The TOMCAT global chemical transport model v1.6: description of chemical mechanism and model evaluation

This paper documents the tropospheric chemical mechanism scheme used in the TOMCAT 3-D chemical transport model. The current scheme includes a more detailed representation of hydrocarbon chemistry than previously included in the model, with the inclusion of the emission and oxidation of ethene, propene, butane, toluene and monoterpenes. The model is evaluated against a range of surface, balloon, aircraft and satellite measurements. The model is generally able to capture the main spatial and seasonal features of high and low concentrations of carbon monoxide (CO), ozone (O3), volatile organic compounds (VOCs) and reactive nitrogen. However, model biases are found in some species, some of which are common to chemistry models and some that are specific to TOMCAT and warrant further investigation. The most notable of these biases are (1) a negative bias in Northern Hemisphere (NH) winter and spring CO and a positive bias in Southern Hemisphere (SH) CO throughout the year, (2) a positive bias in NH O3 in summer and a negative bias at high latitudes during SH winter and (3) a negative bias in NH winter C2 and C3 alkanes and alkenes. TOMCAT global mean tropospheric hydroxyl radical (OH) concentrations are higher than estimates inferred from observations of methyl chloroform but similar to, or lower than, multi-model mean concentrations reported in recent model intercomparison studies. TOMCAT shows peak OH concentrations in the tropical lower troposphere, unlike other models which show peak concentrations in the tropical upper troposphere. This is likely to affect the lifetime and transport of important trace gases and warrants further investigation

Adhesion-induced phase separation of multiple species of membrane junctions

A theory is presented for the membrane junction separation induced by the adhesion between two biomimetic membranes that contain two different types of anchored junctions (receptor/ligand complexes). The analysis shows that several mechanisms contribute to the membrane junction separation. These mechanisms include (i) the height difference between type-1 and type-2 junctions is the main factor which drives the junction separation, (ii) when type-1 and type-2 junctions have different rigidities against stretch and compression, the ``softer'' junctions are the ``favored'' species, and the aggregation of the softer junction can occur, (iii) the elasticity of the membranes mediates a non-local interaction between the junctions, (iv) the thermally activated shape fluctuations of the membranes also contribute to the junction separation by inducing another non-local interaction between the junctions and renormalizing the binding energy of the junctions. The combined effect of these mechanisms is that when junction separation occurs, the system separates into two domains with different relative and total junction densities.Comment: 23 pages, 6 figure

Governance tools for board members : adapting strategy maps and balanced scorecards for directorial action

The accountability of members of the board of directors of publicly traded companies has increased over years. Corresponding to these developments, there has been an inadequate advancement of tools and frameworks to help directorial functioning. This paper provides an argument for design of the Balanced Scorecard and Strategy Maps made available to the directors as a means of influencing, monitoring, controlling and assisting managerial action. This paper examines how the Balanced Scorecard and Strategy Maps could be modified and used for this purpose. The paper suggests incorporating Balanced Scorecards in the Internal Process perspective, ‘internal’ implying here not just ‘internal to the firm’, but also ‘internal to the inter-organizational system’. We recommend that other such factors be introduced separately under a new ‘perspective’ depending upon what the board wants to emphasize without creating any unwieldy proliferation of measures. Tracking the Strategy Map over time by the board of directors is a way for the board to take responsibility for the firm’s performance. The paper makes a distinction between action variables and monitoring variables. Monitoring variables are further divided on the basis of two considerations: a) whether results have been met or not and b) whether causative factors have met the expected levels of performance or not. Based on directorial responsibilities and accountability, we take another look at how the variables could be specified more completely and accurately with directorial recommendations for executives

Direct evidence for coastal iodine particles from <i>Laminaria</i> macroalgae ? linkage to emissions of molecular iodine

International audienceRenewal of ultrafine aerosols in the marine boundary layer may lead to repopulation of the marine distribution and ultimately determine the concentration of cloud condensation nuclei (CCN). Thus the formation of nanometre-scale particles can lead to enhanced scattering of incoming radiation and a net cooling of the atmosphere. The recent demonstration of the chamber formation of new particles from the photolytic production of condensable iodine-containing compounds from diiodomethane (CH2I2), (O'Dowd et al., 2002; Kolb, 2002; Jimenez et al., 2003a; Burkholder and Ravishankara, 2003), provides an additional mechanism to the gas-to-particle conversion of sulphuric acid formed in the photo-oxidation of dimethylsulphide for marine aerosol repopulation. CH2I2 is emitted from seaweeds (Carpenter et al., 1999, 2000) and has been suggested as an initiator of particle formation. We demonstrate here for the first time that ultrafine iodine-containing particles are produced by intertidal macroalgae exposed to ambient levels of ozone. The particle composition is very similar both to those formed in the chamber photo-oxidation of diiodomethane and in the oxidation of molecular iodine by ozone. The particles formed in all three systems are similarly aspherical and behave alike when exposed to increased humidity environments. Direct coastal boundary layer observations of molecular iodine, ultrafine particle production and iodocarbons are reported. Using a newly measured molecular iodine photolysis rate, it is shown that, if atomic iodine is involved in the observed particle bursts, it is of the order of at least 1000 times more likely to result from molecular iodine photolysis than diiodomethane photolysis. A hypothesis for molecular iodine release from intertidal macroalgae is presented and the potential importance of macroalgal iodine particles in their contribution to CCN and global radiative forcing are discussed

Ownership, Activism and Engagement: Institutional Investors as Active Owners

Research Question We research two questions: First, why do some institutional investors operate at a distance from organizations seemingly acting only to “exit” and “trade” shares while others actively engage through various means of “voice”? Second, what processes and behaviour are associated with active ownership? Research Findings/Insights We develop the concept of active ownership by drawing on contrasting theories and images of ownership, identifying antecedents of active ownership and distinguishing between alternative processes of active ownership. Theoretical/Academic Implications Alternative pathways to active ownership contrast the distant, sometimes adversarial nature of shareholder activism with an engaged, collaborative relationship between investors and corporations. Few studies examine active ownership as a process of engagement and mutual exchange between parties taking a generally longer-term perspective towards investment in the firm and its affairs. After modelling active ownership, we develop a research agenda of substantive issues ranging from market and institutional conditions, through investment organization and practice, to board and investor relations. Practitioner/Policy Implications Opening up the multidimensionality of engagement and relations between investors and corporations is crucial to promoting good corporate governance. Policymakers and practitioners require such knowledge when anticipating and developing adjustments to institutions of corporate governance. This article is protected by copyright. All rights reserved

Communitarian perspectives on social enterprise

Concepts of social enterprise have been debated repeatedly, and continue to cause confusion. In this paper, a meta-theoretical framework is developed through discussion of individualist and communitarian philosophy. Philosophers from both traditions build social theories that emphasise either consensus (a unitarist outlook) or diversity (a pluralist outlook). The various discourses in corporate governance reflect these assumptions and create four distinct approaches that impact on the relationship between capital and labour. In rejecting the traditional discourse of private enterprise, social enterprises have adopted other approaches to tackle social exclusion, each derived from different underlying beliefs about the purpose of enterprise and the nature of governance. The theoretical framework offers a way to understand the diversity found within the sector, including the newly constituted Community Interest Company (CIC).</p

Emissions of biogenic volatile organic compounds and subsequent photochemical production of secondary organic aerosol in mesocosm studies of temperate and tropical plant species

Silver birch (Betula pendula) and three Southeast Asian tropical plant species (Ficus cyathistipula, Ficus benjamina and Caryota millis) from the pantropical fig and palm genera were grown in a purpose-built and environment-controlled whole-tree chamber. The volatile organic compounds emitted from these trees were characterised and fed into a linked photochemical reaction chamber where they underwent photo-oxidation under a range of controlled conditions (relative humidity or RH ~65–89%, volatile organic compound-to-NOx or VOC / NOx ~3–9 and NOx ~2 ppbV). Both the gas phase and the aerosol phase of the reaction chamber were monitored in detail using a comprehensive suite of on-line and off-line chemical and physical measurement techniques. Silver birch was found to be a high monoterpene and sesquiterpene but low isoprene emitter, and its emissions were observed to produce measurable amounts of secondary organic aerosol (SOA) via both nucleation and condensation onto pre-existing seed aerosol (YSOA 26–39%). In contrast, all three tropical species were found to be high isoprene emitters with trace emissions of monoterpenes and sesquiterpenes. In tropical plant experiments without seed aerosol there was no measurable SOA nucleation, but aerosol mass was shown to increase when seed aerosol was present. Although principally isoprene emitting, the aerosol mass produced from tropical fig was mostly consistent (i.e. in 78 out of 120 aerosol mass calculations using plausible parameter sets of various precursor specific yields) with condensation of photo-oxidation products of the minor volatile organic compounds (VOCs) co-emitted; no significant aerosol yield from condensation of isoprene oxidation products was required in the interpretations of the experimental results. This finding is in line with previous reports of organic aerosol loadings consistent with production from minor biogenic VOCs co-emitted with isoprene in principally isoprene-emitting landscapes in Southeast Asia. Moreover, in general the amount of aerosol mass produced from the emissions of the principally isoprene-emitting plants was less than would be expected from published single-VOC experiments, if co-emitted species were solely responsible for the final SOA mass. Interpretation of the results obtained from the fig data sets leaves room for a potential role for isoprene in inhibiting SOA formation under certain ambient atmospheric conditions, although instrumental and experimental constraints impose a level of caution in the interpretation of the results. Concomitant gas- and aerosol-phase composition measurements also provide a detailed overview of numerous key oxidation mechanisms at work within the systems studied, and their combined analysis provides insight into the nature of the SOA formed

Intercomparison and evaluation of satellite peroxyacetyl nitrate observations in the upper troposphere-lower stratosphere

Peroxyacetyl nitrate (PAN) is an important chemical species in the troposphere as it aids the long-range transport of NOx and subsequent formation of O3 in relatively clean remote regions. Over the past few decades observations from aircraft campaigns and surface sites have been used to better understand the regional distribution of PAN. However, recent measurements made by satellites allow for a global assessment of PAN in the upper troposphere–lower stratosphere (UTLS). In this study, we investigate global PAN distributions from two independent retrieval methodologies, based on measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument, on board Envisat from the Institute of Meteorology and Climate Research (IMK), Karlsruhe Institute of Technology, and the Department of Physics and Astronomy, University of Leicester (UoL). Retrieving PAN from MIPAS is challenging due to the weak signal in the measurements and contamination from other species. Therefore, we compare the two MIPAS datasets with observations from the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS), in situ aircraft data and the 3-D chemical transport model TOMCAT. MIPAS shows peak UTLS PAN concentrations over the biomass burning regions (e.g. ranging from 150 to  >  200 pptv at 150 hPa) and during the summertime Asian monsoon as enhanced convection aids the vertical transport of PAN from the lower atmosphere. At 150 hPa, we find significant differences between the two MIPAS datasets in the tropics, where IMK PAN concentrations are larger by 50–100 pptv. Comparisons between MIPAS and ACE-FTS show better agreement with the UoL MIPAS PAN concentrations at 200 hPa, but with mixed results above this altitude. TOMCAT generally captures the magnitude and structure of climatological aircraft PAN profiles within the observational variability allowing it to be used to investigate the MIPAS PAN differences. TOMCAT–MIPAS comparisons show that the model is both positively (UoL) and negatively (IMK) biased against the satellite products. These results indicate that satellite PAN observations are able to detect realistic spatial variations in PAN in the UTLS, but further work is needed to resolve differences in existing retrievals to allow quantitative use of the products

The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosol

The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of secondary organic aerosol (SOA) formed during the chamber photo-oxidation of β-caryophyllene/NO_x mixtures were investigated. Nucleation of β-caryophyllene SOA particles occurred almost immediately after oxidation was initiated and led to the formation of fresh SOA with a relatively simpler composition than has been reported for monoterpenes. The SOA yield values ranged from 9.5–26.7% and 30.4–44.5% using a differential mobility particle sizer (DMPS) and an aerosol mass spectrometer (AMS) mass based measurements, respectively. A total of 20 compounds were identified in the SOA by LC-MS/MS, with the most abundant compounds identified as β-caryophyllonic acid and β-caryophyllinic acid/β-nocaryophyllonic acid. The O:C and H:C elemental ratios of products identified in the condensed phase ranged from 0.20 to 1.00 and 1.00 to 2.00, with average values of 0.39 and 1.58, respectively. The increase in the O:C ratio was associated with a decrease in the saturation concentration of the identified compounds. The compounds identified in the lower initial concentration experiments were more oxidised compared to those that were found to be more abundant in the higher initial concentration experiments with average O:C ratios of 0.51 and 0.27, respectively. Photochemical ageing led to a more complex SOA composition with a larger contribution coming from lower molar mass, higher generation products, where both double bonds had been oxidised. This effect was more evident in the experiments conducted using the lower initial precursor concentration; a finding confirmed by the temporal behaviour of key organic mass fragment measured by an Aerosol Mass Spectrometer. Although the composition changed with both initial precursor concentration and ageing, this had no significant measurable effect on the hygroscopic properties of the SOA formed. The latter finding might have been influenced by the difference in pre-treatment of the semivolatile-containing particles prior to their measurements