Mg/Ca ratios in freshwater microbial carbonates: Thermodynamic, kinetic and vital effects

The ratio of magnesium to calcium (Mg/Ca) in carbonate minerals in an abiotic setting is conventionally assumed to be predominantly controlled by (Mg/Ca)solution and a temperature dependant partition coefficient. This temperature dependence suggests that both marine (e.g. foraminiferal calcite and corals) and freshwater (e.g. speleothems and surface freshwater deposits, “tufas”) carbonate deposits may be important archives of palaeotemperature data. However, there is considerable uncertainty in all these settings. In surface freshwater deposits this uncertainty is focussed on the influence of microbial biofilms. Biogenic or “vital” effects may arise from microbial metabolic activity and/or the presence of extracellular polymeric substances (EPS). This study addresses this key question for the first time, via a series of unique through-flow microcosm and agitated flask experiments where freshwater calcite was precipitated under controlled conditions. These experiments reveal there is no strong relationship between (Mg/Ca)calcite and temperature, so the assumption of thermodynamic fractionation is not viable. However, there is a pronounced influence on (Mg/Ca)calcite from precipitation rate, so that rapidly forming precipitates develop with very low magnesium content indicating kinetic control on fractionation. Calcite precipitation rate in these experiments (where the solution is only moderately supersaturated) is controlled by biofilm growth rate, but occurs even when light is excluded indicating that photosynthetic influences are not critical. Our results thus suggest the apparent kinetic fractionation arises from the electrochemical activity of EPS molecules, and are therefore likely to occur wherever these molecules occur, including stromatolites, soil and lake carbonates and (via colloidal EPS) speleothems

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

Kinetic and mechanistic data relevant to the tropospheric degradation of volatile organic compounds (VOC), and the production of secondary pollutants, have previously been used to define a protocol which underpinned the construction of a near-explicit Master Chemical Mechanism. In this paper, an update to the previous protocol is presented, which has been used to define degradation schemes for 107 non-aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). The treatment of 18 aromatic VOC is described in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the reactions of the radical intermediates and the further degradation of first and subsequent generation products. Emphasis is placed on updating the previous information, and outlining the methodology which is specifically applicable to VOC not considered previously (e.g. <font face='Symbol' >a</font>- and <font face='Symbol' >b</font>-pinene). The present protocol aims to take into consideration work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Application of MCM v3 in appropriate box models indicates that the representation of isoprene degradation provides a good description of the speciated distribution of oxygenated organic products observed in reported field studies where isoprene was the dominant emitted hydrocarbon, and that the <font face='Symbol' >a</font>-pinene degradation chemistry provides a good description of the time dependence of key gas phase species in <font face='Symbol' >a</font>-pinene/NO_X photo-oxidation experiments carried out in the European Photoreactor (EUPHORE). Photochemical Ozone Creation Potentials (POCP) have been calculated for the 106 non-aromatic non-methane VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. Where applicable, the values are compared with those calculated with previous versions of the MCM

New Zealand Agribusiness Success: An Approach to exploring the role of strategy, structure and conduct on firm performance

This paper presents a framework to explore agribusiness success in New Zealand. The framework provides the basis for historical analysis. It draws on existing theory based on the structure-conduct-performance paradigm but expanded to take account of firm strategy and the analysis of value chains.Agribusiness, structure, conduct, performance, history, Agribusiness,

Book reviews

Teaching/Communication/Extension/Profession,

Post-Disaster Housing Reconstruction in Sri Lanka: What Methodology?

Research methodology is the procedural framework within which the research is conducted. This includes the overall approach to a problem that could be put into practice in a research process, from the theoretical underpinning to the collection and analysis of data. Choice of methodology depends on the primary drivers: topic to be researched and the specific research questions. Hence, methodological perspectives of managing stakeholder expectations of PDHR context are composed of research philosophies, research strategy, research design, and research techniques. This research belonged to social constructivism or interpretivism within a philosophical continuum. The nature of the study was more toward subjectivism where human behavior favored voluntary stance. Ontological, methodological, epistemological, and axiological positioning carried the characteristics of idealism, ideographic, anti-positivism, and value laden, respectively. Data collection comprises two phases, preliminary and secondary. Exploratory interviews with construction experts in the United Kingdom and Sri Lanka were carried out to refine the interview questions and identify the case studies. Case study interviews during the secondary phase took place in Sri Lanka. Data collected at the preliminary stage were used to assess the attributes of power, legitimacy/proximity, and urgency of stakeholders to the project using Stakeholder Circle™ software. Moreover, the data collected at secondary phase via case studies will be analyzed with NVivo 8. This article aims to discuss these methodological underpinnings in detail applied in a post-disaster housing reconstruction context in Sri Lanka

Learning To Be Affected: Social suffering and total pain at life’s borders.

The practice of Live Sociology in situations of pain and suffering is the author’s focus. An outline of the challenges of understanding pain is followed by a discussion of Bourdieu’s ‘social suffering’ (1999) and the palliative care philosophy of ‘total pain’. Using examples from qualitative research on disadvantaged dying migrants in the UK, attention is given to the methods that are improvised by dying people and care practitioners in attempts to bridge intersubjective divides, where the causes and routes of pain can be ontologically and temporally indeterminate and/or withdrawn. The paper contends that these latter phenomena are the incitement for the inventive bridging and performative work of care and Live Sociological methods, both of which are concerned with opposing suffering. Drawing from the ontology of total pain, I highlight the importance of (i) an engagement with a range of materials out of which attempts at intersubjective bridging can be produced, and which exceed the social, the material, and the temporally linear; and (ii) an empirical sensibility that is hospitable to the inaccessible and non-relational

Covariant Hamiltonian field theory

We study the relationship between the equations of first order Lagrangian field theory on fiber bundles and the covariant Hamilton equations on the finite-dimensional polysymplectic phase space of covariant Hamiltonian field theory. The main peculiarity of these Hamilton equations lies in the fact that, for degenerate systems, they contain additional gauge fixing conditions. We develop the BRST extension of the covariant Hamiltonian formalism, characterized by a Lie superalgebra of BRST and anti-BRST symmetries.Comment: 35 pages, Late

High-resolution x-ray diffraction study of the heavy-fermion compound YbBiPt

YbBiPt is a heavy-fermion compound possessing significant short-range antiferromagnetic correlations below a temperature of $T^{\textrm{*}}=0.7$ K, fragile antiferromagnetic order below $T_{\rm{N}}=0.4$ K, a Kondo temperature of $T_{\textrm{K}} \approx1$ K, and crystalline-electric-field splitting on the order of $E/k_{\textrm{B}}=1\,\textrm{-}\,10$ K. Whereas the compound has a face-centered-cubic lattice at ambient temperature, certain experimental data, particularly those from studies aimed at determining its crystalline-electric-field scheme, suggest that the lattice distorts at lower temperature. Here, we present results from high-resolution, high-energy x-ray diffraction experiments which show that, within our experimental resolution of $\approx6\,\textrm{-}\,10\times10^{-5}$ \AA, no structural phase transition occurs between $T=1.5$ and $50$ K. In combination with results from dilatometry measurements, we further show that the compound's thermal expansion has a minimum at $\approx18$ K and a region of negative thermal expansion for $9<T<18$ K. Despite diffraction patterns taken at $1.6$ K which indicate that the lattice is face-centered cubic and that the Yb resides on a crystallographic site with cubic point symmetry, we demonstrate that the linear thermal expansion may be modeled using crystalline-electric-field level schemes appropriate for Yb$^{3+}$ residing on a site with either cubic or less than cubic point symmetry.Comment: 7 pages, 3 figures, submitted to Phys. Rev.