Thermodynamic model for arsenic speciation in sulfidic waters: A novel use of ab initio computations

Recent discoveries demonstrate that the chemistry of arsenic in sulfidic waters is much more complex that previously believed. One implication is that all earlier thermodynamic data on stabilities of As thioanions require revision. Previously used experimental approaches for determining As thioanion stabilities may be inadequate to deal with the full range of complexity. Here we use computational as well as empirical information to construct a provisional model for equilibrium As thioanion distributions in sulfidic waters. Whereas previous authors have argued for either As(III) or As(V) thioanions, the new model predicts that both are important and can occur simultaneously under commonly encountered pH and ΣS^−II conditions. At the order of magnitude level, the model reasonably predicts the solubility of As₂S₃ in sulfidic solutions, provides tentative peak assignments for published Raman spectroscopic data and plausibly accounts for how sulfide modifies the bacterial toxicity of As. The model yields a thermodynamic justification for how sulfide, which is usually regarded as a reducing agent, can counter-intuitively drive oxidation of As(III) to As(V), as has been observed both in the laboratory and in the field. Despite its uncertain accuracy, the model serves as a useful source of new, testable hypotheses about As geochemistry and highlights crucial experimental data needs.     

Calcite precipitation instability under laminar, open-channel flow

We present a 2D numerical model for the growth of calcite from supersaturated aqueous solutions under laminar, open-channel flow conditions. The model couples solution chemistry, precipitation at solution/calcite interfaces, hydrodynamics, diffusion and degassing. The model output is compared with experimental results obtained using an oversaturated calcite solution produced by mixing CaCl₂ and Na₂CO₃. The precipitation rate is observed to increase when the supersaturated solution flows over an obstruction, leading to a growth instability that causes the formation of terraces. At relatively high flow rates, the most important mechanism for this behaviour seems to be hydrodynamic advection of dissolved species either towards or away from the calcite surface, depending on location relative to the obstruction, which deforms the concentration gradients. At lower flow rates, steepening of diffusion gradients around protrusions becomes important. Enhanced degassing over the obstruction due to shallowing and pressure drop is not important on small scales. Diffusion controlled transport close to the calcite surface can lead to a fingering-type growth instability, which generates porous textures. Our results are consistent with existing diffusive boundary layer theory, but for flow over non-smooth surfaces, simple calcite precipitation models that include empirical correlations between fluid flow rate and calcite precipitation rate are inaccurate.     

GMOs and their contexts: A comparison of potential and actual performance of GM crops in a local agricultural setting

In this paper, I argue that genetically modified organisms (GMOs) have inherent potential to contribute to socially and environmentally sustainable agriculture by virtue of their ‘biological embeddedness’. Their actual ‘performance’ and how this contributes to sustainability depends on the ‘mutual shaping’ of technology and context. While much attention has been given to the design context of GMOs, this paper considers the influence of the application context and of users. A case study investigating the use of insect-resistant and herbicide-tolerant GM cotton in the cotton-growing region of New South Wales in Australia is presented. The study was based on focus groups with farmers and other stakeholders in a cotton-growing community. It demonstrated a range of direct and indirect effects of GM cotton use, both positive and negative for sustainability, and the ways in which these effects were influenced by the local social context. The influences of the biotechnology industry context, in limiting the contributions that gene technologies can make to sustainability, were also considered, and remedies suggested. I argue that the polarity of the GM debate is hindering progress on these issues, and that a more balanced approach to our analysis of GMOs is necessary in order to fully understand, and to influence, their role in the future of rural spaces.     

Probing the (in)compatibilities of social theory and policy relevance in Piers Blaikie’s political ecology

One of Piers Blaikie’s most important contributions to the development of political ecology is his critique of land and resource conservation policy in the global South. In this paper I trace the development of Blaikie’s ideas about the policy relevance of political ecology, focusing particularly on the challenges posed by the introduction of poststructural social theory into the field. I begin by revisiting Blaikie’s earlier critiques of environment and development policy. This will provide the departure point to explore how his thinking on the relationship of theory and policy and of academic and development practices has evolved in subsequent writings. I have invented two personas, “early Blaikie” and “late Blaikie”, to facilitate this task. Second, I want to probe some of the challenges that late Blaikie presents for doing political ecology research, to some extent by pitting early Blaikie against late Blaikie and letting them hash it out. Third, I turn to my own and others’ research and consultation experiences as a way to examine the possibilities for reconciling theoretically driven critiques with policy relevant research.     

Synchronism in compression of the lithosphere in the central Atlantic and Western Tethys at the Tortonian-Messinian transition

The structure of anomalously uplifted areas in transverse ridges of the Vema, S o Paulo, and Romanche fracture zones is considered. It is concluded that their formation and eventual development in the present-day structure of the central Atlantic bottom proceeded during two stages. The first stage that corresponds to a short period at the Tortonian-Messinian transition (10 Ma ago) was marked by transportation of deep-seated rocks into the upper part of the lithosphere along thrust faults with mass motion in the meridional direction along the axis of the Mid-Atlantic Ridge. The second stage was characterized by contrasting highamplitude vertical movements from 10 to 3 Ma ago. It is suggested that near-meridional compression in the domains surrounding the Western Tethys in the Tortonian-Messinian resulted in deformation of the upper lithosphere within large transform fracture zones of the central Atlantic. The deformation that occurred 10 Ma ago was a manifestation of the global neotectonic epoch of the Earth.     

Late Precambrian rifting in the geological history of the western slope of the South Urals

The rift-related geodynamic setting of the Late Precambrian geological evolution on the western slope of the South Urals is reconstructed on the basis of localization of lithotectonic complexes of this age, their formation conditions, and the geochemistry of rocks. The Early Riphean stage comprises accumulation of coarse-clastic rocks intercalating with alkaline volcanic rocks of the Navysh Complex, which is a constituent of the Ai Formation, and emplacement of doleritic and picritic intrusions of the Shuida Complex and melanocratic dolerite and gabbrodolerite of the Yusha Complex. The Middle Riphean stage is characterized by wide-spread coarse-clastic terrigenous rocks of the Mashak Formation that intercalate with volcanic rocks of the bimodal basalt-rhyolite association, the Berdyaush pluton of rapakivi granite, the Kusa-Kopan layered intrusive complex, the Lapyshta Complex of dolerites and picrites, and numerous occurrences of gabbrodolerites. The terrigenous rocks of the Vendian stage include conglomerate, gravelstone, and sandstone of the Asha Group, while igneous rocks comprise alkaline volcanics of the Arsha Complex, alkali gabbroids of the Miseli Complex, and melanocratic syenite of the Avashla Complex. The geological evolution of the region is distinguished by local (failed or aborted) rifting. The occurrence of lithotectonic complexes is controlled by dynamic conditions of rifting. A certain inheritance in the evolution may be traced for the Early and Middle Riphean and partly for the Late Riphean and Vendian.     

Planktonic foraminifers in the southern Bering Sea: Changes in composition and productivity during the Late Pleistocene-Holocene

Taxonomic composition and distribution of planktonic foraminifers are studied in section of Core GC-11 that penetrated through Upper Quaternary sediments of the Bowers Ridge western slope, the southern Bering Sea. As is shown, structure of foraminiferal assemblage and productivity have varied substantially during the last 32000 calendar years in response to changes in surface water temperatures and water mass circulation in the northern part of the Pacific, the Bering Sea included. The productivity was maximal during deglaciation epoch, being notably lower in the Holocene and minimal at the glaciation time.     

Opacitization conditions of hornblende in Bezymyannyi volcano andesites (March 30, 1956 eruption)

The paper is devoted to the conditions under which opacite rims developed around hornblende grains in andesite of the catastrophic eruption (March 30, 1956) of Bezymyannyi volcano, Kamchatka. The opacite rims were produced by a bimetasomatic reaction between hornblende and melt with the development of the following zoning: hornblende → Px + Pl + Ti-Mag → Px + Pl → Px → melt. Biometasomatic reaction was accompanied by the active removal of CaO from the rim, addition of SiO₂, and more complicated behavior of other components. The hornblende also shows reactions of its volumetric decomposition under near-isochemical conditions. The opacite rims developed under isobaric conditions, at a pressure of approximately 6 kbar. The main reason for the instability of the hornblende was the heating of the magma chamber from 890 to 1005°C due to new hot magma portion injection. The time interval between the injection and the start of eruption was estimated from the thickness of the opacite rims and did not exceed 37 days. Hence, the March 30, 1956, eruption was not related to the volcanic activity in November of 1955 but to the injection of a fresh magma portion in February–March of 1956.