Uranium co-precipitation with iron oxide minerals

In oxidizing environments, the toxic and radioactive element uranium (U) is most soluble and mobile in the hexavalent oxidation state. Sorption of U(VI) on Fe-oxides minerals (such as hematite [α-Fe₂O₃] and goethite [α-FeOOH]) and occlusion of U(VI) by Fe-oxide coatings are processes that can retard U transport in environments. In aged U-contaminated geologic materials, the transport and the biological availability of U toward reduction may be limited by coprecipitation with Fe-oxide minerals. These processes also affect the biological availability of U(VI) species toward reduction and precipitation as the less soluble U(IV) species by metal-reducing bacteria.To examine the dynamics of interactions between U(VI) and Fe oxides during crystallization, Fe-oxide phases (containing 0.5 to 5.4 mol% U/(U + Fe)) were synthesized by means of solutions of U(VI) and Fe(III). Wet chemical (digestions and chemical extractions) and spectroscopic techniques were used to characterize the synthesized Fe oxide coprecipitates after rinsing in deionized water. Leaching the high mol% U solids with concentrated carbonate solution (for sorbed and solid-phase U(VI) species) typically removed most of the U, leaving, on average, about 0.6 mol% U. Oxalate leaching of solids with low mol% U contents (about 1 mol% U or less) indicated that almost all of the Fe in these solids was crystalline and that most of the U was associated with these crystalline Fe oxides. X-ray diffraction and Fourier-transform infrared (FT-IR) spectroscopic studies indicate that hematite formation is preferred over that of goethite when the amount of U in the Fe-oxides exceeds 1 mol% U (∼4 wt% U). FT-IR and room temperature continuous wave luminescence spectroscopic studies with unleached U/Fe solids indicate a relationship between the mol% U in the Fe oxide and the intensity or existence of the spectra features that can be assigned to UO₂²⁺ species (such as the IR asymmetric υ₃ stretch for O = U = O for uranyl). These spectral features were undetectable in carbonate- or oxalate-leached solids, suggesting solid phase and sorbed U(VI)O₂²⁺ species are extracted by the leach solutions. Uranium L₃-edge x-ray absorption spectroscopic (XAFS) analyses of the unleached U-Fe oxide solids with less than 1 mol% U reveal that U(VI) exists with four O atoms at radial distances of 2.19 and 2.36 Å and second shell Fe at a radial distance at 3.19 Å.Because of the large ionic radius of UO₂²⁺ (∼1.8 Å) relative to that of Fe³⁺ (0.65 Å), the UO₂²⁺ ion is unlikely to be incorporated in the place of Fe in Fe(III)-oxide structures. Solid-phase U(VI) can exist as the uranyl [U(VI)O₂²⁺] species with two axial U-O double bonds and four or more equatorial U-O bonds or as the uranate species (such as γ-UO₃) without axial U-O bonds. Our findings indicate U⁶⁺ (with ionic radii of 0.72 to 0.8 Å, depending on the coordination environment) is incorporated in the Fe oxides as uranate (without axial O atoms) until a point of saturation is reached. Beyond this excess in U concentration, precipitating U(VI) forms discrete crystalline uranyl phases that resemble the uranyl oxide hydrate schoepite [UO₂(OH)₂·2H₂O]. Molecular modeling studies reveal that U⁶⁺ species could bond with O atoms from distorted Fe octahedra in the hematite structure with an environment that is consistent with the results of the XAFS. The results provide compelling evidence of U incorporation within the hematite structure.     

A New Model for Heat Flow in Extensional Basins: Estimating Radiogenic Heat Production

Radiogenic heat production (RHP) represents a significant fraction of surface heat flow, both on cratons and in sedimentary basins. RHP within continental crust—especially the upper crust—is high. RHP at any depth within the crust can be estimated as a function of crustal age. Mantle RHP, in contrast, is always low, contributing at most 1 to 2 mW/m² to total heat flow. Radiogenic heat from any noncrystalline basement that may be present also contributes to total heat flow. RHP from metamorphic rocks is similar to or slightly lower than that from their precursor sedimentary rocks. When extension of the lithosphere occurs—as for example during rifting—the radiogenic contribution of each layer of the lithosphere and noncrystalline basement diminishes in direct proportion to the degree of extension of that layer. Lithospheric RHP today is somewhat less than in the distant past, as a result of radioactive decay. In modeling, RHP can be varied through time by considering the half lives of uranium, thorium, and potassium, and the proportional contribution of each of those elements to total RHP from basement. RHP from sedimentary rocks ranges from low for most evaporites to high for some shales, especially those rich in organic matter. The contribution to total heat flow of radiogenic heat from sediments depends strongly on total sediment thickness, and thus differs through time as subsidence and basin filling occur. RHP can be high for thick clastic sections. RHP in sediments can be calculated using ordinary or spectral gamma-ray logs, or it can be estimated from the lithology.     

Tracking recent recovery from eutrophication in a high arctic lake (Meretta Lake, Cornwallis Island, Nunavut, Canada) using fossil diatom assemblages

Meretta Lake (Resolute Bay, Cornwallis Island, Nunavut, Canada) is a high arctic lake that received raw sewage for almost 50 years from the Canadian Department of Transport Base. The lake was sampled from 1968–72 during the International Biological Programme, as part of the Char Lake Project. As the number of users at the Transport Base declined throughout the 1990s, so too did the lake's nutrient levels, and Meretta Lake is now classified as oligotrophic. A previous diatom-based paleolimnological study revealed marked species assemblage shifts coincident with sewage inputs beginning in the late 1940s; however, because the core was taken at a time when nutrient levels were still relatively high (i.e., 1993), the diatom record did not yet track any signs of recovery. In this present study, we examined fossil diatom assemblages from a sediment core taken in 2001. Our results indicate a shift to the pre-impact diatom assemblages in the most recent sediments, indicating that the paleolimnological record is tracking the decreased nutrient inputs to this high arctic lake, and confirms that no significant lags exist in these largely ice-covered lakes.     

Pauperizing the pastoral periphery: the marginalization of herding communities in the world's dry lands

Environmental degradation and other socio-economic problems are too often discerned in contemporary pastoral systems in the wake of global economic change. This paper identifies cases where pastoral people respond to external pressures and opportunities in positive ways and adapt to changes. We hope that by doing this a framework of pastoral adaptations can be developed. The first part of this paper focuses on impacts of global economic change, which are mostly negative in nature. Through an extensive literature search in geography, anthropology, range management, and development field, the second part introduces cases that we categorize as positive adaptations.     

Rethinking Precolonial Plant Cultivation on the Northwest Coast of North America

The indigenous peoples of the Northwest Coast of North America are widely believed to have been true “hunter‐fisher‐gatherers,” lacking plant cultivation of any kind. This depiction of the region's indigenous inhabitants emerged within early colonial accounts and was perpetuated within the literatures of geography, anthropology, and archaeology. Still, there is ample evidence of plant cultivation available from archival, archaeological, and ethnographic sources. In particular, the peoples of coastal British Columbia created large gardens of edible estuarine plants, using sophisticated indigenous technologies. The oversight of these practices in written representations of the region reveals consistent patterns of bias, emanating from the agendas of colonial agents and early academics alike. In turn, this bias has undermined aboriginal traditions of cultivation and indigenous land claims.     

Volatiles in glasses from Mauna Loa Volcano,Hawai'i: implications for magma degassing and contamination,and growth of Hawaiian volcanoes

Glasses from Mauna Loa pillow basalts, recent subaerial vents, and inclusions in olivine were analyzed for S, Cl, F, and major elements by electron microprobe. Select submarine glasses were also analyzed for H₂O and CO₂ by infrared spectroscopy. The compositional variation of these tholeiitic glasses is dominantly controlled by crystal fractionation and they indicate quenching temperatures of 1,115-1,196 °C. Submarine rift zone glasses have higher volatile abundances (except F) than nearly all other submarine and subaerial glasses with the maximum concentrations increasing with water depth. The overwhelming dominance of degassed glasses on the submarine flanks of Mauna Loa implies that much of volcano's recent submarine growth involved subaerially erupted lava that reached great water depths (up to 3.1 km) via lava tubes. Anomalously high F and Cl in some submarine glasses and glass inclusions indicate contamination possibly by fumarolic deposits in ephemeral rift zone magma chambers. The relatively high CO₂ but variable H₂O/K₂O and S/K₂O in some submarine rift zone glasses indicates pre-eruptive mixing between degassed and undegassed magma within Mauna Loa's rift system. Volatile compositions for Mauna Loa magmas are similar to other active Hawaiian volcanoes in S and F, but are less Cl-rich than Ll'ihi glasses. However, Cl/K2O ratios are similar. Mauna Loa and Ll'ihi magmas have comparable, but lower H₂O than those from Kilauea. Thus, Kilauea's source may be more H₂O-rich. The dissimilar volatile distribution in glasses from active Hawaiian volcanoes is inconsistent with predictions for a simple, concentrically zoned plume model.     

Flexure of the Indian plate and intraplate earthquakes

The flexural bulge in central India resulting from India's collision with Tibet has a wavelength of approximately 670 km. It is manifest topographically and in the free-air gravity anomaly and the geoid. Calculations of the stress distribution within a flexed Indian plate reveal spatial variations throughout the depth of the plate and also a function of distance from the Himalaya. The wavelength (and therefore local gradient) of stress variation is a function of the effective elastic thickness of the plate, estimates of which have been proposed to lie in the range 40–120 km. The imposition of this stress field on the northward moving Indian plate appears fundamental to explaining the current distribution of intraplate earthquakes and their mechanisms. The current study highlights an outer trough south of the flexural bulge in central India where surface stresses are double the contiguous compressional stresses to the north and south. The Bhuj, Latur and Koyna earthquakes and numerous other recent reverse faulting events occurred in this compressional setting. The N/S spatial gradient of stress exceeds 2 bars/km near the flexural bulge. The overall flexural stress distribution provides a physical basis for earthquake hazard mapping and suggests that areas of central India where no historic earthquakes are recorded may yet be the locus of future damaging events.     

Some reflections on World Heritage

Summary This paper presents some initial reflections on the emergence of the World Heritage Convention in 1972, the significance of the appellation 'world' and the interpretation of 'heritage'. The dichotomous definition of heritage has found decreasing support in practice and occasioned changes in the original Operational Guidelines for implementing the Convention .