The non-oxidative dissolution of galena nanocrystals: Insights into mineral dissolution rates as a function of grain size, shape, and aggregation state

The acidic, non-oxidative dissolution of galena (PbS) nanocrystals has been studied in detail using transmission electron microscopy (TEM) to follow the evolution of the size and shape of the nanocrystals before and after dissolution experiments, X-ray photoelectron spectroscopy (XPS) to follow particle chemistry, and dissolution rate analysis to compare dissolution rates between nanocrystalline and bulk galena. Dissolution characteristics were also studied as a function of nanocrystal access to bulk vs. confined solution due to the degree of proximity of next-nearest grains. Nearly monodisperse galena nanocyrstals with an average diameter of 14.4 nm were synthesized for this study, and samples were exposed to pH 3, deoxygenated HCl solutions for up to 3 h at 25 °C. Detailed XPS analysis showed the nanocrystals to be free of unwanted contamination, surface complexes, and oxidative artifacts, except for small amounts of lead-containing oxidation species in both pre- and post-dissolution samples which have been observed in fresh, natural bulk galena. Depending on the calculation methods used, galena nanocrystals, under the conditions of our experiments, dissolve at a surface area normalized rate of one to two orders of magnitude faster than bulk galena under similar conditions. We believe that this reflects the higher percentage of reactive surface area on nanocrystalline surfaces vs. surfaces on larger crystals. In addition, it was shown that {1 1 1} and {1 1 0} faces dissolve faster than {1 0 0} faces on nanocrystals, rationalized by the average coordination number of ions on each of these faces. Finally, dissolution was greatly inhibited for galena nanocrystal surfaces that were closely adjacent (1-2 nm, or less) to other nanocyrstals, a direct indication of the properties of aqueous solutions and ion transport in extremely confined spaces and relevant to dissolution variations that have been suspected within aggregates.     

Hydrological model parameter (in)stability – “crash testing” the HBV model under contrasting flood seasonality conditions

This paper investigates the transferability of calibrated HBV model parameters under stable and contrasting conditions in terms of flood seasonality and flood generating processes (FGP) in five Norwegian catchments with mixed snowmelt/rainfall regimes. We apply a series of generalized (differential) split-sample tests using a 6-year moving window over (i) the entire runoff observation periods, and (ii) two subsets of runoff observations distinguished by the seasonal occurrence of annual maximum floods during either spring or autumn. The results indicate a general model performance loss due to the transfer of calibrated parameters to independent validation periods of ?5 to ?17%, on average. However, there is no indication that contrasting flood seasonality exacerbates performance losses, which contradicts the assumption that optimized parameter sets for snowmelt-dominated floods (during spring) perform particularly poorly on validation periods with rainfall-dominated floods (during autumn) and vice versa.     

A comparative simulation study of coupled THM processes and their effect on fractured rock permeability around nuclear waste repositories

This paper presents an international, multiple-code, simulation study of coupled thermal, hydrological, and mechanical (THM) processes and their effect on permeability and fluid flow in fractured rock around heated underground nuclear waste emplacement drifts. Simulations were conducted considering two types of repository settings (1) open emplacement drifts in relatively shallow unsaturated volcanic rock, and (2) backfilled emplacement drifts in deeper saturated crystalline rock. The results showed that for the two assumed repository settings, the dominant mechanism of changes in rock permeability was thermal–mechanically induced closure (reduced aperture) of vertical fractures, caused by thermal stress resulting from repository-wide heating of the rock mass. The magnitude of thermal–mechanically induced changes in permeability was more substantial in the case of an emplacement drift located in a relatively shallow, low-stress environment where the rock is more compliant, allowing more substantial fracture closure during thermal stressing. However, in both of the assumed repository settings in this study, the thermal–mechanically induced changes in permeability caused relatively small changes in the flow field, with most changes occurring in the vicinity of the emplacement drifts.     

Evolution of the modern Nile delta promontories: development of accretional features during shoreline retreat

The active accretional features that have developed along the modern Nile Delta promontories during shoreline retreat are analysed using topographic maps, remote imagery, ground and hydrographic surveys, together providing 15 time-slice maps (1922–2000) at Rosetta and 14 time-slice maps (1909–2000) at Damietta. Small double sandy spits developed and persisted at Rosetta between 1986 and 1991. At Damietta, a much larger single spit, 9 km long, formed approximately east of the mouth of the Damietta Nile branch between 1955 and 1972, although its source has now been depleted. Both the Rosetta and Damietta inlets are associated with submerged mouth bars that accumulated prior to the damming of the Nile, but that continue to contribute to local sedimentation problems, particularly at Rosetta. The development of the active accretional features along the Nile promontories reflects a combination of factors including sediment availability, transport pathways from source areas, a decrease in the magnitude of Nile flood discharges, as well as the impact of protective structures at the river mouths.     

Microvertebrates from the Rhaetian basal bone bed of Saltford,near Bath,SW England

The famous Rhaetian bone bed (Late Triassic, 205 Ma) is well known because it marks a major switch in depositional environment from terrestrial red beds to fully marine conditions throughout the UK and much of Europe. The bone bed is generally cemented and less than 10 cm thick. However, we report here an unusual case from Saltford, near Bath, S.W. England where the bone bed is unconsolidated and up to nearly 1 m thick. The exposure of the basal beds of the Westbury Formation, Penarth Group includes a bone bed containing a diverse Rhaetian marine microvertebrate fauna dominated by sharks, actinopterygian fishes and reptiles. Despite the unusual sedimentary character of the bone bed, we find similar proportions of taxa as in other basal Rhaetian bone beds (55–59 % Lissodus teeth, 13–16 % Rhomphaiodon teeth, 12–14 % Severnichthys teeth, 6–9% Gyrolepis teeth, 3–4% undetermined sharks’ teeth, 1–3% undetermined bony fish teeth, and < 1% of each of Hybodus, Parascylloides, and Sargodon), the only differences being in the proportions of Rhomphaiodon teeth, which can represent 30–40 % of specimens elsewhere. This suggests that taphonomic bias of varying Rhaetian bone beds may be comparable despite different sedimentary settings, and that the proportions of taxa say something about their original proportions in the ecosystem.     

Capitalism, masculinity and whiteness in the dialectical landscape: The case of Tarzan and the Tycoon

The intent of this paper is to explore how ‘reel’ and ‘real’ landscapes can be rendered dialectic. The analysis focuses on the filming of Tarzan's Secret Treasure (1941) at the wildlife preserve of Wakulla Springs in Florida, which was administered by the financial tycoon Ed Ball. Using Mitchell's recent commentaries on ‘good’ and ‘bad’ dialectics as our entry point, we offer two readings of this cinematic process. The first renders the on and off screen Wakulla Springs as ideological fodder, serving to valorise capital, masculinity and whiteness. The second reading addresses how this place has been actively constructed from discourses pertaining to class, gender and race, such that Wakulla exists as a series of fully relational spaces within diverse contexts, both ‘real’ and ‘reel’. In structuring our analysis in this manner, we hope to make clear why it does indeed matter for film geographers to acknowledge the conceptual presumptions brought to bear in the framing of the real and the reel as objects of analysis. This revised version was published online in August 2006 with corrections to the Cover Date.     

The weathering and element fluxes from active volcanoes to the oceans: a Montserrat case study

The eruptions of the Soufrière Hills volcano on Montserrat (Lesser Antilles) from 1995 to present have draped parts of the island in fresh volcaniclastic deposits. Volcanic islands such as Montserrat are an important component of global weathering fluxes, due to high relief and runoff and high chemical and physical weathering rates of fresh volcaniclastic material. We examine the impact of the recent volcanism on the geochemistry of pre-existing hydrological systems and demonstrate that the initial chemical weathering yield of fresh volcanic material is higher than that from older deposits within the Lesser Antilles arc. The silicate weathering may have consumed 1.3% of the early CO₂ emissions from the Soufrière Hills volcano. In contrast, extinct volcanic edifices such as the Centre Hills in central Montserrat are a net sink for atmospheric CO₂ due to continued elevated weathering rates relative to continental silicate rock weathering. The role of an arc volcano as a source or sink for atmospheric CO₂ is therefore critically dependent on the stage it occupies in its life cycle, changing from a net source to a net sink as the eruptive activity wanes. While the onset of the eruption has had a profound effect on the groundwater around the Soufrière Hills center, the geochemistry of springs in the Centre Hills 5 km to the north appear unaffected by the recent volcanism. This has implications for the potential risk, or lack thereof, of contamination of potable water supplies for the island’s inhabitants.     

A literary geography of Soweto

Humanist inspired literary geography offers one avenue of enquiry into the study of place. Its prime intention is to untangle the subjective, personalised construction and connotations of place meaning. African literature offers a rich source of information into the black urban experience. The presentation focuses upon the literary interpretation of Soweto, South Africa's largest black township. The Sowetan environment emerges as a landscape of placelessness in which the overwhelming emphasis by white and black writers alike is upon relating appalling conditions in an austere and hostile environment.     

Climate Change Impact on Hydrological Extremes: Preliminary Results from the Polish-Norwegian Project

This paper presents the background, objectives, and preliminary outcomes from the first year of activities of the Polish–Norwegian project CHIHE (Climate Change Impact on Hydrological Extremes). The project aims to estimate the influence of climate changes on extreme river flows (low and high) and to evaluate the impact on the frequency of occurrence of hydrological extremes. Eight “twinned” catchments in Poland and Norway serve as case studies. We present the procedures of the catchment selection applied in Norway and Poland and a database consisting of near-natural ten Polish and eight Norwegian catchments constructed for the purpose of climate impact assessment. Climate projections for selected catchments are described and compared with observations of temperature and precipitation available for the reference period. Future changes based on those projections are analysed and assessed for two periods, the near future (2021–2050) and the far-future (2071–2100). The results indicate increases in precipitation and temperature in the periods and regions studied both in Poland and Norway.     

Thermodynamic modeling assisted by multivariate statistical image analysis as a tool for unraveling metamorphic P-T-d evolution: an example from ilmenite-garnet-bearing metapelite of the Peloritani Mountains, Southern Italy

An ilmenite-garnet-bearing schist from the medium-grade metapelite complex of the Mandanici Unit in the Peloritani Mountains has been investigated to constrain the P-T conditions attained in this sector of the southern European Hercynian chain. Microprobe investigations assisted by statistical handling of X-ray maps via principal component analysis allowed us to better elucidate the porphyroblast-matrix relationships, the geometry of the elemental distribution in garnet porphyroblasts and the average volume percentage of the reactant garnet during retrograde metamorphic evolution. Selected microprobe data were then used to constrain, by means of P-T pseudosections, the main P-T stages of the metamorphic evolution, using the XRF bulk-rock chemistry as the equilibrium chemical composition for the prograde and peak stages and an effective bulk-rock composition for the retrograde one. Peak metamorphic P-T estimates (~530?°C; 0.9?GPa) are consistent with a Hercynian crustal thickening stage at middle-lower crustal conditions, while subsequent evolution, constrained at 420–460?°C; 0.30–0.60?GPa, depicts a retrograde clockwise P-T trajectory linked to exhumation under likely extensional shearing conditions. The results obtained in this paper lead to envisage a new scenario for the crustal evolution of the Peloritani Mountains and stimulate a revision of previous interpretations in the light of the new investigation techniques.