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

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.     

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.     

Weibull statistical analysis of granite bending strength

Summary  This paper describes and discusses the adequacy of Weibull statistical analysis to analyse the bending strength of granite. The experimental results show that strength variability is related with a specific origin of failure. This conclusion is based on analysing the influence of the surface condition (extrinsic defects) on the bending strength results treated by the Weibull statistics. The conclusions drawn from this study have been validated by analysing the results of the critical flaw dimension estimated by applying the linear elastic fracture mechanics (LEFM) formulae. Results obtained from fractographic examination also have been used to describe the location of the origin of the fracture and understand the distribution of defects; i.e., there is a unimodal distribution of defects (intrinsic defects), despite the fact that some outlier values are normally observed in the fractured surfaces. Correspndence: P. M. Amaral, Department of Materials Engineering, Instituto Superior Técnico, Technical University of Lisbon, Av. Rovisco Pais, 1049-001 Lisboa, Portugal     

Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: II. Metal removal mechanisms and potential mobility

Column bioreactors were used for studying mechanisms of metal removal, assessment of long-term stability of spent reactive mixtures, as well as potential metal mobility after treating highly contaminated acid mine drainage (AMD; pH 2.9–5.7). Several physicochemical, microbiological, and mineralogical analyses were performed on spent reactive mixtures collected from 4 bioreactors, which were tested in duplicate for two hydraulic retention times (7.3d and 10d), with downward flow over an 11-month period. Consistent with the high metal concentrations in the AMD feed, and with low metal concentrations measured in the treated effluent, the physicochemical analyses indicated very high concentrations of metals (Fe, Mn, Cd, Ni, and Zn) in the top and bottom layers of the reactive mixtures from all columns. Moreover, the concentrations of Fe (50.8–57.8 g/kg) and Mn (0.53–0.70 g/kg) were up to twice as high in the bottom layers, whereas the concentrations of Cd (6.77–13.3 g/kg), Ni (1.80–5.19 g/kg) and Zn (2.53–13.2 g/kg) were up to 50-times higher in the top layers. Chemical extractions and elemental analysis gave consistent results, which indicated a low fraction of metals removed as sulfides (up to 15% of total metals recovered in spent reactive mixtures). Moreover, Fe and Mn were found in a more stable chemical form (residual fraction was 42–74% for Mn and 30–77% for Fe) relative to Cd, Ni or Zn, which seemed more weakly bound (oxidisable/reducible fractions) and showed higher potential mobility. Besides identifying (oxy)hydroxide and carbonate minerals, the mineralogical analyses identified metal sulfides containing Fe, Cd, Ni and Zn. Metal removal mechanisms were, therefore, mainly adsorption and other binding mechanisms with organic matter (for Cd, Ni and Zn), and the precipitation as (oxy)hydroxide minerals (for Fe and Mn). After 15 months, however, the column bioreactors did not lose their capacity for removing metals from the AMD. Although the metals were immobile during the bioreactor treatment, their mobility could increase from spent reactive mixtures, if stored inappropriately. Metal recovery by acidic leaching of spent substrates at the end of bioreactor operation could be an alternative.     

Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

National-scale estimation of potentially harmful element ambient background concentrations in topsoil using parent material classified soil:stream–sediment relationships

Regulatory authorities require estimates of ambient background concentrations (ABCs) of potentially harmful elements (PHEs) in topsoil; such data are currently not available in many countries. High resolution soil geochemical data exist for only part of England and Wales, whilst stream sediment data cover the entire landscape. A novel methodology is presented for estimating soil equivalent ABCs for PHEs from high-resolution (HR) stream sediment geochemical data grouped by common parent materials (PM), using arsenic (As) as an example. Geometric mean (GM) values for local PM groups are used to investigate different approaches for transforming sediment to soil equivalent concentrations. Holdout validation is used to assess: (i) the optimum number of samples for calculating local GM values, and (ii) the optimum scale at which to group data when using linear regression analysis to estimate GM soil ABCs from local sediment geochemical values. Holdout validation showed that the smallest differences were generally observed when five observations were used to calculate the GM and that these should be grouped over the smallest possible area in order to encompass soils over PMs with elevated GM As concentrations. Geometric mean ABCs are estimated and mapped for As in mineral soil across all of England and Wales within delineations of PM polygons. Errors for the estimation of soil equivalent GM As ABCs based on sediment data for an independent validation set were of a similar magnitude to those from holdout validation applied to the original data suggesting the approach is robust. The estimates of soil equivalent ABCs suggest that As exceeds the regulatory threshold used in risk assessments for residential land use (20 mg kg⁻¹) across 16% of the landscape of England and Wales. The applicability of the method for cognate landscapes, and potential refinements is discussed.     

First U–Pb SHRIMP age of the Hauterivian stage, Neuquén Basin, Argentina

A high-resolution ion-microprobe (SHRIMP) U–Pb zircon age from a tuff layer intercalated in the ammonoid bearing sedimentary succession of the Neuquén Basin in Argentina provides a robust geochronologic date to add to the absolute ages and to improve the relative chronology of the Early Cretaceous Hauterivian stage. The tuff layer appears interbedded between shales of the upper member (Agua de la Mula) of the Agrio Formation within the Spitidiscus riccardii ammonoid zone (base of the Late Hauterivian) yielding a date of 132.5 ± 1.3 Ma. This date confirms and supports an accurate correlation between the ammonoid biostratigraphy of the Neuquén Basin with the Western Mediterranean Province of the Tethys during the Early Cretaceous and matches with the most recently published time scale. It also casts doubts on the validity of K–Ar ages on glauconite-grains recently reported from the Lower Cretaceous of the Vocontian Basin of France.