Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As−1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O₂), hypoxic (2% O₂, 98% N₂), and anoxic (5% H₂, 95% N₂) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (−1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations.     

Microbial mass-dependent fractionation of chromium isotopes

Mass-dependent fractionation of Cr isotopes occurs during dissimilatory Cr(VI) reduction by Shewanella oneidensis strain MR-1. Cells suspended in a simple buffer solution, with various concentrations of lactate or formate added as electron donor, reduced 5 or 10 μM Cr(VI) to Cr(III) over days to weeks. In all nine batch experiments, ⁵³Cr/⁵²Cr ratios of the unreacted Cr(VI) increased as reduction proceeded. In eight experiments covering a range of added donor concentrations up to 100 μM, isotopic fractionation factors were nearly invariant, ranging from 1.0040 to 1.0045, with a mean value somewhat larger than that previously reported for abiotic Cr(VI) reduction (1.0034). One experiment containing much greater donor concentration (10 mM lactate) reduced Cr(VI) much faster and exhibited a lesser fractionation factor (1.0018). These results indicate that ⁵³Cr/⁵²Cr measurements should be effective as indicators of Cr(VI) reduction, either bacterial or abiotic. However, variability in the fractionation factor is poorly constrained and should be studied for a variety of microbial and abiotic reduction pathways.     

Integrating diverse methods to understand climate-land interactions in East Africa

The questions of how land use change affects climate, and how climate change affects land use, require examination of societal and environmental systems across space at multiple scales, from the global climate to regional vegetative dynamics to local decision making by farmers and herders. It also requires an analysis of causal linkages and feedback loops between systems. These questions and the conceptual approach of the research design of the Climate-Land Interaction Project (CLIP) are rooted in the classical human-environment research tradition in Geography.This paper discusses a methodological framework to quantify the two-way interactions between land use and regional climate systems, using ongoing work by a team of multi-disciplinary scientists examining climate-land dynamics at multiple scales in East Africa. East Africa is a region that is undergoing rapid land use change, where changes in climate would have serious consequences for people’s livelihoods, and requiring new coping and land use strategies. The research involves exploration of linkages between two important foci of global change research, namely, land use/land cover (LULC) and climate change. These linkages are examined through modeling agricultural systems, land use driving forces and patterns, the physical properties of land cover, and the regional climate. Both qualitative and quantitative methods are being used to illustrate a diverse pluralism in scientific discovery.     

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.     

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     

Large and giant hydrocarbon accumulations in the transitional continent-ocean zone

The petroleum resource potential is considered for the Atlantic, West Pacific, and East Pacific types of deepwater continental margins. The most considerable energy resources are concentrated at the Atlantic-type passive margins in the zone transitional to the ocean. The less studied continental slope of backarc seas of the generally active margins of the West Pacific type is currently not so rich in discoveries as the Atlantic-type margin, but is not devoid of certain expectations. In some of their parameters, the margins bounded by continental slopes may be regarded as analogs of classical passive margins. At the margins of the East Pacific type, the petroleum potential is solely confined to transform segments. In the shelf-continental-slope basins of the rift and pull-apart nature, petroleum fields occur largely in the upper fan complex, and to a lesser extent in the lower graben (rift) complex. In light of world experience, the shelf-continental-slope basins of the Arctic and Pacific margins of Russia are evaluated as highly promising.     

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.     

Oxygen Isotope Evidence for Chemical Interaction of Ki lauea Historical Magmas with Basement Rocks

Klauea historical summit lavas have a wide range in matrix ¹⁸O_VSMOWvalues (4·9–5·6) with lower values in rockserupted following a major summit collapse or eruptive hiatus.In contrast, ¹⁸O values for olivines in most of these lavasare nearly constant (5·1 ± 0·1). The disequilibriumbetween matrix and olivine ¹⁸O values in many samples indicatesthat the lower matrix values were acquired by the magma afterolivine growth, probably just before or during eruption. BothMauna Loa and Klauea basement rocks are the likely sources ofthe contamination, based on O, Pb and Sr isotope data. However,the extent of crustal contamination of Klauea historical magmasis probably minor (< 12%, depending on the assumed contaminant)and it is superimposed on a longer-term, cyclic geochemicalvariation that reflects source heterogeneity. Klauea's heterogeneoussource, which is well represented by the historical summit lavas,probably has magma ¹⁸O values within the normal mid-ocean ridgebasalt mantle range (5·4–5·8) based on thenew olivine ¹⁸O values. KEY WORDS: Hawaii; Klauea; basalt; oxygen isotopes; crustal contamination