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.

Humoral immunity following chickenpox is influenced by geography and ethnicity

Objectives To investigate the contribution of ethnicity and geographical location to varicella-zoster virus (VZV) serostatus and antibody concentrations. Methods The presence and concentrations of antibodies to VZV were measured in 639 Bangladeshi women born in Bangladesh (BBB), 94 Bangladeshi women born in the UK (BUK) and 262 White women born in the UK (WUK). The results were anaylsed in relation to demographic and social data. Results BBB women were significantly less likely to be VZV seropositive at all ages than both BUK and WUK women. However, the odds of a Bangladeshi-born woman being seropositive increased by 1.04 for each year under the age of 15 spent in the UK. In contrast, antibody concentrations were significantly lower in ethnic Bangladeshi women, irrespective of country of birth. White, but not Bangladeshi women, showed evidence of antibody boosting over time despite the latter having more exposure to children. Conclusion Geographical location during childhood is the major influence on age of primary infection with VZV while the level of antibody is related to ethnicity. Since the risk of re-infection with VZV following both natural infection and vaccination is increased as antibody concentrations fall, these results have implications for VZV vaccination programmes particularly in non-White populations.

Moisture transport in mid-latitude cyclones

We discuss how synoptic-scale variability controls the transport of atmospheric water vapour by mid-latitude cyclones. Idealised simulations are used to investigate quantitatively what factors determine the magnitude of cyclone moisture transport. It is demonstrated that large-scale ascent on the warmconveyor belt and shallow cumulus convection are equally important for ventilating moisture from the boundary layer into the free troposphere, and that ventilated moisture can be transported large distances eastwards and polewards by the cyclone, before being returned to the surface as precipitation. The initial relative humidity is shown to have little affect on the ability of the cyclone to transport moisture, whilst the absolute temperature and meridional temperature gradient provide much stronger controls. Scaling arguments are presented to quantify the dependence of moisture transport on large-scale and boundary-layer parameters. It is shown that ventilation by shallow convection and warm-conveyor belt advection vary in the same way with changes to large-scale parameters. However, shallow convective ventilation has a much stronger dependence on boundary-layer parameters than warm-conveyor belt ventilation.

Community mix, affordable housing and metropolitan planning strategy in Melbourne

Income segregation across Melbourne’s residential communities is widening, and at a pace faster than in some other Australian cities. The widening gap between Melbourne’s rich and poor communities raises fears about concentrations of poverty and social exclusion, particularly if the geography of these communities is such that they and their residents are increasingly isolated from urban services and employment centres. Social exclusion in our metropolitan areas and the government responses to it are commonly thought to be the proper domain of social and economic policy. The role of urban planning is typically neglected, yet it helps shape the economic opportunities available to communities in its attempts to influence the geographical location of urban services, infrastructure and jobs. Under the current metropolitan strategy ‘Melbourne 2030’ urban services and transport infrastructure are to be concentrated within Principal Activity Centres spread throughout the metropolitan area and it is the intention that lower-income households should have ready access to these activity centres. However, the Victorian state government has few housing policy instruments to achieve this goal and there are fears that community mix may suffer as house prices and rents are bid up in the vicinity of Principal Activity Centres, and lower-income households are displaced. But are these fears justified by the changing geography of house prices in the metropolitan region? This is the key research question addressed in this paper which examines whether the Victorian practice of placing reliance on the market to deliver affordable housing, while intervening to promote a more compact pattern of urban settlement, is effective.

On the response of the Antarctic Circumpolar Current transport to climate change in coupled climate models

The CMIP3 (IPCC AR4) models show a consistent intensification and poleward shift of the westerly winds over the Southern Ocean during the 21st century. However, the responses of the Antarctic Circumpolar Currents (ACC) show great diversity in these models, with many even showing reductions in transport. To obtain some understanding of diverse responses in the ACC transport, we investigate both external atmospheric and internal oceanic processes that control the ACC transport responses in these models. While the strengthened westerlies act to increase the tilt of isopycnal surfaces and hence the ACC transport through Ekman pumping effects, the associated changes in buoyancy forcing generally tend to reduce the surface meridional density gradient. The steepening of isopycnal surfaces induced by increased wind forcing leads to enhanced (parameterized) eddy-induced transports that act to reduce the isopycnal slopes. There is also considerable narrowing of the ACC that tends to reduce the ACC transport, caused mainly by the poleward shifts of the subtropical gyres and to a lesser extent by the equatorward expansions of the subpolar gyres in some models. If the combined effect of these retarding processes is larger than that of enhanced Ekman pumping, the ACC transport will be reduced. In addition, the effect of Ekman pumping on the ACC is reduced in weakly stratified models. These findings give insight into the reliability of IPCC-class model predictions of the Southern Ocean circulation, and into the observed decadal-scale steady ACC transport.

Bistability of the Atlantic overturning circulation in a global climate model and links to ocean freshwater transport

The possibility of a rapid collapse in the strength of the Atlantic meridional overturning circulation (AMOC), with associated impacts on climate, has long been recognized. The suggested basis for this risk is the existence of two stable regimes of the AMOC (‘on’ and ‘off’), and such bistable behaviour has been identified in a range of simplified climate models. However, up to now, no state-of-the-art atmosphere-ocean coupled global climate model (AOGCM) has exhibited such behaviour, leading to the interpretation that the AMOC is more stable than simpler models indicate. Here we demonstrate AMOC bistability in the response to freshwater perturbations in the FAMOUS AOGCM - the most complex AOGCM to exhibit such behaviour to date. The results also support recent suggestions that the direction of the net freshwater transport at the southern boundary of the Atlantic by the AMOC may be a useful physical indicator of the existence of bistability. We also present new estimates for this net freshwater transport by the AMOC from a range of ocean reanalyses which suggest that the Atlantic AMOC is currently in a bistable regime, although with large uncertainties. More accurate observational constraints, and an improved physical understanding of this quantity, could help narrow uncertainty in the future evolution of the AMOC and to assess the risk of a rapid AMOC collapse.

Climate model calculations of the impact of aerosols from road transport and shipping

Road transport and shipping are copious sources of aerosols, which exert a 9 significant radiative forcing, compared to, for example, the CO2 emitted by these sectors. An 10 advanced atmospheric general circulation model, coupled to a mixed-layer ocean, is used to 11 calculate the climate response to the direct radiative forcing from such aerosols. The cases 12 considered include imposed distributions of black carbon and sulphate aerosols from road 13 transport, and sulphate aerosols from shipping; these are compared to the climate response 14 due to CO2 increases. The difficulties in calculating the climate response due to small 15 forcings are discussed, as the actual forcings have to be scaled by large amounts to enable a 16 climate response to be easily detected. Despite the much greater geographical inhomogeneity 17 in the sulphate forcing, the patterns of zonal and annual-mean surface temperature response 18 (although opposite in sign) closely resembles that resulting from homogeneous changes in 19 CO2. The surface temperature response to black carbon aerosols from road transport is shown 20 to be notably non-linear in scaling applied, probably due to the semi-direct response of clouds 21 to these aerosols. For the aerosol forcings considered here, the most widespread method of 22 calculating radiative forcing significantly overestimates their effect, relative to CO2, 23 compared to surface temperature changes calculated using the climate model.

A geography of the UK commercial property market

This paper revisits some ideas that were first raised seriously in the mid-90s; that it should be possible to establish linkages (in spatial terms) between local economic factors and sector performance in commercial real estate markets. There have been a number of developments in the quality and quantity of relevant data over the intervening period that make it appropriate to return to have another look at some of these ideas in a more ‘modern’ technological context. Using data from several sources this exploratory paper seeks therefore to look at some of the spatial patterns that can be derived from the data. It examines the extent to which it is possible to make linkages and visualise the geographical structure of those markets and their change over time. Naturally there remain strong limitations on the extent to which it is possible to achieve ‘good’ results in this kind of analysis, and one major intention of the paper is to encourage a debate about how data sets can be developed and improved to allow these methods to be taken further.