The Fe-C system at 5 GPa and implications for Earth’s core     

Nancy L. Chabot  Andrew J. Campbell  David S. Draper  Munir Humayun  Elizabeth Cottrell 《Geochimica et cosmochimica acta》2008,72(16):4146-4158

Earth’s core may contain C, and it has been suggested that C in the core could stabilize the formation of a solid inner core composed of Fe₃C. We experimentally examined the Fe-C system at a pressure of 5 GPa and determined the Fe-C phase diagram at this pressure. In addition, we measured solid metal/liquid metal partition coefficients for 17 trace elements and examined the partitioning behavior between Fe₃C and liquid metal for 14 trace elements. Solid metal/liquid metal partition coefficients are similar to those found in one atmosphere studies, indicating that the effect of pressure to 5 GPa is negligible. All measured Fe₃C/liquid metal partition coefficients investigated are less than one, such that all trace elements prefer the C-rich liquid to Fe₃C. Fe₃C/liquid metal partition coefficients tend to decrease with decreasing atomic radii within a given period. Of particular interest, our 5 GPa Fe-C phase diagram does not show any evidence that the Fe-Fe₃C eutectic composition shifts to lower C contents with increasing pressure, which is central to the previous reasoning that the inner core may be composed of Fe₃C.  相似文献   

Neoliberalizing environmental governance? Land trusts, private conservation and nature on the Oak Ridges Moraine     

Shannon Logan  Gerda R. Wekerle 《Geoforum》2008,(6):2097-2108

With recent changes in the ways that state agencies are implementing their environmental policies, the line between public and private is becoming increasingly blurred. This includes shifts from state-led implementation of environmental policies to conservation plans that are implemented and managed by multi-sectoral networks of governments, the private sector and environmental non-governmental organizations (ENGOs). This paper examines land trusts as private conservation initiatives that become part of neoliberal governance arrangements and partnerships that challenge our conceptions of environmental preservation and democratic participation. The paper starts with an examination of the concept of neoliberalized environmental governance. Next, it addresses the shifting social constructions of property and land in the context of protecting large scale ecosystems. Through a case study of the extension of new environmental governance arrangements on the Oak Ridges Moraine in Ontario, we examine the relationships that have formed between different levels of the state and environmental non-governmental organizations. Finally, we analyze the expansion of land trusts and private conservation initiatives that are predicated on private land ownership and the commodification of nature, the emerging discourses and practices of private conservation, and how these are implicated in the privatization and neoliberalization of nature.  相似文献   

The persistence of lead from past gasoline emissions and mining drainage in a large riparian system: Evidence from lead isotopes in the Sacramento River, California   总被引：1，自引：0，他引：1  

C.E. Dunlap  C.N. Alpers  H.E. Taylor  A.R. Flegal 《Geochimica et cosmochimica acta》2008,72(24):5935-5948

Lead concentrations and isotope ratios measured in river water colloids and streambed sediment samples along 426 km of the Sacramento River, California reveal that the influence of lead from the historical mining of massive sulfide deposits in the West Shasta Cu-mining district (at the headwaters of the Sacramento River) is confined to a 60 km stretch of river immediately downstream of that mining region, whereas inputs from past leaded gasoline emissions and historical hydraulic Au-mining in the Sierra Nevadan foothills are the dominant lead sources in the remaining 370 km of the river. Binary mixing calculations suggest that more than 50% of the lead in the Sacramento River outside of the region of influence of the West Shasta Cu-mining district is derived from past depositions of leaded gasoline emissions. This predominance is the first direct documentation of the geographic extent of gasoline lead persistence throughout a large riparian system (>160,000 km²) and corroborates previous observations based on samples taken at the mouth of the Sacramento River. In addition, new analyses of sediment samples from the hydraulic gold mines of the Sierra Nevada foothills confirm the present-day fluxes into the Sacramento River of contaminant metals derived from historical hydraulic Au-mining that occurred during the latter half of the 19th and early part of the 20th centuries. These fluxes occur predominantly during periods of elevated river discharge associated with heavy winter precipitation in northern California. In the broadest context, the study demonstrates the potential for altered precipitation patterns resulting from climate change to affect the mobility and transport of soil-bound contaminants in the surface environment.  相似文献   

The composition and crystallinity of the near-surface regions of weathered alkali feldspars     

Martin R. Lee  Mark E. Hodson  Maureen MacKenzie  Caroline L. Smith 《Geochimica et cosmochimica acta》2008,72(20):4962-4975

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.  相似文献   

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   

Microbial mass-dependent fractionation of chromium isotopes   总被引：1，自引：0，他引：1  

Eric R. Sikora  Thomas M. Johnson  Thomas D. Bullen 《Geochimica et cosmochimica acta》2008,72(15):3631-3641

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.  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   

Models in geography revisited     

N.J. Clifford 《Geoforum》2008,39(2):675-686

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.  相似文献