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.     

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.     

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.     

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.     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.