of the observations except in the Southern Hemisphere for springtime high latitudes. The vertical ozone distribution is generally well represented by the model up to the mesopause region. Nevertheless, in the upper stratosphere, the model generally underestimates the amount of ozone as well as the latitudinal tilting of ozone isopleths at high latitude. Ozone variability is analyzed and compared with measurements. The comparison shows that the phase and amplitude of the seasonal variation as well as shorter timescale variations are well represented by the model at various latitudes and heights. Finally, the impact of incorporating ozone radiative feedback on the model climatology is isolated. It is found that the incorporation of ozone radiative feedback results in a cooling of ∼8 K in the summer stratopause region, which corrects a warm bias that results when climatological ozone is used.

Synthesis of thiolated and acrylated nanoparticles using thiol-ene click chemistry: towards novel mucoadhesive materials for drug delivery

Thiol- and acrylate-functionalized nanoparticles have been synthesized from pentaerythritol tetrakis(3-mercapto-propionate) and pentaerythritol tetraacrylate using thiol-ene click chemistry. Using Raman and 1H NMR spectroscopy as well as Ellman's assay, it was demonstrated that excess pentaerythritol tetraacrylate in the feed mixture led to nanoparticles with free acrylate groups on their surface, whereas nanoparticles with thiolated surfaces could be synthesized using feed mixtures with excess pentaerythritol tetrakis(3-mercapto-propionate). The possibility of fluorescent labelling of thiolated nanoparticles has been demonstrated through their reaction with fluorescein-5-maleimide. The thiolated nanoparticles were found to be mucoadhesive and exhibited retention on mucosal surface of porcine urinary bladder.

Wave activity in the tropical tropopause layer in seven reanalysis and four chemistry climate model data sets

Sub-seasonal variability including equatorial waves significantly influence the dehydration and transport processes in the tropical tropopause layer (TTL). This study investigates the wave activity in the TTL in 7 reanalysis data sets (RAs; NCEP1, NCEP2, ERA40, ERA-Interim, JRA25, MERRA, and CFSR) and 4 chemistry climate models (CCMs; CCSRNIES, CMAM, MRI, and WACCM) using the zonal wave number-frequency spectral analysis method with equatorially symmetric-antisymmetric decomposition. Analyses are made for temperature and horizontal winds at 100 hPa in the RAs and CCMs and for outgoing longwave radiation (OLR), which is a proxy for convective activity that generates tropopause-level disturbances, in satellite data and the CCMs. Particular focus is placed on equatorial Kelvin waves, mixed Rossby-gravity (MRG) waves, and the Madden-Julian Oscillation (MJO). The wave activity is defined as the variance, i.e., the power spectral density integrated in a particular zonal wave number-frequency region. It is found that the TTL wave activities show significant difference among the RAs, ranging from ∼0.7 (for NCEP1 and NCEP2) to ∼1.4 (for ERA-Interim, MERRA, and CFSR) with respect to the averages from the RAs. The TTL activities in the CCMs lie generally within the range of those in the RAs, with a few exceptions. However, the spectral features in OLR for all the CCMs are very different from those in the observations, and the OLR wave activities are too low for CCSRNIES, CMAM, and MRI. It is concluded that the broad range of wave activity found in the different RAs decreases our confidence in their validity and in particular their value for validation of CCM performance in the TTL, thereby limiting our quantitative understanding of the dehydration and transport processes in the TTL.

Measurements of NO, NOy, N2O, and O3 during SPURT: implications for transport and chemistry in the lowermost stratosphere

We present measurements of NO, NOy, O3, and N2O within the lowermost stratosphere (LMS) over Europe obtained during the SPURT project. The measurements cover all seasons between November 2001 and July 2003. They span a broad band of latitudes from 30° N to 75° N and a potential temperature range from 290 to 380 K. The measurements represent a comprehensive data set of these tracers and reveal atmospheric transport processes that influence tracer distributions in the LMS. Median mixing ratios of stratospheric tracers in equivalent latitude-potential temperature coordinates show a clear seasonal cycle related to the Brewer-Dobson circulation, with highest values in spring and lowest values in autumn. Vertical tracer profiles show strong gradients at the extratropical tropopause, suggesting that vertical (cross-isentropic) mixing is reduced above the tropopause. Pronounced meridional gradients in the tracer mixing ratios are found on potential temperature surfaces in the LMS. This suggests strongly reduced mixing along isentropes. Concurrent large gradients in static stability in the vertical direction, and of PV in the meridional direction, suggest the presence of a mixing barrier. Seasonal cycles were found in the correlation slopes ΔO3/ΔN2O and ΔNOy/ΔN2O well above the tropopause. Absolute slope values are smallest in spring indicating chemically aged stratospheric air originating from high altitudes and latitudes. Larger values were measured in summer and autumn suggesting that a substantial fraction of air takes a "short-cut" from the tropical tropopause region into the extratropical LMS. The seasonal change in the composition of the LMS has direct implications for the ozone chemistry in this region. Comparisons of measured NO with the critical NO value at which net ozone production changes from negative to positive, imply ozone production up to 20 K above the local tropopause in spring, up to 30 K in summer, and up to 40 K in autumn. Above these heights, and in winter, net ozone production is negative.

Technical note: a simple procedure for removing temporal discontinuities in ERA-Interim upper stratospheric temperatures for use in nudged chemistry-climate model simulations

This note describes a simple procedure for removing unphysical temporal discontinuities in ERA-Interim upper stratospheric global mean temperatures in March 1985 and August 1998 that have arisen due to changes in satellite radiance data used in the assimilation. The derived temperature adjustments (offsets) are suitable for use in stratosphere-resolving chemistry-climate models that are nudged (relaxed) to ERA-Interim winds and temperatures. Simulations using a nudged version of the Canadian Middle Atmosphere Model (CMAM) show that the inclusion of the temperature adjustments produces temperature time series that are devoid of the large jumps in 1985 and 1998. Due to its strong temperature dependence, the simulated upper stratospheric ozone is also shown to vary smoothly in time, unlike in a nudged simulation without the adjustments where abrupt changes in ozone occur at the times of the temperature jumps. While the adjustments to the ERA-Interim temperatures remove significant artefacts in the nudged CMAM simulation, spurious transient effects that arise due to water vapour and persist for about 5 yr after the 1979 switch to ERA-Interim data are identified, underlining the need for caution when analysing trends in runs nudged to reanalyses.

Surface chemistry of alanine on Cu{111}: Adsorption geometry and temperature dependence

Adsorption of l-alanine on the Cu{111} single crystal surface was investigated as a model system for interactions between small chiral modifier molecules and close-packed metal surfaces. Synchrotron-based X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy are used to determine the chemical state, bond coordination and out-of-plane orientation of the molecule on the surface. Alanine adsorbs in its anionic form at room temperature, whilst at low temperature the overlayer consists of anionic and zwitterionic molecules. NEXAFS spectra exhibit a strong angular dependence of the π ⁎ resonance associated with the carboxylate group, which allows determining the tilt angle of this group with respect to the surface plane (48° ± 2°) at room temperature. Low-energy electron diffraction (LEED) shows a p(2√13x2√13)R13° superstructure with only one domain, which breaks the mirror symmetry of the substrate and, thus, induces global chirality to the surface. Temperature-programmed XPS (TP-XPS) and temperature-programmed desorption (TPD) experiments indicate that the zwitterionic form converts into the anionic species (alaninate) at 293 K. The latter desorbs/decomposes between 435 K and 445 K.