Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite   总被引：1，自引：0，他引：1  

Wenyi Zhu  Nathan Yee  E. Danielle Rhine  John R. Reinfelder 《Geochimica et cosmochimica acta》2008,72(21):5243-5250

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.  相似文献   

Nanoscale study of As biomineralization in an acid mine drainage system     

K. Benzerara  G. Morin  J. Miot  C. Casiot  F. Farges  G.E. Brown Jr. 《Geochimica et cosmochimica acta》2008,72(16):3949-3963

Spatial and seasonal variations of the oxidation of Fe(II) and As(III) have been previously documented in the Carnoulès (Gard, France) Acid Mine Drainage (AMD) by bulk analyses. These variations may be correlated with the variations in the activity of indigenous As(III)- and Fe(II)-oxidizing bacteria living in the As-rich Carnoulès water. The activity of these bacteria indeed plays an important role in the nature and composition of the solid phases that sequester arsenic at this site. In order to better understand the interactions of microbes with Fe and As in the Carnoulès AMD, we combined Transmission Electron Microscopy (TEM) and Scanning Transmission X-ray Microscopy (STXM) to collect near-edge X-ray absorption fine structure (NEXAFS) spectra at high spatial and energy resolution and to perform high spatial resolution imaging at the 30-50 nm scale. Spectromicroscopy was performed at the C K-edge, Fe L_2,3-edge, and As L_2,3-edge, which allowed us to locate living and/or mineralized bacterial cells and to characterize Fe and As oxidation states in the vicinity of those cells. TEM was used to image the same areas, providing higher resolution images and complementary crystallographic and compositional information through electron diffraction and EDXS analysis. This approach provides unique information on heterogeneous geochemical processes that occur in a complex microbial community in an AMD environment at the micrometer and submicrometer-scale. Bacterial cells in the Carnoulès AMD were frequently associated with mineral precipitates, and a variety of biomineralization patterns were observed. While many mineral precipitates were not associated with bacterial cells, they were associated with pervasive organic carbon. Finally, abundant biomineralized organic vesicles were observed in the Carnoulès AMD. Such vesicles may have been overlooked in highly mineralized extreme environments in the past and may represent an important component in a common biomineralization process in such environments.  相似文献   

Geochemistry, petrology and ages of the lunar meteorites Kalahari 008 and 009: New constraints on early lunar evolution     

A.K. Sokol  V.A. Fernandes  T. Schulz  A. Bischoff  R.N. Clayton  K. Nishiizumi  L. Schultz  K. Mezger 《Geochimica et cosmochimica acta》2008,72(19):4845-4873

Kalahari 008 and 009 are two lunar meteorites that were found close to each other in Botswana. Kalahari 008 is a typical lunar anorthositic breccia; Kalahari 009 a monomict breccia with basaltic composition and mineralogy. Based on minor and trace elements Kalahari 009 is classified as VLT (very-low-Ti) mare basalt with extremely low contents of incompatible elements, including the REE. The Lu-Hf data define an age of 4286 ± 95 Ma indicating that Kalahari 009 is one of the oldest known basalt samples from the Moon. It provides evidence for lunar basalt volcanism prior to 4.1 Ga (pre-Nectarian) and may represent the first sample from a cryptomare. The very radiogenic initial ¹⁷⁶Hf/¹⁷⁷Hf (εHf = +12.9 ± 4.6), the low REE, Th and Ti concentrations indicate that Kalahari 009 formed from re-melting of mantle material that had undergone strong incompatible trace element depletion early in lunar history. This unusually depleted composition points toward a hitherto unsampled basalt source region for the lunar interior that may represent a new depleted endmember source for low-Ti mare basalt volcanism. Apparently, the Moon became chemically very heterogeneous at an early stage in its history and different cumulate sources are responsible for the diverse mare basalt types.Evidence that Kalahari 008 and 009 may be paired includes the similar fayalite content of their olivine, the identical initial Hf isotope composition, the exceptionally low exposure ages of both rocks and the fact that they were found close to each other. Since cryptomaria are covered by highland ejecta, it is possible that these rocks are from the boundary area, where basalt deposits are covered by highland ejecta. The concentrations of cosmogenic radionuclides and trapped noble gases are unusually low in both rocks, although Kalahari 008 contains slightly higher concentrations. A likely reason for this difference is that Kalahari 008 is a polymict breccia containing a briefly exposed regolith, while Kalahari 009 is a monomict brecciated rock that may never have been at the surface of the Moon.Altogether, the compositions of Kalahari 008 and 009 permit new insight into early lunar evolution, as both meteorites sample lunar reservoirs hitherto unsampled by spacecraft missions. The very low Th and REE content of Kalahari 009 as well as the depletion in Sm and the lack of a KREEP-like signature in Kalahari 008 point to a possible source far from the influence of the Procellarum-KREEP Terrane, possibly the lunar farside.  相似文献   

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

G.R. Helz  J.A. Tossell 《Geochimica et cosmochimica acta》2008,72(18):4457-4468

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.  相似文献   

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

A. Wendy Russell 《Geoforum》2008,39(1):213-222

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.  相似文献   

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

Christopher A. Airriess  Wei Li  Karen J. Leong  Angela Chia-Chen Chen  Verna M. Keith 《Geoforum》2008,39(3):1333-1346

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.  相似文献   

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

M. G. Leonov  Yu. A. Morozov  A. V. Nikitin 《Geotectonics》2008,42(2):81-104

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.  相似文献   

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

M. N. Shapiro  A. V. Solov’ev  J. K. Hourigan 《Geotectonics》2008,42(6):469-487

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.  相似文献