Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.     

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

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.     

THOUGHTS ON MAPPING BY PHOTOGRAMMETRY

Topics of immediate practical interest formed the basis of the Address. Particular emphasis was placed upon problems of point transfer, pre-marking of ground control points, aerial triangulation by observation of independent models, and the status of photogrammetric operators.     

Mixed-function oxygenases as biological monitors around petroleum hydrocarbon development sites: Potential for induction by diesel and other drilling mud base oils containing reduced levels of polycyclic aromatic hydrocarbons

The use of oil-based drilling muds has been discouraged in hydrocarbon exploration and production in the marine environment but these muds are presently being used to a considerable degree in the United Kingdom and Norwegian sectors of the North Sea. Field studies in the North Sea have demonstrated only localized impacts around individual drilling sites,^1,2 even including those sites where ‘toxic’ diesel oils were employed as base fluids in drilling muds. Yet the question of disposal of cuttings contaminated with oil from drilling muds remains somewhat controversial. The induction of mixed-function oxygenases (MFO) has been validated on a number of occasions in the field as a sensitive index of low level hydrocarbon exposure (reviewed by Payne),³ including sites in the North Sea where diesel-based muds were used.⁴ The present study demonstrates that any potential for induction by hydrocarbon contaminated cuttings will probably be reduced by substitution of low-aromatic base oils for diesel in drilling mud formulations.     

Chalk shore platform erosion in the vicinity of sea defence structures and the impact of construction methods

Erosion of the intertidal chalk platform in the vicinity of groynes and seawalls is evident to the naked eye along many stretches of the engineered coastline of southeast England, leading to undermining and eventually failure of these structures. However, quantification of the magnitude and spatial extent of the erosion has been difficult to date because of a lack of data about the past elevation of the platform. The application of softcopy photogrammetry makes it possible to recreate past platform elevations from historic air photographs and to compare these with elevations from modern air photographs. Coastal sea defence structures have been installed along the chalk coast east of Brighton at various dates over the past 70 years. During this period, the construction methods have changed from predominantly manual labour to a reliance on heavy machines. The analysis of erosion patterns around structures built since the 1970s using heavy machinery show that surface lowering is 4 to 25 times greater in the vicinity of these structures than across the platform as a whole. In contrast, there is no similar pattern of increased erosion around structures built using predominantly manual labour in the 1930s. A four fold increase in average surface lowering is found also along a vehicle trackway that crosses the mid platform. Depressions developed by enhanced lowering in the front of seawalls generate their own dynamic of increased erosion by trapping pebbles and cobbles that enhance the abrasion of the chalk through bedload transport under standing waves in front of the walls.     

Video observations of marine gravel transport

In an analysis of video observations of gravel transport in the West Slent, UK, collective and individual characteristics of 458 bursts of bedload have been examined and the transport velocity and distance of 1680 individual particles in a consecutive succession of burst events determined. Infrequent, long duration, high stress events account for 60% of total transport in only 24% of the total time with the mean free path and transport velocity for particles being 0.16 m and 0.22 m/s, respectively. Clear links between intense intermittent turbulence and bedload transport revealed in this study, suggest progress in modelling requires a clearer understanding of near bed flow structure.     

A detailed survey near Mount Eratosthenes Eastern Mediterranean

A detailed marine survey made to the South West of Mount Eratosthenes is described. The results show the existence of a narrow zone of WNW trending deformed sediment west of the mount surrounded by an evaporite sequence in different stages of deformation.This work was intended to settle the conflict between the results of three previous interpretations of the tectonic structure of this area. We see the area being characterised by five areas with different degrees of tectonic deformation yet showing little causal relationship to overburden of Nile Cone sediments. A fault controlled cliff coincides with the previously described salt wall and strike slip fault yet we see no evidence for its diapiric origin nor positive evidence for strike slip motion along it. We concur with the previously observed area of higher free-air gravity anomalies termed the Eratosthenes tectonic zone, although it is traversed by several boundaries between areas of different deformation. Our results thus show some agreements and some re-interpretations of the observations. This complicated region is not yet fully understood however.     

Petroleum geochemistry of the Kimmeridge Clay of onshore Southern and Eastern England

The Kimmeridge Clay is considered a major oil source rock for the North Sea hydrocarbon province. The formation is also developed onshore in an organic-rich mudstone facies. This paper examines the possibility of onshore oil generation from the Kimmeridge Clay. Geochemically, onshore basin margin sediments contain rich, potential source horizons with mainly Type l/Type ll oil-prone kerogen, but are immature. Some deeper Cleveland Basin sediments have reached marginal maturity. Burial history reconstruction suggests significant formation palaeoburial depths in central areas of the Cleveland and Wessex Basins. Computed vitrinite isoreflectance contours show the Wealden and Isle of Wight Kimmeridge Clay to be thermally mature. Basin modelling suggests an early Palaeogene onset of oil generation in parts of the Cleveland Basin, while maximum oil generation could have been reached by the formation base in the Isle of Wight area during the late Cretaceous. Although basin subsidence ceased in the Neogene, in the Weald and Isle of Wight, where the formation is still deeply buried, oil generation probably continued for some time during uplift. Thus significant quantities of oil could have been generated. Whether or not this oil is present today however, would depend on the correct timing of suitable migration and trap structures.     

An evaluation of temperature scales for silica diagenesis in diatomaceous sequences including a new approach based on the Miocene Monterey Formation,California

Geologic relations indicate that silica phases transformed in the Monterey Formation in two zones that persist over a narrow depth/temperature range and do not stratigraphically overlap. The wide and overlapping range of reported temperatures of these transformations is mainly a result of the many uncertainties inherent in the different methods used to estimate temperature and does not indicate that phases transform throughout these ranges. Our approach to a reliable temperature scale for silica diagenesis combines as empirical zonation of silica phases with temperature calibration from a sequence at maximum temperature and depth of burial.