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.     

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.     

Exurbia from the bottom-up: Confronting empirical challenges to characterizing a complex system

We describe empirical results from a multi-disciplinary project that support modeling complex processes of land-use and land-cover change in exurban parts of Southeastern Michigan. Based on two different conceptual models, one describing the evolution of urban form as a consequence of residential preferences and the other describing land-cover changes in an exurban township as a consequence of residential preferences, local policies, and a diversity of development types, we describe a variety of empirical data collected to support the mechanisms that we encoded in computational agent-based models. We used multiple methods, including social surveys, remote sensing, and statistical analysis of spatial data, to collect data that could be used to validate the structure of our models, calibrate their specific parameters, and evaluate their output. The data were used to investigate this system in the context of several themes from complexity science, including have (a) macro-level patterns; (b) autonomous decision making entities (i.e., agents); (c) heterogeneity among those entities; (d) social and spatial interactions that operate across multiple scales and (e) nonlinear feedback mechanisms. The results point to the importance of collecting data on agents and their interactions when producing agent-based models, the general validity of our conceptual models, and some changes that we needed to make to these models following data analysis. The calibrated models have been and are being used to evaluate landscape dynamics and the effects of various policy interventions on urban land-cover patterns.     

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.     

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.     

The posthumous tectonics and mechanism of exhumation of granitic plutons: The case of the Transbaikal region and the Tien Shan

The study of granitic plutons of the Baikal Highland and the Tien Shan has made it possible to establish new features of their posthumous (after incorporation into the consolidated Earth’s crust) structural reworking and to understand the implications of the cataclastic flow for the exhumation of the crystalline basement in the studied regions. It is shown that granitic plutons undergo appreciable structural transformation at the stages of tectonic reactivation that is significantly separated in time from the moment of formation of plutons as geological bodies. The 3D cataclastic deformation is the main mode of structural reworking of granitic plutons, while the cataclastic flow is the main form of their mobility. Newly recognized slice structures characterize the volumetric deformation of granites.     

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.     

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.     

Crystalline basement and fold complex of the Volga-Ural, Pericaspian, and Fore-Caucasus petroliferous basins

3D models of apparent magnetization and density of rocks allow us to provide insights into the deep structure of the Volga-Ural, Pericaspian, and Fore-Caucasus petroliferous basins. In the Volga-Ural Basin, some Riphean rifts reveal close spatial relations to Paleoproterozoic linear zones, presumably of the rift nature as well. The structure of the Paleoproterozoic Toropets-Serdobsk Belt is interpreted in detail. Rocks with petrophysical properties inherent to basic volcanics are established in the pre-Paleozoic basement of the marginal zone of the Pericaspian Basin. These rocks locally spread beyond the boundary escarpment and may be regarded as a part of the Riphean plume-related basaltic province. It is shown that the Pericaspian Basin was formed on the place of a triple junction of Riphean rifts: the Sarpa and Central Pericaspian oceanic branches and the continental branch of the Pachelma Aulacogen. The drastically different petrophysical properties of the basement beneath Baltica and the Astrakhan Arch indicate that this arch is an element of the large terrane that was attached to Baltica in the Vendian. The suture along which the Astrachan Terrane is conjugated with the basement of the central and southern segments of the Karpinsky Ridge is traced beneath the Paleozoic complex. A system of northwest-verging thrust faults formed during the collision between Scythia and Eurasia is mapped in the basement of the junction zone between the Karpinsky Ridge and Scythian Platform (Terrane). According to geological data, this event took place in the Early Paleozoic.     

Lateral protrusions in the structure of the Earth’s lithosphere

The factual material and modeling results concerning the geology of specific structural elements defined as lateral protrusions, or flowing layers, are considered. The formation of such structural elements is a fundamental phenomenon that controls many features of the structural evolution and geodynamics of platform basement and foldbelts. A lateral protrusion, or flowing layer, is a spatially constrained, nearly horizontal geological body with attributes of 3D tectonic flow (rheid deformation) and lateral transport of rock masses. Flowing layers are large lateral protrusions that play important role in the structure of the continental and oceanic lithosphere. They embody the internal mobility of huge rock bodies and confirm the possibility of their lateral redistribution at different depths of the continental lithosphere. The lateral displacement of rocks within such assemblies may occur in the regime of cold deformation, heating, metamorphism, and ductile flow of rocks under subsolidus conditions or in the process of their partial melting.