Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.     

Flexural isostatic response of the Alps to increased Quaternary erosion recorded by foreland basin remnants,SE France

We test the hypothesis that flexural isostatic compensation of the mass removed by enhanced Quaternary erosion is responsible for uplift of the Western European Alps and their forelands. We use two well‐preserved and well‐dated (1.8 Ma) abandonment surfaces of foreland basin remnants in SE France (the Chambaran and Valensole plateaux) as passive benchmarks for tilting of the foreland. Estimating their initial slope from morphometric scaling relationships, we determine bulk post‐depositional tilting of 0.5–0.8% for these surfaces. The calculated isostatic response of the Alpine lithosphere to erosional unloading, using the method recently proposed by Champagnac et al. [Geology 35 (2007) 195–198] , yields a predicted tilting of 0.3–0.4% in the considered areas, explaining approximately half of the determined post‐depositional tilting. Such long‐term deformation being insensitive to cyclic loading/unloading because of glaciations, we suspect the other half to be related to as yet undetermined long‐wavelength and long‐lived tectonic process(es).     

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.     

Dynamic properties of green water event in the overtopping of extreme waves on a fixed dock

A statistical model is developed to predict wave overtopping volume and rate of extreme waves on a fixed deck. The probability density function for the volume and rate of overtopping water are formulated based on the truncated Weibull distribution with the assumption of local sinusoidal profile for small amplitude waves. Sensitivity to the wave nonlinearity parameter and deck clearance is discussed. The statistical model is compared to laboratory data of the instantaneous free surface elevation measured in front of a fixed deck, and overtopping volume and overtopping rate measured at the leading edge of the deck. The statistical theory compared well with the measured exceedance probability seaward of the deck. The model prediction of the exceedance probability of deck overtopping gave qualitatively good agreement for large overtopping values.     

Estuary/ocean exchange and tidal mixing in a Gulf of Maine Estuary: A Lagrangian modeling study

A Lagrangian particle method embedded within a 2-D finite element code, is used to study the transport and ocean–estuary exchange processes in the well-mixed Great Bay Estuarine System in New Hampshire, USA. The 2-D finite element model, driven by residual, semi-diurnal and diurnal tidal constituents, includes the effects of wetting and drying of estuarine mud flats through the use of a porous medium transport module. The particle method includes tidal advection, plus a random walk model in the horizontal that simulates sub-grid scale turbulent transport processes. Our approach involves instantaneous, massive [O(500,000)] particle releases that enable the quantification of ocean–estuary and inter-bay exchanges in a Markovian framework. The effects of the release time, spring–neap cycle, riverine discharge and diffusion strength on the intra-estuary and estuary–ocean exchange are also investigated.The results show a rather dynamic interaction between the ocean and the estuary with a fraction of the exiting particles being caught up in the Gulf of Maine Coastal Current and swept away. Three somewhat different estimates of estuarine residence time are calculated to provide complementary views of estuary flushing. Maps of residence time versus release location uncover a strong spatial dependency of residence time within the estuary that has very important ramifications for local water quality. Simulations with and without the turbulent random walk show that the combined effect of advective shear and turbulent diffusion is very effective at spreading particles throughout the estuary relatively quickly, even at low (1 m²/s) diffusivity. The results presented here show that a first-order Markov Chain approach has applicability and a high potential for improving our understanding of the mixing processes in estuaries.     

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.