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.

Adaptive modelling, estimation and fusion from data: a neurofuzzy approach

In a world of almost permanent and rapidly increasing electronic data availability, techniques of filtering, compressing, and interpreting this data to transform it into valuable and easily comprehensible information is of utmost importance. One key topic in this area is the capability to deduce future system behavior from a given data input. This book brings together for the first time the complete theory of data-based neurofuzzy modelling and the linguistic attributes of fuzzy logic in a single cohesive mathematical framework. After introducing the basic theory of data-based modelling, new concepts including extended additive and multiplicative submodels are developed and their extensions to state estimation and data fusion are derived. All these algorithms are illustrated with benchmark and real-life examples to demonstrate their efficiency. Chris Harris and his group have carried out pioneering work which has tied together the fields of neural networks and linguistic rule-based algortihms. This book is aimed at researchers and scientists in time series modeling, empirical data modeling, knowledge discovery, data mining, and data fusion.

Winners and losers from industry reforms in the developing world: experiences from the electricity and mining sectors

The reform of previously state-owned and operated industries in many Less Developed Countries (LDCs) provide contrary experiences to those in the developed world, which have generally had more equitable distributional impacts. The economic reform policies proposed by the so-called 'Washington Consensus' state that privatisation provides governments with opportunities to raise revenues through the sale of under-performing and indebted state industries, thereby reducing significant fiscal burdens, and, at the same time, facilitating influxes of foreign capital, skills and technology, with the aim of improving operations and a "trickle-down" of benefits. However, experiences in many LDCs over the last 15-20 years suggest that reform has not solved the problem of chronic public-sector debt, and that poverty and socio-economic inequalities have increased during this period of 'neo-liberal' economics. This paper does not seek to challenge the policies themselves, but rather argues that the context in which reform has often taken place is of fundamental significance. The industry-centric policy advice provided by the IFIs typically causes a 'lock-in' of inequitably distributed 'efficiency gains', providing minimal, if any, benefits to impoverished groups. These arguments are made using case study analysis from the electricity and mining sectors.

Contested and contesting identities: minority languages vs. the teaching of 'world' languages within the global cultural economy

This paper juxtaposes postmodernist discourses on language, identity and cultural power with historical forms of language inequalities grounded in the nation-state. The discussion is presented in three sections. The first section focuses on the mixed legacies of language-state relations within the pluralist nation-state, colonial and postcolonial language policies. The second section examines the concept of linguistic minority rights beyond the nation-state. This incorporates discussion of transmigration, the breaking up of previous power blocs in Eastern Europe and the role of language in the articulation of emergent 'ethnic' nationalisms. The third section examines the concept of multilingualism within the interactive cultural landscape defined by 'informationalism'. Discussing the collective impact of these variables on the shaping of new cultural, economic and political inequalities, the paper highlights the tensions in which the concept of linguistic minority rights exists in the world today.

Orientational behaviour of thermotropic and lyotropic liquid crystal polymer systems under shear flow

A comparison is made of the development of global orientation during shearing of lyotropic solutions of hydroxypropylcellulose with that observed for the thermotropic phase of hydroxypropylcellulose. At shear rates the behaviour of the two systems is similar, both during steady-state shear, and in terms of relaxation following cessation of shear flow. At low shear rates, the levels of orientation observed for the thermotropic system are substantially greater than observed for the lyotropic solutions. The relationship of these differences to variations in molecular parameters, viscous stress and to director tumbling is discussed.

Political economy of state-building: power after peace

The purpose of this volume is to examine and evaluate the impact of international state-building interventions on the political economy of post-conflict countries over the last 20 years. It analyses how international interventions have shaped political and economic dynamics and structures – both formal and informal – and what kind of state, and what kind of state-society relations have been created as a result, through three different lenses: first, through the approaches taken by different international actors like the UN, the International Financial Institutions, or the European Union, to state-building; second, through detailed analysis of key state-building policies; and third, through a wide range of country case studies. Amongst the recurring themes that are highlighted by the book’s focus on the political economy of state-building, and that help to explain why international state-building interventions have tended to fall short of the visions of interveners and local populations alike are evidence of important continuities between war-time and “post-conflict” economies and authority structures, which are often consolidated as a consequence of international involvement; tensions arising from what are often the competing interests and values held by different interveners and local actors; and, finally, the continuing salience of economic and political violence in state-building processes and war-to-peace transitions. The book aims to offer a more nuanced understanding of the complex impact of state-building practices on post-conflict societies, and of the political economy of post-conflict state-building.

Acetone enhances the direct analysis of procyanidin- and prodelphinidin-based condensed tannins in lotus species by the butanol-HCl-iron assay

The butanol-HCl spectrophotometric assay is widely used for quantifying extractable and insoluble condensed tannins (CT, syn. proanthocyanidins) in foods, feeds, and foliage of herbaceous and woody plants, but the method underestimates total CT content when applied directly to plant material. To improve CT quantitation, we tested various cosolvents with butanol-HCl and found that acetone increased anthocyanidin yields from two forage Lotus species having contrasting procyanidin and prodelphinidin compositions. A butanol-HCl-iron assay run with 50% (v/v) acetone gave linear responses with Lotus CT standards and increased estimates of total CT in Lotus herbage and leaves by up to 3.2-fold over the conventional method run without acetone. The use of thiolysis to determine the purity of CT standards further improved quantitation. Gel-state 13C and 1H–13C HSQC NMR spectra of insoluble residues collected after butanol-HCl assays revealed that acetone increased anthocyanidin yields by facilitating complete solubilization of CT from tissue.

Responsible tourism and sustainability: the case of Kumarakom in Kerala, India

This paper discusses the notion of ‘responsible tourism’ and its current use within the tourism literature. We argue that the concept as used currently means everything and therefore adds nothing to the conceptual terrain of tourism trends and nomenclatures. We then introduce our own understanding of the concept arguing that while responsible tourism is linked to sustainability initiatives such as alternative tourism, ecotourism, ethical tourism, green tourism, soft tourism, pro-poor tourism, geo-tourism, integrated tourism, community-based tourism, etc it also demarcates an analytical realm of its own. We suggest that the practical use of the term in areas where it has been adopted (such as South Africa and Kerala for instance) suggests a rather restricted use. We identified this realm as the tourism sector-specific manifestation of the corporate social responsibility (CSR) agenda. Following Flyvberg's [(2006). Five misunderstandings about case-study research. Qualitative Inquiry, 12(2), 219–245] call for exemplars and paradigmatic case studies to advance knowledge in a particular domain, the responsible tourism initiative in Kumarakon, Kerala, is presented. Discussion of the case study traces the particular governance context of Kerala and the position of tourism in the state economy. The responsible tourism initiatives at the state level and local level are then described highlighting the ‘how’ of the implementation and the impact that it has produced. Generic, non-prescriptive principles that could be said to be necessary in some form for the successful translation of responsible tourism principles to practices are then identified. Such an approach is contrasted with one that places faith in the voluntary adoption of ‘responsible’ practices by the private sector on its own. It is argued that responsible tourism can make a contribution to practice provided the conceptual terrain is delineated against other forms of tourism and if research within the terrain can unpack the particular forms of challenges that are thrown up by the delineation itself.

Making sense of survival: refining the treatment of state preferences in neorealist theory

The assumption that ‘states' primary goal is survival’ lies at the heart of the neorealist paradigm. A careful examination of the assumption, however, reveals that neorealists draw upon a number of distinct interpretations of the ‘survival assumption’ that are then treated as if they are the same, pointing towards conceptual problems that surround the treatment of state preferences. This article offers a specification that focuses on two questions that highlight the role and function of the survival assumption in the neorealist logic: (i) what do states have to lose if they fail to adopt self-help strategies?; and (ii) how does concern for relevant losses motivate state behaviour and affect international outcomes? Answering these questions through the exploration of governing elites' sensitivity towards regime stability and territorial integrity of the state, in turn, addresses the aforementioned conceptual problems. This specification has further implications for the debates among defensive and offensive realists, potential extensions of the neorealist logic beyond the Westphalian states, and the relationship between neorealist theory and policy analysis.

Haircut undone? The Greek drama and prospects for investment arbitration

As a result of the sovereign debt crisis that engulfed Europe in 2010, investors are much more likely to pursue dispute resolution options when faced with losses. This paper seeks to examine the position of investors who suffered losses in the Greek haircut of 2012 in the context of investment treaty arbitration. The paper evaluates arguments that investments in Greek sovereign bonds have been expropriated by the introduction of retrofit CACs and that compensation is payable as a result of the protections offered by BITs. The paper investigates whether sovereign bonds come within the definition of protected investment in BITs, assesses the degree to which CACs act as a jurisdictional bar to investor-state claims and attempts an evaluation of whether claims could be successful. The analysis uses as an illustration recent cases brought against Greece at ICSID. The paper concludes by considering whether the Greek haircut was expropriatory and reflects on the possible outcome of current arbitrations.

Gaussian anamorphosis in the analysis step of the EnKF: a joint state-variable/observation approach

The analysis step of the (ensemble) Kalman filter is optimal when (1) the distribution of the background is Gaussian, (2) state variables and observations are related via a linear operator, and (3) the observational error is of additive nature and has Gaussian distribution. When these conditions are largely violated, a pre-processing step known as Gaussian anamorphosis (GA) can be applied. The objective of this procedure is to obtain state variables and observations that better fulfil the Gaussianity conditions in some sense. In this work we analyse GA from a joint perspective, paying attention to the effects of transformations in the joint state variable/observation space. First, we study transformations for state variables and observations that are independent from each other. Then, we introduce a targeted joint transformation with the objective to obtain joint Gaussianity in the transformed space. We focus primarily in the univariate case, and briefly comment on the multivariate one. A key point of this paper is that, when (1)-(3) are violated, using the analysis step of the EnKF will not recover the exact posterior density in spite of any transformations one may perform. These transformations, however, provide approximations of different quality to the Bayesian solution of the problem. Using an example in which the Bayesian posterior can be analytically computed, we assess the quality of the analysis distributions generated after applying the EnKF analysis step in conjunction with different GA options. The value of the targeted joint transformation is particularly clear for the case when the prior is Gaussian, the marginal density for the observations is close to Gaussian, and the likelihood is a Gaussian mixture.

Synthesis, characterization and physical properties of the skutterudites YbxFe2Ni2Sb12 (0≤x≤0.4)

The skutterudites YbxFe2Ni2Sb12 (0≤x≤0.4) have been prepared by solid-state reaction and characterised by powder X-ray diffraction. The compounds crystallise in the cubic space group Im View the MathML source3¯ (a≈9.1 Å) with Yb atoms partially filling the voids in the skutterudite framework. A neutron time-of-flight diffraction experiment for Fe2Ni2Sb12 confirms the disorder of Fe and Ni atoms on the transition-metal site. Electrical resistivity, Seebeck coefficient and thermal conductivity measurements indicate that the thermoelectric performance of the skutterudites shows a marked dependence on the Yb content. Magnetic measurements over the temperature range 2≤T/K≤300 show paramagnetic behaviour for all compounds. Decomposition studies under an oxidising atmosphere at elevated temperatures have also been carried out by thermogravimetric analysis.

Do laws influence the cost of real estate brokerage services? A state fixed effects approach

A FTC-DOJ study argues that state laws and regulations may inhibit the unbundling of real estate brokerage services in response to new technology. Our data show that 18 states have changed laws in ways that promote unbundling since 2000. We model brokerage costs as measured by number of agents in a state-level annual panel vector autoregressive framework, a novel way of analyzing wasteful competition. Our findings support a positive relationship between brokerage costs and lagged house price and transactions. We find that change in full-service brokers responds negatively (by well over two percentage points per year) to legal changes facilitating unbundling