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.     

Models in geography revisited

Agent based models (ABMs) have many applications, and illustrate a rapidly developing field of enquiry, spanning both the physical-mathematical and human-social sciences. ABMs are seen as most appropriate in situations where decisions or actions are distributed around particular locations, and in which structure is viewed as emergent from the interaction between individuals. ABMs may be used either as representational devices, to reproduce the patterns observed or desired in the system of interest, or as foundational tools contributing to the development of social or economic theory. The role and status of models and modelling is itself an instantiation of a wider debate concerning representation and explanation. Today, a case can be made that the nature of explanation and the use of scientific interpretation reflect much less definite and exclusive positions and permit more diverse approaches than hitherto. The underlying proposition of this commentary is, therefore, that the time is right for a positive application of ABMs within the discipline of geography, and for a rediscovery and reappraisal of the richness and depth of insight in the model-building enterprise more generally. First, the context for ABM development and application is set with reference to the agency-structure debate. Second, some aspects of the heritage of models in geography is presented, based upon reviews of two benchmark publications bearing that title. Next, some of the most significant characteristics, uses, potentials and limitations of ABMs, are reviewed. Finally, some constructive ways forward are suggested, as informed by theory and method from the interpretative social sciences.     

Models of natural and human dynamics in forest landscapes: Cross-site and cross-cultural synthesis

We synthesize the study of coupled natural and human systems across sites and cultures through a process of simplification and abstraction based on multiple dimensions of human-nature connectedness: satisfaction of basic needs, psycho-cultural connectedness and regulation of use of natural resources. We thus provide both a place-based and general understanding of value-driven anthropogenic environmental change and response. Two questions guide this research: what are the crucial stakeholder values that drive land use decisions and thus land cover change? And how can knowledge of these values be used to make decisions and policies that sustain both the human and natural systems in a place? To explore these questions we build simulation models of four study sites, two in the State of Texas, United States, and two in Venezuela. All include protected areas, though they differ in the specifics of vegetation and land use. In the Texas sites, relatively affluent individuals are legally converting forests to residential, commercial, and industrial uses, while in Venezuela landless settlers are extra-legally converting forests for purposes of subsistence agriculture. Contemporary modeling techniques now facilitate simulations of stakeholder and ecosystem dynamics revealing emergent patterns. Such coupled human and natural systems are currently recognized as a form of biocomplexity. Our modeling framework is flexible enough to allow adaptation to each of the study sites, capturing the essential features of the respective natural and anthropogenic land use changes and stakeholder reactions. The interactions between human stakeholders are simulated using multi-agent models that act on forest landscape models, and receive feedback of the effects of these actions on ecological habitats and hydrological response. The multi-agent models employ a formal logic-based method for the Venezuelan sites and a decision analysis approach using multi-attribute utility functions for the Texas sites, differing more in style and emphasis than in substance. Our natural-systems models are generic and can be tailored according to site-specific conditions. Similar models of tree growth and patch transitions are used for all the study sites and the differing responses to environmental variables are specified for each local species and terrain conditions.     

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.     

Church-based social capital, networks and geographical scale: Katrina evacuation, relocation, and recovery in a New Orleans Vietnamese American community

This research examines the role of social capital and networks to explain the evacuation, relocation, and recovery experiences of a Vietnamese American community in New Orleans, Louisiana in the aftermath of Hurricane Katrina. As the single largest community institution, the parish church’s complex bonding and bridging social capital and networks proved particularly critical in part because of its historically based ontological security. The process of evacuation, but especially relocation and recovery, was dependent on deploying co-ethnic social capital and networks at a variety of geographical scales. Beyond the local or community scale, extra-local, regional, and national scales of social capital and networks reproduced a spatially redefined Vietnamese American community. Part of the recovery process included constructing discursive place-based collective-action frames to successfully contest a nearby landfill that in turn engendered social capital and networks crossing ethnic boundaries to include the extra-local African American community. Engaging social capital and networks beyond the local geographical scale cultivated a Vietnamese American community with an emergent post-Katrina cultural and political identity.     

Lateral structural variability in zone of eocene island-arc-continent collision,Kamchatka

The lateral variability of structural elements in the collision zone of the Cretaceous-Paleocene Achaivayam-Valagin island arc with the northeastern Asian margin is considered. The similarity and difference of Eocene collision structural elements in the north and the south of Kamchatka are shown. In northern Kamchatka, the continent-arc boundary is traced along the Lesnaya-Vatyn Thrust Fault, which completed its evolution about 45 Ma ago. The thin, near-horizontal allochthon of this thrust, composed of island-arc rocks, overlies the deformed but unmetamorphosed terrigeneous sequences of the Asian margin. The general structure of this suture in the Kamchatka Isthmus and southern Koryakia is comparable with the uppermost subduction zone, where a thin lithospheric wedge overlaps intensely deformed sediments detached from the plunging plate. In southern Kamchatka (Malka Uplift of the Sredinny Range), the arc-continent collision started 55–53 Ma ago with thrusting of island-arc complexes over terrigenous rocks of continental margin. However, the thickness of the allochthon was much greater than in the north. Immediately after this event, both the autochthon and lower part of allochthon were deformed and subsided to a significant depth. This subsidence gave rise to metamorphism of both the autochthon (Kolpakov and Kamchatka groups, Kheivan Formation) and lower allochthon (Andrianovka and Khimka formations). The anomalously fast heating of the crust was most likely related to the ascent of asthenospheric masses due to slab breakoff, when the Eurasian Plate was plunging beneath the Achaivayam-Valagin arc.     

Geobarometry for Peridotites: Experiments in Simple and Natural Systems from 6 to 10 GPa

Experiments with peridotite minerals in simple (MgO–Al₂O₃–SiO₂,CaO–MgO–SiO₂ and CaO–MgO–Al₂O₃–SiO₂)and natural systems were conducted at 1300–1500°Cand 6–10 GPa using a multi-anvil apparatus. The experimentsin simple systems demonstrated consistency with previous lowerpressure experiments in belt and piston–cylinder set-ups.The analysis of spatial variations in pyroxene compositionswithin experimental samples was used to demonstrate that pressureand temperature variations within the samples were less than0·4 GPa and 50°C. Olivine capsules were used in natural-systemexperiments with two mineral mixtures: SC1 (olivine + high-Alorthopyroxene + high-Al clinopyroxene + spinel) and J4 (olivine+ low-Al orthopyroxene + low-Al clinopyroxene + garnet). Theexperiments produced olivine + orthopyroxene + garnet ±clinopyroxene assemblages, occasionally with magnesite and carbonate-richmelt. Equilibrium compositions were derived by the analysisof grain rims and evaluation of mineral zoning. They were comparedwith our previous experiments with the same starting mixturesat 2·8–6·0 GPa and the results from simplesystems. The compositions of minerals from experiments withnatural mixtures show smooth pressure and temperature dependencesup to a pressure of 8 GPa. The experiments at 9 and 10 GPa producedandradite-rich garnets and pyroxene compositions deviating fromthe trends defined by the lower pressure experiments (e.g. higherAl in orthopyroxene and Ca in clinopyroxene). This discrepancyis attributed to a higher degree of oxidation in the high-pressureexperiments and an orthopyroxene–high-P clinopyroxenephase transition at 9 GPa. Based on new and previous resultsin simple and natural systems, a new version of the Al-in-orthopyroxenebarometer is presented. The new barometer adequately reproducesexperimental pressures up to 8 GPa. KEY WORDS: garnet; mineral equilibrium; multi-anvil apparatus; orthopyroxene; geobarometry     

Lithospheric Origin of Oligocene-Miocene Magmatism in Central Chile: U-Pb Ages and Sr-Pb-Hf Isotope Composition of Minerals

Establishing the petrogenesis of volcanic and plutonic rocksis a key issue in unraveling the evolution of distinct subduction-relatedtectonic phases occurring along the South American margin. Thisis particularly true for Cenozoic times when large volumes ofmagma were produced in the Andean belt. In this study we havefocused on Oligo-Miocene magmatism in central Chile at 33°S.Our data include field and petrographic observations, whole-rockmajor and trace element analyses, U–Pb zircon dating,and Pb, Sr, and Hf isotope analyses of plagioclase, clinopyroxene,and zircon mineral separates. Combined with earlier dating resultsthe new zircon ages define a 28·8–5·2 Maperiod of plutonic and volcanic activity that ceased as a consequenceof flattening subduction of the Nazca–Farallon plate.Rare earth elements patterns are variable, with up to 92 timeschondrite concentrations for light rare earth elements yielding(La/Yb)_N between 3·6 and 7·0, and an absence ofEu anomalies. Initial Pb isotope signatures are in the rangeof 18·358–19·023 for ²⁰⁶Pb/ ²⁰⁴Pb, 15·567–15·700for ²⁰⁷Pb/ ²⁰⁴Pb and 38·249–39·084 for ²⁰⁸Pb/²⁰⁴Pb. Initial ⁸⁷Sr/ ⁸⁶Sr are mostly in the range of 0·70369–0·70505,with two more radiogenic values at 0·7066. Initial Hfisotopic compositions of zircons yield exclusively positiveHf_i ranging between + 6·9 and + 9·6. The newlydetermined initial isotope characteristics of the Oligo-Miocenemagmas suggest that the mantle source lithologies are differentfrom both those of Pacific mid-ocean ridge basalt and oceanisland basalt, plotting in the field of reference values forsubcontinental lithospheric mantle, characterized by moderatelarge ion lithophile element–high field strengh elementdepletion and high ²³⁸U/ ²⁰⁴Pb. A Hf model age of 2 Ga is estimatedfor the formation of the subcontinental mantle–continentalcrust assemblage in the region, suggesting that the initialSr and Pb isotope ratios inferred for the source of the Oligo-Mioceneparental magmas are the result of later Rb and U enrichmentcaused by mantle metasomatism. A time-integrated model Rb/Srof 0·039 and µ 16 are estimated for the sourceof the parental magmas, consistent with ratios measured in peridotitexenoliths from continental areas. Evolution from predominant(>90%) basaltic–gabbroic to andesitic–dioriticmagmas seems to involve a combination of (1) original traceelement differences in the metasomatized subcontinental mantle,(2) different degrees of partial melting and (3) fractionalcrystallization in the garnet- and spinel-peridotite stabilityfields. The genesis of more differentiated magmas reaching rhyolitic–graniticcompositions most probably also includes additional crystalfractionation at both shallow mantle depths and within the crust,possibly leading to some very minor assimilation of crustalmaterial. KEY WORDS: calc-alkaline magmatism; Oligo-Miocene; U–Pb dating; Sr–Pb–Hf isotopes; central Chile