Quantitative textural analysis of packings of elongate crystals

The spatial distribution of grains in a solidifying igneous rock controls the physical properties of the crystal mush, and in turn is controlled by the rate of crystal growth and accumulation. A predominant non-spherical habit for igneous minerals brings into question the use of spherical particles in reference packings used for quantification of spatial distribution. Furthermore, variations of crystal clustering/ordering with length scale require spatial statistics which take into account the distribution of particles beyond nearest neighbours. Using random close packings of spherocylinders, we demonstrate the importance of aspect ratio for the aggregation index (usually known as R) and show that packings of spherical particles have more structure than packings of rods. The spatial distribution functions demonstrate that the plagioclase grains in the colonnade from the Holyoke basalt are clustered on a length scale of 0.5 mm. Understanding the controls on grain spatial distribution in igneous rocks will depend on the application of these techniques to well-understood environments.     

The effects of metamorphism on O and Fe isotope compositions in the Biwabik Iron Formation, northern Minnesota

The Biwabik Iron Formation of Minnesota (1.9 Ga) underwent contact metamorphism by intrusion of the Duluth Complex (1.1 Ga). Apparent quartz–magnetite oxygen isotope temperatures decrease from ∼700°C at the contact to ∼375°C at 2.6 km distance (normal to the contact in 3D). Metamorphic pigeonite at the contact, however, indicates that peak temperatures were greater than 825°C. The apparent O isotope temperatures, therefore, reflect cooling, and not peak metamorphic conditions. Magnetite was reset in δ¹⁸O as a function of grain size, indicating that isotopic exchange was controlled by diffusion of oxygen in magnetite for samples from above the grunerite isograd. Apparent quartz–magnetite O isotope temperatures are similar to calculated closure temperatures for oxygen diffusion in magnetite at a cooling rate of ∼5.6°C/kyr, which suggests that the Biwabik Iron Formation cooled from ∼825 to 400°C in ∼75 kyr at the contact with the Duluth Complex. Isotopic exchange during metamorphism also occurred for Fe, where magnetite–Fe silicate fractionations decrease with increasing metamorphic grade. Correlations between quartz–magnetite O isotope fractionations and magnetite–iron silicate Fe isotope fractionations suggest that both reflect cooling, where the closure temperature for Fe was higher than for O. The net effect of metamorphism on δ¹⁸O–δ⁵⁶Fe variations in magnetite is a strong increase in δ¹⁸O_Mt and a mild decrease in δ⁵⁶Fe with increasing metamorphic grade, relative to the isotopic compositions that are expected at the low temperatures of initial magnetite formation. If metamorphism of Iron Formations occurs in a closed system, bulk O and Fe isotope compositions may be preserved, although re-equilibration among the minerals may occur for both O and Fe isotopes. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Isotopic studies of leaf water. Part 1: A physically based two-dimensional model for pine needles

Understanding of isotopic variations in leaf water is important for reconstruction of paleoclimate and assessment of global biochemical processes. We report here a study of isotopic distributions within a single needle of two pine species, Pinus resinosa Ait and Pinus strobes L., with the objective of understanding how isotopic compositions of leaf water are controlled by environmental and physiological variables. A 2D model was developed to simulate along-leaf isotopic variations and bulk leaf water isotopic compositions. In addition to variables common to all leaf water isotopic models, this 2D model also takes into account the specific geometry and dimensions of pine needles and the isotopic transport in xylem and mesophyll. The model can successfully simulate oxygen isotopic variations along a single needle and averaged over a leaf (bulk leaf water). The simulations suggest that isotopic composition of the bulk leaf water does not always depend only upon the average transpiration rate, which in turn raises questions about using leaf water isotopic values to estimate transpiration rates. An unsuccessful attempt to simulate along-needle hydrogen isotopic variations suggests that certain unknown biological process(es) may not have been incorporated into our 2D model, and if so, it calls for a reevaluation of all other models for hydrogen isotopic simulations of leaf water since they too lack these processes.Existing leaf water isotopic models are reviewed in this work. In particular, we evaluate the most frequently used model, the stomatal boundary layer model (also referred to as the Craig-Gordon model). We point out that discrepancy between the boundary layer model and the measured bulk leaf water seems to depend upon relative humidity. Using our 2D model, we show that this humidity dependency is a result of an interplay between environmental and physiological conditions: if the transpiration rate of plant leaves decreases with increasing relative humidity, our 2D model can reproduce the pattern of isotopic discrepancy between boundary layer model predictions and observations, enabling us to understand better the reason behind this discrepancy.     

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.     

Globalisation in practice: On the politics of boiling pigswill

This paper is about ‘material politics’. It argues that this may be understood as a material ordering of the world in a way that contrasts this with other and equally possible alternative modes of ordering. It also suggests that while material politics may well involve words, it is not discursive in kind. This argument is made for the mundane and material practice of boiling pigswill that the 2001 UK foot and mouth outbreak showed to have a layered importance. Boiling pigswill was a political technique in at least three different ways. First it made difference, dividing the rich from the poor by separating disease free countries from those in which foot and mouth is endemic. Second, it joined times and places by linking past agricultural practices with those of the contemporary world, and linking Britain with the world. And third, it also showed a way of limiting food scarcity on a world wide scale because it allowed food to be recycled, albeit on a small scale, in a region of plenty. ‘Politics’ is often linked to debate, discussion, or explicit contestation. Alternatively, it is sometimes seen as being embedded in and carried by artefacts. For the case of boiling pigswill neither approach is satisfactory. The first privileges the life of the mind while in the second politics is linked too strongly to a single order. The version of politics presented here foregrounds both materiality and difference. And it involves articulation: the question is not whether something is political all by itself but whether it can be called political as part of the process of analysing it.     

Mapping ambivalence: Exploring the geographies of community change and rails-to-trails development using photo-based Q method and PPGIS

As the literature on trail development suggests, recreational trail projects can generate conflicts and controversies, particularly when built on abandoned rail corridors through developed areas. These conflicts are often understood as “not in my back yard” (NIMBY) reactions, suggesting a spatial proximity to conflict which increases as one draws closer to the proposed trail. This research seeks to understand local residents’ perceptions and reactions to recreational trail development in the City of Delaware (Ohio, USA). It addresses two spatially infused questions: Does the potential for conflict related to trail development increase as people live closer to a potential trail (the NIMBY factor)? Can important qualitative factors about favorable and unfavorable land uses including potential recreational trail sites be defined using a participatory methodology and then represented in GIS? The study used a mixed-method approach to collect and analyze qualitative data from a group of local residents. Each participant was interviewed and asked to sort 19 pictures related to trail development. After each of the sorts, participants were asked to explain why they ranked the pictures the way they did. Results of the picture sorts were then analyzed using Q method and mapped with GIS. The results show that spatial proximity matters in the context of trail development and potential NIMBY reactions to trails. Significant differences were found in the picture sorts that reveal the importance of proximity and location, although in a manner contrary to the assumptions in the writings on rails-to-trails. Through combining qualitative methods, Q analysis and PPGIS analysis, the research shows that qualitative place-based studies are capable of generating insights about the complexities of situated geographic change such as recreational trail development.     

Origin of Fe-Ti Oxide Ores in Mafic Intrusions: Evidence from the Panzhihua Intrusion, SW China

Economic concentrations of Fe–Ti oxides occur as massive,conformable lenses or layers in the lower part of the Panzhihuaintrusion, Emeishan Large Igneous Province, SW China. Mineralchemistry, textures and QUILF equilibria indicate that oxidesin rocks of the intrusion were subjected to extensive subsolidusre-equilibration and exsolution. The primary oxide, reconstructedfrom compositions of titanomagnetite in the ores and associatedintergrowths, is an aluminous titanomagnetite (Usp₄₀) with 40wt % FeO, 34 wt % Fe₂O₃, 16·5 wt % TiO₂, 5·3 wt% Al₂O₃, 3·5 wt % MgO and 0·5 wt % MnO. This compositionis similar to the bulk composition of the oxide ore, as inferredfrom whole-rock data. This similarity strongly suggests thatthe ores formed from accumulation of titanomagnetite crystals,not from immiscible oxide melt as proposed in earlier studies.The occurrence of oxide ores in the lower parts of the Panzhihuaintrusion is best explained by settling and sorting of densetitanomagnetite in the ferrogabbroic parental magma. This magmamust have crystallized Fe–Ti oxides relatively early andabundantly, and is likely to have been enriched in Fe and Tibut poor in SiO₂. These features are consistent with fractionationof mantle-derived melts under relatively high pressures (10kbar), followed by emplacement of the residual magma at 5 kbar.This study provides definitive field and geochemical evidencethat Fe–Ti oxide ores can form by accumulation in ferrogabbro.We suggest that many other massive Fe–Ti oxide depositsmay have formed in a similar fashion and that high concentrationsof phosphorus or carbon, or periodic fluctuation of fO₂ in themagma, are of secondary importance in ore formation. KEY WORDS: ELIP; Fe–Ti oxide ore; layered intrusion; Panzhihua; QUILF     

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